Beginning Cosmetic Chemistry

Beginning Cosmetic Chemistry Third Edition
■ Perry Romanowski, Randy Schueller
Practical Knowledge for the

Cosmetic Industry
Allured Business Media

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Carol Stream, IL 60188
USA
Beginning Cosmetic Chemistry, Third Edition
ISBN: 978-1-932633-53-5
Copyright 2009, by Allured Publishing Corporation. All Rights Reserved.
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Beginning Cosmetic Chemistry, Third Edition
Introduction
Section I: Welcome to the Industry: Terms, Tools and Tips
1. Your Career in Cosmetic Science
Perry Romanowski, Randy Schueller . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Your Primer of Technical Terms and Chemical Jargon

Perry Romanowski, Randy Schueller . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3. Cosmetic Ingredient Nomenclature

Anthony J. O’Lenick Jr. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4. INCI Names: International Harmonization

Anthony J. O’Lenick Jr. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5. Material Safety Data Sheets

6. Building Effective Supplier Relationships

Section II: Basic Cosmetic Science: Biology of hair and skin;

Chemistry of Raw Materials
7. Inside the Hair: An Advanced Hair Biology Model
Randy Schueller and Perry Romanowski . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
8. New Directions for Sensitive Skin Research

Jennifer A. Davis and R. Randall Wickett, PhD. . . . . . . . . . . . . . . . . . . . . . . . . 81
9. Axillary Odor: Its Physiology, Microbiology and Chemistry

J. C. Parekh. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
10. Conditioning Agents for Hair and Skin

11. Surfactant Science

Anthony J. O’Lenick Jr. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
12. Oils of Nature

13. Understanding Emulsions

Perry Romanowski, Randy Schueller . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
14. Silicone Chemistry

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Table of Contents Beginning Cosmetic Chemistry
15. Creating Colorful Cosmetics

Luigi Rigano. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
16. Pigments: Achieving the Effect

Bud Brewster. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
17. The Science of Reactive Hair Care Products

18. The Essence of Fragrance

Randy Schueller and Perry Romanowski . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
19. Common Scents

Perry Romanowski, Randy Schueller, Stephen Herman. . . . . . . . . . . . . . . . . . 187
20. Microorganisms and Personal Care Products

David C. Steinberg. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Section III: Product Development: From Beaker to Bottle

21. Lab Notebooks: The “Write” Stuff
22. Laboratory Notebooks: Valuable Indicators of Intellectual

Property
Dolores T. Kenney, Esq. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
23. Laboratory Batching of Cosmetic Products

24. Successful Product Development

25. Formulating Cosmetic Emulsions: A Beginner’s Guide

Ken Klein . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
26. The Aging of Polymer-Stabilized Creams:

A Rheological Viewpoint
Slobodanka Tamburic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
27. Gels and sticks

28. Aerosols for Apprentices

v
Beginning Cosmetic Chemistry Table of Contents
29. Encapsulation Technologies: Tailored Solutions for Delivery

Todd Ostergaard, Scott Hawkins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
30. What Every Formulator Needs to Know about Fragrance

Felix Buccelato. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
31. Fragrance in Emulsion and Surfactant Systems

Steve Herman. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
32. Fundamentals of Formulating Hair Care Products

33. Introduction to Shampoo Thickening

Anna M. Howe, Amy E. Flowers, Brian Yang. . . . . . . . . . . . . . . . . . . . . . . . . . 313
34. Innovations in Hair Styling Technology

35. Understanding “Mild” Cosmetic Products

36. Formulating for Efficacy

Johann W. Wiechers, Caroline L. Kelly and Trevor G. Blease,
J. Chris Dederen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
37. Formulating for Sensitive Skin

Zoe Diana Draelos. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
38. The ABCs of SPF

39. Self-Tanners: Formulating with Dihydroxyacetone

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
40. The Dry Facts About Wet Perspiration

Zoe Diana Draelos. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
41. Improving the Appearance of Facial Pores

Y. Katsuta, T. Iida and S. Inomata, S. Yoshida. . . . . . . . . . . . . . . . . . . . . . . . . 403
42. A Light-Diffusing Concept for Antiaging Effects in Makeup

Formulations
E. Desmarthon, D. Hericher and M. Seu-Salerno . . . . . . . . . . . . . . . . . . . . . . 409
43. Cosmetic Product Packaging

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Table of Contents Beginning Cosmetic Chemistry
44. Emerging Technologies and the Future of Cosmetic Science

Section IV: Does It Work: Product Testing, Regulatory

Compliance and Claims Support
45. Evaluating Raw Materials and Finished Products
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
46. Preservative Efficacy Testing: Accelerating the Process

John I. Yablonski and Sharon E. Mancuso . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
47. The Century of Progressive Regulation

Rachel Chapman . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
48. Mind Over Matter: Cosmetic Claim Substantiation Issues

Facing the Future
Johann W. Wiechers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
49. The Regulatory Interface: When is it a Cosmetic and

When a Drug?
Jean L. Fourcroy, M.D., Ph.D., M.P.H., Uniformed Services. . . . . . . . . . . . . . 479
50. Correlating Porosity and Tensile Strength of Chemically

Modified Hair
Ali N. Syed and Hasan Ayoub. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
51. In Vivo Quantitative Evaluation of Gloss

P. Clémenceau, S. Breugnot and B. Pouet. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 495
52. Evaluating Shampoo Foam

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
53. What You Should Know About Testing on Human Hair

54. Evaluating Shine on Hair

Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
Introduction
If you work in the cosmetic industry-in any capacity-you need this book!
Whether you are a formulating chemist, a microbiologist, a process engineer, an
industry vendor, a marketing manager, a cosmetologist or even a science student
who would like to work in this industry, THIS BOOK WILL HELP YOU! So
read on, and we’ll tell you why...
To everyone who is new to this industry, welcome! We hope this book, the
third edition of our best-selling Beginning Cosmetic Chemistry, will be helpful
to you as you start your career. On the other hand, if you’ve been around the
industry for awhile and you’re familiar with Beginning Cosmetic Chemistry, we
hope you’ll find plenty of new and updated information that wasn’t in the first
two books.
With this edition, we will re-emphasize the importance of providing
introductory technical information to those who would like to improve their
understanding of cosmetic science. As we noted in the original edition, we
started this book because we were frustrated with the lack of technical resources
available for beginners in our industry. We believed then, and continue to
believe now, that this lack of introductory material has an increasingly negative
impact on our industry’s ability to recruit and retain fresh talent.
We’re proud to say that, through the dedication of Allured Business Media,
much progress has been made in this regard. Cosmetics & Toiletries magazine
has been the only publication with a column specifically dedicated to providing
technical information for beginners. We applaud their commitment to the
beginning cosmetic chemist.
For better or worse, things keep changing. Since the first edition of
Beginning Cosmetic Chemistry, thousands of new chemical raw materials and
new formulations have been developed, billions of new marketing concepts
have been tested (okay, we’re exaggerating for dramatic effect), and hundreds, if
not thousands, of new cosmetic regulations have been enacted (seriously!). So,
rather than simply reprinting the 2nd edition, we decided it was time to update
it with a substantial amount of new information. Hence, the book you now hold
in your hands.
We hope you find it be a valuable resource for many years to come!
Randy Schueller
Perry Romanowski
I. Welcome to the Industry:
Terms, Tools and Tips

Chapter 1
Your Career in Cosmetic

Science
Reviewing the key steps to product development and the
specialized fields within which scientists work.
key words: careers, contract manufacturers, testing laboratories,

quality control, analytical methods, claims support, safety
I t is fun to speculate that, at some point in ancient history, an early Homo sapien
discovered that mud makes the skin feel soft. Thus, the first cosmetic product
was born—as was the first cosmetic chemist. Over time, an entire industry evolved
to support the development and production of cosmetics. As the industry grew, so
did the need for skilled scientists.
Today, the cosmetic industry is a multibillion-dollar enterprise that relies on
chemists (and other scientists) to accomplish a multitude of key functions. As a
scientist, it is important that you understand not only the part you play in the indus-
try, but also the roles of other scientists and their relationship to you. This chapter
reviews the various roles of scientists in the cosmetic industry.
Product Development
Product development or formulating chemists create products designed to meet
specific consumer needs. These products include cosmetics (hair- and skincare
products) as well as certain over-the-counter (OTC) drugs, such as toothpastes and
antiperspirants. To accomplish this task, formulators identify raw materials with the
desired functionalities and combine these materials in the proper ratios to yield an
acceptable finished product that performs as intended and remains stable.
Knowledge base: Formulating chemists need a solid knowledge of general
chemistry, particularly surfactants and emulsification. They must also have a thor-
ough appreciation of the specific chemistry and functionality of the thousands
of cosmetic raw materials available. In addition, they often require a specialized
knowledge of specific product types, such as aerosols, or drug categories, such as
fluoride treatments.
Beyond basic cosmetic science, formulators must be aware of how market-
ing decisions, cost constraints, manufacturing conditions, and esthetic concerns,
such as appearance and odor, can impact product development. A formulator may
3
4
Your Career in Cosmetic Science Beginning Cosmetic Chemistry
develop the world’s most effective toothpaste, but if it costs US$10,000 per ounce
to produce, looks terrible and tastes even worse, no one will buy it.
Industry Overview Sidebar

To understand the roles of cosmetic scientists, it is important to know
what types of companies make up the industry.
Raw material suppliers: Cosmetic products are made up of ingredients
supplied by raw material vendors. These vendors use various chemical and
physical processes to convert feedstocks, such as petroleum distillates and
natural oils, into materials useful in cosmetic products. The thousands of
chemical suppliers in this industry make everything from salt to vitamins.
Fragrance vendors: A specialized subcategory of raw material suppli-
ers is fragrance vendors who design and manufacture the fragrances used
in cosmetic products.
Finished goods marketers: These companies make finished cosmetic
products, such as makeup, shampoo, deodorant, skin lotion and fragrance.
They generate product ideas, create and test prototypes, and manufacture
finished goods, which are ultimately sold to consumers via retail outlets,
salons, wholesale clubs or some form of direct marketing.
Contract manufacturers: Many finished goods marketers do not have
the ability or the desire to make all the products they want to sell. Instead,
they use the services of contract manufacturers, who specialize in batching
and filling finished products.
Testing laboratories: For a variety of reasons, finished goods manufac-
turers may choose to have their products tested by outside laboratories. For
example, it may be easier to have an outside lab conduct skin-moisturization
testing because the test protocol requires careful monitoring of human panel-
ists. Similarly, it may be advantageous to have an outside lab run particle-size
analysis because the equipment is expensive. Testing labs perform these and
many other vital functions in the cosmetic industry.
All of these companies employ a variety of chemists, biologists, engineers
and other professionals.
Duties: Formulators are found wherever cosmetic products are created, usually
in finished goods companies, contract manufacturers and raw materials suppliers.
Formulators typically research useful raw materials (by reviewing trade literature
and supplier information), create innovative formulations, prepare actual batches,
and test them for functionality and stability. In addition, formulating chemists per-
form a variety of other functions and are involved in many of the duties performed
by the other chemists.
Professional backgrounds: Formulators come from a variety of backgrounds.
Some enter this industry straight from college. Typically, product development
chemists have a science degree, usually a bachelor’s in chemistry. Some have
5
Beginning Cosmetic Chemistry Chapter 1
degrees in biology or related science. A few US colleges offer specialized cosmetic

programs (Table 1.1).
However, most formulators learn the necessary skills from trade literature and
peers, and on the job. The Society of Cosmetic Chemists and the Center for Pro-
fessional Advancement offer continuing education programs that offer specialized
training. Some scientists enter the industry as analytical chemists and transfer to
product development. Others come from related fields, such as the paint, coating
and textile industries.
Table 1.1. Cosmetic science programs in the United States
United States Massachusetts College of Pharmacy

175 Longwood Avenue
Arnold and Marie Schwartz College
Boston, MA 02115
Pharmacy and Health Sciences
Website: http://www.universities.com/
Long Island University
On-Cam-pus/Massachusetts_
75 Dekalb Avenue
College_of_Pharmacy__Health_
Brooklyn, NY 11201
Science_Masters_degree_Industrial_
Division Director: David R. Taft, Ph.D.
and_Physical_Pharmacy_222942.html
Phone: (718) 488-1101
Notes: Massachusetts College of
Website: http://www.brooklyn.liu.edu/
Pharmacy & Health Science—
pharmacy/div_pharmaceutics_
Master’s degree—Industrial and
Master_phar.html
Physical Pharmacy and Cosmetic
Notes: Master of Science Degree-
Sciences (MS, PhD).
Pharmaceutics with specialization in:
Industrial Pharmacy
Cosmetic Science Monell Chemical Senses Center
University of Pennsylvania
3500 Market Street
The City College of New York
Philadelphia, PA 19104-3308
Department of Chemistry
Phone: (267) 519-4700
138th Street and Convent Avenue
Fax: (215) 898-2084
New York, NY 10031
Email: mcsc@monell.org
Dr. Simon Simms, Chair;
Website: http://www.monell.org/
Room: MR–1024
Phone: 212-650-8402
Fax: 212-650-6107 Rutgers University
Email: chem@sci.ccny.cuny.edu College of Pharmacy
Website: http://www.sci.ccny.cuny.edu/ PO Box 789
chemistry/ Piscataway, NJ 08855
Marc C. Kollar, Assistant Dean
Phone: (732) 445-2675 600
Fairleigh Dickinson University
Fax: (732) 445-5767
1000 River Road
Email: kollar@rci.rutgers.edu
Teaneck, NJ 07666
Website: http://pharmacy.rutgers.edu/
Program Coordinator: Dr. James A.
Dougherty
Phone: 201-692-2487 St. John’s University
Email: jdough@fdu.edu 8000 Utopia Parkway
Website: http://ucoll.fdu.edu/ns1/ Queens, New York 11439
science.html Website: http://www.stjohns.edu/
6
Table 1.1. continued
University of Cincinnati University of Oklahoma

College of Pharmacy College of Pharmacy
Mail Location 4 Oklahoma City, OK 73190
Cincinnati, OH 40221 Michael E. Burton, Pharm.D. Professor
Gerald B. Kasting, Ph.D., Professor, & Chair, Dept. of Pharmacy: Clinical
Pharmaceutics & Cosmetic Science, and Administrative Sciences
College of Pharmacy, University of Phone: (405) 271-6878 x47259
Cincinnati Email: Michael-Burton@ouhsc.edu
Phone: 513-558-0749 Website: http://pharmacy.ouhsc.edu/
Email: gerald.kasting@uc.edu
Website: http://pharmacy.uc.edu/ University of Rhode Island
Notes: UC’s master’s of science track in College of Pharmacy
cosmetic science, one of only three 145 Fogarty Hall
such programs in the United States, Kingston, RI 02881
is available on campus and through Ronald Jordan Interim Dean
a new distance learning option. The Phone: 401-874-2761
college recently launched a novel MS Email: ronjordan@uri.edu
track in drug development in which Website: http://www.uri.edu/pharmacy/
students focus on the scientific and
regulatory aspects of drug discovery/ University of South Florida
development. College of Pharmacy
3515 E. Fletcher Road
University of Maryland Tampa, FL 33613
School of Pharmacy Phone: 813 974-2804
20 N Pine Street Fax: (813) 974-5911
Baltimore, MD 21201 Email:
Natalie Eddington, Dean Website: http://web1.cas.usf.edu/MAIN/
Fax: 410-706-4012 contentDisplay.cfm?contentID=152
Email: neddingt@rx.umaryland.edu
Website: http://www2.pharmacy. University of Southern California
umaryland.edu/ School of Pharmacy
1985 Zonal Avenue
University of Minnesota Los Angeles, CA 90033
College of Pharmacy Phone: (323) 442-1369
Minneapolis, MN 55455 Fax: (323) 442-1681
Phone: 612-624-1900 Website: http://www.usc.edu/schools/
Fax: 612-624-2974 pharmacy/
Website: http://www.pharmacy.
umn.edu/ University of Southern Mississippi
Department of Polymer Science
University of Missouri-Rolla PO Box 10076
Department of Chemistry Hattiesburg, MS 39406
Rolla, MO 65401 Phone: 601.266.4868
Philip Whitefield Professor & Chairman Fax: 601.266.5504
Department of Chemistry Email:
Phone: 573-341-4420 Website: http://www.usm.edu/polymer/
Email: chem@mst.edu
Website: http://chem.mst.edu/
7
University of Tennessee Italy

College of Pharmacy
University of Siena, Italy
Memphis, TN 38163
Website: http://www.unisi.it/farmacia/
Dick Gourley, Pharm.D., Professor
cosmetici/masterelearning.htm
and Dean
Phone: 901-448-6036
Fax: 901-448-7053 UK
Email: dgourley@utmem.ed University of the Arts London
Website: http://pharmacy.utmem.edu/ 65 Davies Street
London
Duquesne University/Mylan School W1K 5DA
of Pharmacy Phone: 0207 514 6000
600 Forbes Ave.
Pittsburgh, PA 15282 London College of Fashion
J. Douglas Bricker, Ph.D. Dean 20 John Princes Street
Phone: 412.396.6393. London W1G 0BJ
Website: http://www.pharmacy.duq.edu Phone: (0)207 514 7400
Notes: Master’s degree Industrial and Email: enquiries@fashion.arts.ac.uk
Physical Pharmacy and Cosmetic
Sciences (MS, PhD). China
University Of Puerto Rico Chia Nan University of Pharmacy and

Address Science Chia Nan University of
Address: Pharmacy and Science
Address: 60 ,Erh-Jen RD .,Sec.1 ,Jen-Te
Phone: (787) 758-2525 ,Tainan,Taiwan ,R.O.C
Website: www.upr.edu Phone: (886)6-266-4911
Notes: This program focuses on the
application of pharmaceutical sci- Yung Ta Institute of Technology &
ences and pharmacy to the study Commerce
of pharmaceuticals production and 316,Chung Shan Rd., Linti ,
distribution, and prepares individuals Linlo,Pingtung Hsien, Taiwan, R.O.C.
to manage pharmacies. Phone: 08-7233733
Temple University Scotland

1801 N. Broad Street University of Strathclyde
Philadelphia, PA 19122 16 Richmond Street, Glasgow G1 1XQ.
Director for Graduate Studies Daniel J. Scotland, United Kingdom
Canney, Ph.D., Department of Phar- Prof Gillian Eccleston
maceutical Sciences Phone: (0)141 548 2510 (Ext. 2510)
Phone: 215.204.7000 Email: g.m.eccleston@strath.ac.uk
Email: info@temple.edu
Website: www.temple.edu/
Quality
QC/QA: Quality control/quality assurance (QC/QA) chemists work for finished
product manufacturers, raw materials suppliers and contract manufacturers. They
ensure that products meet specified company standards by evaluating incoming
raw materials and outgoing finished products.
8
The duties of QC/QA chemists include sampling chemicals from storage con-
tainers and performing various analyses, such as for pH, viscosity, IR, solids and
percent trace minerals. They can also check labels, calibrate and maintain instru-
ments, and document batch histories.
Since QC/QA chemists are integral to the ongoing manufacturing process, it
is critical that they perform their work on a timely, efficient basis to avoid costly
production delays. To this end, they must have thorough knowledge and experience
in performing tests used to analyze samples.
QC/QA chemists, typically trained as analytical chemists, come from different
educational backgrounds and often have varying levels of industrial experience.
Because production lines often run around the clock to keep up with demand, this
work often involves working in shifts.
Analytical methods development: Many well-staffed companies employ
analytical chemists to develop the methods that QC/QA chemists use to test raw
materials and finished products. These methods include wet-chemical tests and
instrumental analyses, including titration, spectrophotometric analysis, HPLC, gas
chromatography and NMR.
During the development of new products with unusual analytical requirements,
it is often important that formulators consult with methods development chemists
early in the process. Otherwise, it may be very late before the team realizes that
no suitable method exists to assay the property.
Methods development chemists must have a solid background in general chem-
istry and be particularly familiar with instrumental analysis. To develop methods
using the latest technology, they must extensively review current developments in
analytical chemistry. Many method development chemists have advanced gradu-
ate degrees.
Microbiology: Microbiologists are an important technical link in the devel-
opment and manufacture of cosmetic products. In many ways, they function like
QC chemists since they determine whether incoming raw materials and finished
products meet company specifications. However, their focus is on whether materials
are acceptably free from microbial contamination. Typically, microbiologists sample
incoming chemicals and finished batches, then inoculate and conduct plate counts
to establish bacteria count.
Beyond quality control, microbiologists can also play a critical role in formula-
tion development. They often help select the optimal preservative system for a
product. They are especially important when developing and testing products with
proclaimed antimicrobial activity.
Microbiologists require detailed knowledge of the types of microorganisms that
may infiltrate cosmetic products as well as conditions of manufacturing, storage
and usage that may promote microorganism growth. They must also have detailed
knowledge of chemical preservatives and understand the effects raw materials
have on preservation systems. For example, nonionic surfactants can inactivate
parabenzoic acid derivatives. Microbiologists typically hold degrees in biology, but
they may also be chemists or biochemists.
9
Process Engineering
Chemists (or their engineering cousins, the chemical engineers) who special-
ize in process engineering solve problems encountered when “scaling up”—the
process of transferring a formula from laboratory-sized batches to production-size
quantities. Problems often occur during scale up due to drastic differences in the
impact of the physical forces that are experienced in the laboratory versus the
manufacturing plant.
Process engineers understand how sheer, heat transfer and mixing conditions
can impact the quality of finished goods. Their duties include working with chem-
ists to understand the idiosyncrasies of specific formulations while keeping up
with current technology of production equipment, such as mixers, pumps, and
heating and cooling systems. Process engineers usually hold degrees in chemical
or mechanical engineering.
Regulatory
Claims support: Another specialization is substantiating product performance
claims. Claims appear on television and radio, and in package copy, print advertising
and sales materials, such as brochures and pamphlets. Claims-support scientists
must be familiar with the basic properties of cosmetic raw materials and skilled at
interpreting claims language.
In addition, claims-support chemists must develop creative testing criteria. In
some cases, preestablished test methodology may already be in place, such as stan-
dard “regression tests,” which quantify skin moisturization. However, other areas
are more subjective, such as evaluating shine on hair. Everyone has a preferred
method; no universally accepted way to substantiate such claims exists. For this
reason, claims support scientists must be knowledgeable of the many tests available.
They usually hold degrees in related science areas.
Safety/toxicology: Many companies have specialists who deal with chemical
safety or government regulations. For example, environmental specialists ensure
that a company and its products comply with current environmental regulations.
Other regulatory chemists make sure that the company complies with employee
health, safety rules, labeling requirements and so forth. These scientists are increas-
ingly important as more companies begin to operate globally and must be aware
of the regulations in every country where they do business.
Regulatory scientists have degrees in various areas and, typically, a wide range
of experience. Because rules and regulations are constantly changing, this job is
quite dynamic.
Ingredients Suppliers
Synthesis chemists: Just as finished goods manufacturers hire formulating
chemists to create finished products, ingredient suppliers employ synthesis chemists
to develop raw materials. These chemists derive chemical reactions that convert co-
conut oil, petroleum and other feedstocks into functional, salable raw materials.
Synthesis chemists must have a strong background in organic chemistry and be
able to creatively develop novel reaction pathways to produce new raw materials.
10
They should also have a general idea of the properties a finished raw material will
have and how they will be economically useful.
Synthesis chemists usually have advanced degrees in specialized areas of organic
synthesis, such as esterification reactions or polymerization.
Technical applications development: Once raw materials are developed, the
manufacturer must understand their properties to sell them effectively. To this end,
many suppliers employ applications chemists that determine how finished-product
manufacturers might use a raw material.
Essentially, the duties and background of this job are the same as of the product
development chemist, except that these chemists work for an ingredient supplier.
Applications chemists may also work across several industries—personal-care,
detergents, paints and coatings and so forth.
Technical sales: Raw material suppliers frequently employ chemists on their
sales teams because people with technical backgrounds are more likely to suggest
meaningful applications. Generally, they communicate more effectively with for-
mulating chemists and their internal technical support.
Technical salespeople perform the same type of tasks as other salespeople, such
as meeting with clients, giving presentations and providing support to accounts.
While a degree in chemistry or a related field usually suffices, an MBA or sales/
marketing experience is often required as well.
Perfumery
Chemists who specialize in formulating fragrances are known as “perfumers.”
Perfumers have a large palette of organic chemicals with which to formulate fra-
grances; some perfumes contain as many as 600 materials. Perfumers must have
a thorough understanding of the potential interaction between fragrance raw
materials and other ingredients to help formulators create finished products with
appropriate fragrance characteristics.
In addition to the required technical skills, perfumers must have a highly
developed sense of smell and the ability to commit smells to memory. Most fra-
grance vendors provide perfumers with extensive training programs to cultivate
these specialized skills. Many perfumers are employed exclusively by fragrance
vendors. However, many finished goods companies employ fragrance coordinators
to administrate the process of fragrance selection.
The cosmetic industry is an arena providing a wealth of jobs for scientists. All
are critical to the success of product development, manufacturing, sales and, ulti-
mately, the company and the industry.
Published August 1996 Cosmetics & Toiletries magazine.
References
1. Career Opportunities in Cosmetic Science, Society of Cosmetic Chemists (1995)
2. http://sciencecareers.sciencemag.org/career_development/previous_issues/articles/
2450/not_just_a_pretty_face/(parent)/
3. http://sciencecareers.sciencemag.org/career_development/previous_issues/articles/
2450/cosmetics_research_reaching_beyond_the_fantasy/(parent)/
Chapter 2
Your Primer of Technical

Terms and Chemical
Jargon
A “dictionary” of the terms you may encounter in the
formulation lab.
key words: product types, ingredients, organizations, process,

testing, marketing, regulatory
T o function in a scientific environment, you not only need the appropriate

technical skills but you must also speak the correct technical language. Every
industry has its own jargon that you must understand if you are to succeed. The
cosmetic industry is certainly no exception. As an example, imagine yourself as a
new formulator. On your very first day at work, you are given a directive in the Can
You Decipher This? Sidebar
Obviously, the example we have presented here is exaggerated, but it illustrates
the type of technical jargon you must know as a cosmetic chemist. If you aren’t
familiar with some of the terms in this extremely cryptic message—or if you are
relatively new to the industry—you should find this chapter particularly helpful.
In it, we try to provide a concise summary of many such terms.
Because we could not possibly define every common term in this industry,
we’ve excluded general chemical terms that you most likely learned in school. For
example, pH is a very important term in the cosmetic industry, but it is not defined
here as you should be familiar with it from your technical training. Conversely, we
have included nonchemical terms, such as consumer perception and tress testing
as it is unlikely you encountered them previously.
It is important to realize that we are providing only informal definitions. Our
intent is to familiarize you with these terms so you won’t be intimidated the first
time you encounter them on the job. Therefore, we urge you to review the industry
references for further information.
For the sake of our discussion, we’ve grouped similar terms into eight categories
and then arranged them alphabetically within the categories.
11
12
Your Primer of Technical Terms and Chemical Jargon Beginning Cosmetic Chemistry
Can You Decipher This?

Formulate a product using fatty acids for micelle formation and SLS for
foam height. Use only certified dyes that don’t violate the Delany clause. If
the product has an SPF, make sure it complies with the OTC Monograph,
that the ingredient statement uses INCI terminology and that the formula
contains no CFCs or VOCs. Furthermore, check the product for compliance
with OTC and FDA regulations and ensure claims support is acceptable
for FTC and NAD. Also, we may have an OSHA inspection, so prepare an
MSDS ASAP.
The Industry
Contract manufacturer (or Private Label): A manufacturer outside your
company hired to produce a product for you. Many companies employ contract
manufacturers because they don’t have the capability to produce all their own
products. This practice is particularly common with aerosol products.
Finished Goods manufacturer: A company that creates and markets personal
care or cosmetics.
Fragrance house: Supplier of fragrance materials. Very few manufacturers
of personal care products actually produce their own fragrances. Instead, they rely
on outside vendors to prepare them.
Green: A philosophy in which companies strive to produce personal care
products that are environmentally friendly, energy efficient, and contain minimally
processed chemicals. Also known as the Natural Movement.
Supplier (or Vendor): A company that sells a chemical raw material, pack-
aging component or other item or services used in the preparation of cosmetic
products.
Testing facility: Independent companies that specialize in conducting chemi-
cal, physical, and other analytical testing of cosmetic products and raw materials.
Additionally, testing companies may conduct safety evaluations, consumer tests,
and environmental impact studies.
The Product Types

Aerosol: Product dispensed from a sealed container by a pressurized propellant
gas. Hair spray is a good example.
Emulsion: A fine dispersion of one insoluble liquid in another, e.g. oil dispersed
in water. Emulsions also usually contain surfactants and/or other stabilizing ingre-
dients that allow the two liquids to form a stable system. Creams and lotions are
common emulsions (see “surfactant”).
Gel: A semisolid liquid, often clear. Gels are commonly used in hair care, skin
care and toothpastes.
Non-aerosol: Product dispensed as a mist from a container fitted with a pump
or other user activated dispensing system. Used as an environmentally friendly
alternative to aerosols since they lack propellant.
13
Solution: A mixture of mutually soluble components (alcohol and soluble salts

in water, for example).
Stick: A solid form of cosmetic designed to deliver color, fragrance or other active
compounds to skin. Most often used for lipsticks, deodorants or antiperspirants.
The Science
Desquamation: The process of sloughing off dead skin cells.
Collagen: A protein responsible for skin strength and elasticity. The breakdown
of collagen is the primary cause of wrinkles.
Cortex: Inner layer of the hair shaft responsible for the fiber’s strength. Hair
coloring products deposit color within the cortex, which helps inhibit removal
making it last longer.
Cuticle: Outer layer of the hair composed of keratin protein. This structure
is responsible for hair feel, manageability and shine. Hair conditioners primarily
work on improving this surface.
Keratin: A class of proteins that are insoluble in water and have a character-
istic hardness. Animal hooves and horns, as well as human nails, skin and hair, are
composed of keratin.
Static flyaway: Built-up static electrical charges on hair, causing hair to stand
out in disarray because individual hair shafts repel each other. Usually occurs in
dry weather and low humidity.
Stratum corneum: The outermost layer of skin (and part of the epidermis),
comprised primarily of dead cells. Cosmetics are designed to act primarily on this
layer.
Substantivity: The tendency of materials to resist being easily removed. For
example, some sunscreen lotions are substantive because they form a film on the skin
that is relatively water-insoluble. Also, cationic conditioning agents are substantive
because they are electrostatically attracted to the hair (see “conditioning agent”).
Surface tension: The tendency of a fluid’s surface to act as a stretched elastic
membrane. Surface tension is the reason a drop of water is spherical.
The Ingredients
Amphoteric surfactant: Characterized by the ability to react as an acid or a
base, yielding either H+ or OH- ions, depending upon the chemical environment.
Particularly known for its mildness (see “surfactant,” “zwitterion”).
Anionic surfactant: Characterized by a negative charge on its hydrophilic
portion. Well-suited to cleansing products due to its ability to disperse oily dirt
(see “surfactant”).
Cationic surfactant: Characterized by a positive charge on its hydrophilic
portion. This charge is attracted to the negatively charged proteins in skin and
hair, making this material useful as a conditioning agent (see “conditioning agent,”
“surfactant”).
CFC: Acronym for chlorofluorocarbon. This class of materials, commonly used
as aerosol propellants in personal care products until the late 1970s, are claimed
to deplete stratospheric ozone.
14
Chemical feedstock: Raw material used by suppliers to make chemicals. For

example, coconut oil is the feedstock for many surfactants.
Colorants: Add color to a product or an applied surface. The federal govern-
ment strictly regulates the pigments and dyes used in the US cosmetic industry.
Conditioning agent: Improves the feel of hair and skin. For example, hair
conditioners leave hair smooth, soft and static-free.
Detergent: A type of surfactant used in cleaning preparations (see
“surfactant”).
Emollient: When applied to hair or skin, leaves that surface feeling
smoother.
Emulsifier: A type of surfactant that allows oil soluble and water soluble com-
ponents to remain mixed (see “emulsion,” “surfactant”).
EO/PO: Ethylene oxide/propylene oxide. Added to nonionic surfactants to
increase their water solubility. Materials containing these ether linkages are known
as ethoxylates and propoxylates (see “nonionic surfactant”).
Fatty acid: Long-chain hydrocarbon with a carboxylated end. Basic precursor
of many cosmetic raw materials.
FD&C: Abbreviation for Food, Drug and Cosmetic that the US Food and Drug
Administration uses to use to classify a category of certified dyes used in personal
care products. This system has been modified but is still found on some labels.
Fragrance: Synthetic and/or naturally derived aromatic chemical(s) added to
personal care products to produce a specific aroma.
Gelling Agent: Polymeric compound used to create clear, highly thickened
or “gelled” personal care products.
Humectant: Class of ingredients that attract and bind water. Typically used
for moisturizing and conditioning hair and skin. It is also used to improve stabil-
ity of formulas exposed to air. Common examples include glycerin and propylene
glycol.
Lipid: A class of long-chain hydrocarbons that is insoluble in water. Includes
fats, waxes and oils.
Micelle: A (usually) spherical conglomeration of surface active molecules
formed in solution. The polar groups on the molecules align toward the water
phase and the nonpolar groups tend to point toward the oil or nonpolar phase.
This phenomenon allows groups of molecules to form spherical cells. Micelle
formation is the basis for most emulsification. Liposomes are a form of micelles
(see “emulsion,” “surfactant”).
Moisturizer: Ingredient or product that combats the effects of dryness, e.g. a
hair conditioner or skin lotion.
Nonionic surfactant: Characterized by neutral (no net) charge. Immune to the
effects of pH, it is a good solubilizing agent and provides flexibility in formulating
(see “solubilizer,” “surfactant”).
Occlusive Agent: Compound that inhibits the evaporation of water from the
skin leading to moisturization and an improvement in the look and feel. The most
common one is petrolatum.
15
Oil phase: The oil soluble or nonpolar components of an emulsion (see

“emulsion”).
Pearlizing agent: Gives a product an opaque, shiny or glossy “pearl”
appearance.
Polymer: Long-chain, macromolecules used in a variety of personal care ap-
plications including thickening, conditioning, and hair styling.
Preservative: Prevents microbial growth (contamination by bacteria, yeasts,
molds, and so on). A good preservation system is critical to ensure a product’s
stability in use.
Protein: Ingredient based on amino acids that are commonly used in personal
care products for conditioning effects.
Quat: Shortened name of quaternary ammonium compound. Characterized
by the presence of a nitrogen atom bonded on four sides. Quats are useful because
the protonated nitrogen is positively charged, causing it to be attracted to hair and
skin where its hydrocarbon backbone can provide conditioning benefits.
Raw material: Chemical used to make personal care products.
Rheological additive: Used to adjust a product’s viscosity or flow
characteristics.
Silicones: Cosmetic raw materials containing a significant portion of silicone.
Typically used for providing surfaces with shine and slickness. Common examples
include dimethicone and cyclomethicone.
Solubilizer: A type of surfactant used to disperse an insoluble chemical, like
a fragrance oil, in a product (see “surfactant”).
Surfactant: A shortened form of “surface active agent.” This class of chemicals
reduces surface tension; thereby allowing oil and water to form stable mixtures (see
“emulsion,” “solubilizer”).
Suspending agent: Raw material used to immobilize bubbles or large particles
in a cosmetic formulation to create a uniformly distributed look.
Viscosity: A measure of a liquid’s thickness and flow. Water is typically the
benchmark as the lowest viscosity possible.
VOC: Acronym for volatile organic compound. Alcohol and hydrocarbon pro-
pellants are prime examples. Recent worldwide legislation has restricted the use of
these materials, in attempts to reduce the environmental impact of cosmetics.
Water phase: The water soluble portion of an emulsion (see “emulsion”).
The Process
Batching: The preparation of a given quantity of a cosmetic product. It is
important to keep track of the products you make by assigning a discrete “batch
number” to each batch you make. In the laboratory, a batch can be as small as a
few hundred grams; production batches, on the other hand, may be as large as
several thousand gallons.
Formula: The chemicals that make up a product, given as their relative propor-
tions (usually expressed as weight-to-weight percentages). Unless the product is
made simply by mixing everything at once, the procedure should also be outlined
(see “manufacturing procedure”).
16
HLB: Acronym for Hydrophile/Lipophile Balance, a system that helps you

select appropriate surfactants for creating stable emulsions.
Table 2.1. A representative sampling of organizations in the

cosmetic industry
ACS American Chemical Society

ASTM American Standards of Testing Materials (an excellent resource for
test methodologies)
Colipa European lobbying organization (Belgium)
CTFA Cosmetic, Toiletry and Fragrance Association (now PCPC)
CTPA Cosmetic, Toiletry and Perfumery Association (UK)
DOT US Department of Transportation
EU European Union
FDA US Food and Drug Administration (primary regulatory agency for
cosmetic industry)
FTC US Federal Trade Commission
ICMAD Independent Cosmetic Manufacturers and Distributors
IFSCC International Federation Societies of Cosmetic Chemists
JCIA Japanese Cosmetic Industry Association
NAD National Advertising Division of the Council of Better Business
Bureaus
OSHA US Occupational Safety and Health Administration
PCPC Personal Care Products Council (Formerly CTFA)
SCC Society of Cosmetic Chemists (primary professional organization
for cosmetic chemists in the United States)
SCS Society of Cosmetic Scientists (UK)
Lot number: An alphanumeric code that uniquely identifies when and where a
specific batch (lot) of material was produced. Lot numbers are assigned to batches
of chemical raw materials as well as finished products.
Manufacturing procedure: The “recipe” that tells how to make a product
given a specific formula. A good manufacturing procedure includes a description of
the equipment required to make the batch, along with step-by-step instructions.
Mill: A piece of equipment used to reduce particle size and achieve a uniform
distribution of materials within the finished product.
Mixer: A piece of equipment used to blend components of a formula. Some
mixers are simple stirring devices; others provide specialized mixing, such as high
shear (see “emulsion”).
Pilot plant: Most large companies have facilities for producing large test batches
of formulations before manufacturing full scale production batches. A pilot batch
may be several to several hundred gallons. Production of these batches should ap-
proximate actual production conditions.
17
QA/QC: Acronym for quality assurance/quality control, the group(s) in a company

responsible for testing and ensuring that both incoming components (chemicals
and packaging) and finished products meet predetermined specifications.
Scale up: The process of determining the conditions necessary to produce a
formula on a larger scale (see “pilot plant”).
Shear: The cutting force required to mix components together in cosmetic
formulations.
Specification: The range of values acceptable for a specific product charac-
teristic. For example, a product may have a pH specification of 6.0–7. 0. If the
product’s pH falls outside this range, it is considered “out of spec” and, therefore,
unacceptable. Specifications ensure that products and incoming raw materials are
the same from batch to batch and remain stable, and that the consumer will not
perceive any differences among batches.
Testing
Clinical testing: Generally refers to any test (usually for safety or efficacy) done
on human subjects under clinical conditions. With skin care products, often refers
to a moisturization study, also known as the Kligman regression study.
Consumer perception: The impression a user has of a product’s esthetic and
functional characteristics. This test is important because many critical product
properties, such as fragrance, are subjective. Thus, technical tests for quality do
not anticipate consumer perception (see “consumer testing”).
Consumer testing: Any evaluation of consumer perception. Consumer test-
ing, or market research, can help determine if a consumer will like, use, or buy a
product (see “consumer perception”).
Curl retention testing: A test to determine the efficacy of hair-holding polymers
under exaggerated temperature and humidity conditions. Curls are prepared from
hair tresses; the hair styling formula is applied to the tresses so a series of linear
measurements can determine the amount of curl retained over a specified time.
Draize test: A procedure performed on rabbits to evaluate the eye irritation
of cosmetic raw materials and finished products.
Efficacy testing: Evaluates a product’s performance.
Flashpoint: A laboratory measurement of the temperature at which a material
ignites when exposed to a flame under controlled conditions. This data is important
in establishing requirements for shipping and storage of flammable materials.
Foam height testing: Determines ability of a surfactant to lather or produce
bubbles (see “surfactant”).
Inhalation testing: Establishes the dangers associated with chemicals that
enter the body via the lungs. Especially important for aerosol products, which are
likely to be inhaled.
LD50 testing: Determines the potential ingestion toxicity of a raw material or
finished product by finding dose at which 50% of test organisms die.
RIPT: Repeat insult patch testing. Conducted on humans, this test determines
the irritation potential of cosmetic products or raw materials.
18
Salon testing: Evaluations conducted by cosmetologists to determine a prod-

uct’s performance under controlled use conditions.
Stability testing: Series of experiments that determine how a product or raw
material changes over time. Establishes an estimated shelf life.
Tensile testing: Special type of hair testing in which fibers are measured for
their cross sectional area and pulled to determine the breaking profile.
TEWL: Acronym for transepidermal water loss test; it is used to determine the
moisturizing capability of a skin product.
Tress testing: Evaluations of hair care products conducted on hair tresses to
simulate actual product usage under controlled laboratory conditions.
Weight study: A parameter that may be evaluated during stability testing. For
certain products, it is critical to determine the amount of water (or other solvent)
lost or gained through the package since this change may impact formula stability
(see “stability testing”).
Marketing
Ingredient statement (LOI): The list of ingredients (chemicals) contained
in a product. Ingredient statements must appear on cosmetic product packages in
the United States, EU and most other countries. The format must meet specific
requirements in each.
Packaging: The container (and its component parts) to house a cosmetic
product. Packaging types/parts include bottles, caps, pumps, aerosol cans, tubes,
boxes, vials and wrappings.
Trade name: Designation a supplier gives a compound.
Regulatory
CIR: Acronym for cosmetic ingredient review. A Personal Care Product Council
committee that assesses the safety data related to specific cosmetic raw materials
and publishes reports of its findings.
CFR: Acronym for Code of Federal Regulations. A government publication
containing the rules and regulations of the United States, including those related
to the manufacture and sale of cosmetic products.
Claims: Statements made about the performance or benefits of a personal
care product. Establishing support for claims is an important part of new product
development.
Cosmetic: (as defined in the US Federal Register) “Articles intended to be
rubbed, poured, sprinkled or sprayed on, or introduced into, or otherwise applied
to the human body or any part thereof for cleansing, beautifying, promoting attrac-
tiveness, or altering the appearance, and articles intended for use as a component
of any such articles; except that such term shall not include soap.”
Delany Clause: An amendment to the Federal Food, Drug and Cosmetics Act
that states that the FDA “shall not approve for use in food any chemical additive found
to induce cancer in man, or, after tests, found to induce cancer in animals.”
19
Drug: (as defined in the US Federal Register): “Articles intended for use in the
cure, mitigation, treatment, or prevention of disease in man...and articles (other
than food) intended to affect the structure or any function of the body of man.”
EU: European Union.
FFDCA: Federal Food, Drug & Cosmetic Act
FPLA: Fair Packaging and Labeling Act
INCI: International Nomenclature of Cosmetic Ingredients
MSDS: Material safety data sheet. This literature is designed to alert workers
to potentially hazardous characteristics of a compound.
NDA: FDA acronym for “New Drug Application.” This expensive, lengthy
process to get a chemical approved as a new drug is required if your product makes
drug claims and your active ingredient does not fall within current OTC monograph
guidelines (see “OTC monograph”).
OTC drug: Legal drugs that do not require a prescription and can be sold
“over the counter.”
OTC monograph: FDA document establishing active ingredients and defining
allowable concentrations in OTC drugs (see “OTC drug”).
PCPC: Personal Care Products Council. New name for the CTFA.
SPF: Acronym for sun protection factor. A rating that establishes a product’s
ability to protect the skin from UV radiation.
Published 1995 Cosmetics & Toiletries magazine.
For Further Reading

CR Robbins, Chemical & Physical Behavior of Human Hair 4th edition,
Springer-Verlag, NY (2001)
Code of Federal Regulations, Title 21
Cosmetic Bench Reference, Allured Publishing Corp, Carol Stream, IL
(2007)
K Othmer, Encyclopedia of Chemical Technology Vol 8, John Wiley & Sons,
NY (2008)
Van Nostrand’s Scientific Encyclopedia, 10th edition, Van Nostrand and Rein-
hold Co., NY (2008)
Chapter 3
Cosmetic Ingredient
Nomenclature
Naming of cosmetic ingredients.
key words: CTFA, INCI System, FDA, Drug, Cosmetic, Personal

Care Products Council
N o more difficult situation exists than occurs when two or more people cannot
communicate because they speak different languages. Confusion, misun-
derstandings and problems are likely to develop in such a world. Now consider
a highly technical world, a world made up of many chemical compounds, with
very different properties that are blended together in different combinations and
ratios to make products that consumers are going to apply to their person. Now
consider the safety of the many compounds and the plethora of formulations con-
taining them. It becomes clear that as scientists, we need to speak a language that
clearly communicates the concepts behind our science, in a manner that is clearly
understood by our associates, as well as safety professionals and regulators. This
information needs to be communicated in a way that is informative and consumer
friendly. Now, we begin to define the attributes of the system needed for the per-
sonal care industry.
Every student of organic chemistry should be familiar with the IUPAC system of
chemical nomenclature. Imagine a world where the full IUPAC names were applied
to cosmetic bottles. The names would not only be confusing and incomprehensible,
but the required label would simply not fit on the bottle.
In order to understand what is necessary in our industry and to comply with
various regulations, it is first necessary to understand the regulatory role and the
interrelationships between the different groups participating in the process. One
key group is the Food and Drug Administration (FDA). The FDA provides answers
to questions critical to our industry on their Web site, www.fda.com. Answers to
important questions are shown in Table 3.1.
21
22
Cosmetic Ingredient Nomenclature Beginning Cosmetic Chemistry
Table 3.1. The Food and Drug Administration (FDA)
What does the law say about cosmetic safety and labeling?
The two most important laws pertaining to cosmetics marketed in the United
States are the Federal Food, Drug, and Cosmetic Act (FD&C Act) and the
Fair Packaging and Labeling Act (FPLA).
The FD&C Act prohibits the marketing of adulterated or misbranded cosmetics
in interstate commerce. Violations of the Act involving product composition—
whether they result from ingredients, contaminants, processing, packaging,
or shipping and handling—cause cosmetics to be adulterated and subject to
regulatory action. Under the FD&C Act, a cosmetic is adulterated if—
• “it bears or contains any poisonous or deleterious substance which may
render it injurious to users under the conditions of use prescribed in the
labeling thereof, or under conditions of use as are customary and usual”
[with an exception made for hair dyes];
• “it consists in whole or in part of any filthy putrid, or decomposed
substance”;
• “it has been prepared, packed, or held under insanitary conditions whereby
it may have become contaminated with filth, or whereby it may have been
rendered injurious to health”;
• “its container is composed, in whole or in part, of any poisonous or del-
eterious substance which may render the contents injurious to health”;
or
• except for hair dyes, “it is, or it bears or contains, a color additive which is
unsafe within the meaning of section 721(a)” of the FD&C Act. (FD&C
Act, sec. 601)
Improperly labeled or deceptively packaged products are considered mis-
branded and subject to regulatory action. Under the FD&C Act, a cosmetic
is considered misbranded if—
• “its labeling is false or misleading in any particular”;
• its label does not include all required information;
• the required information is not adequately prominent and conspicuous;
• “its container is so made, formed, or filled as to be misleading”;
• it is a color additive, other than a hair dye, that does not conform to ap-
plicable regulations issued under section 721 of the FD&C Act; and
• “its packaging or labeling is in violation of an applicable regulation is-
sued pursuant to section 3 or 4 of the Poison Prevention Packaging Act
of 1970.” (FD&C Act, sec. 602)
23
In addition, under the authority of the FPLA, FDA requires an ingredient

declaration to enable consumers to make informed purchasing decisions.
Cosmetics that fail to comply with the FPLA are considered misbranded
under the FD&C Act.
It is important to understand that Congress passes the laws that govern the
United States. To put those laws into effect, Congress authorizes certain
government agencies, including FDA, to create and enforce regulations, but
only as authorized under the law. A change in FDA’s statutory authority over
cosmetics would require Congress to change the law.
Does FDA approve cosmetics before they go on the market?
FDA’s legal authority over cosmetics is different from other products regu-
lated by the agency, such as drugs, biologics, and medical devices. Cosmetic
products and ingredients are not subject to FDA premarket approval au-
thority, with the exception of color additives. However, FDA may pursue
enforcement action against violative products, or against firms or individuals
who violate the law.
Who is responsible for substantiating the safety of cosmetics?
Cosmetic firms are responsible for substantiating the safety of their products
and ingredients before marketing. Failure to adequately substantiate the
safety of a cosmetic product or its ingredients prior to marketing causes the
product to be misbranded unless the following warning statement appears
conspicuously on the principal display panel of the product’s label:
“Warning—The safety of this product has not been determined.”
(21 CFR 740.10)
In addition, regulations prohibit or restrict the use of several ingredients in
cosmetic products and require warning statements on the labels of certain
types of cosmetics.
In general, except for color additives and those ingredients which are pro-
hibited or restricted from use in cosmetics by regulation, a manufacturer
may use any ingredient in the formulation of a cosmetic provided that the
ingredient and the finished cosmetic are safe, the product is properly labeled,
and the use of the ingredient does not otherwise cause the cosmetic to be
adulterated or misbranded under the laws that FDA enforces.
Can FDA order the recall of a hazardous cosmetic from the
market?
Recalls of cosmetics are voluntary actions taken by manufacturers or distribu-
tors to remove from the marketplace products that represent a hazard or gross
deception, or that are somehow defective. FDA categorizes a firm’s action
24
as a recall (as opposed to a market withdrawal) when it determines that the

product hazard or defect represents a violation of the FD&C Act.
FDA is not authorized to require recalls of cosmetics but does monitor
companies that conduct a product recall and may request a product recall if
the firm is not willing to remove dangerous products from the market with-
out FDA’s written request. Recalls are addressed in Title 21 of the Code of
Federal Regulations (CFR), sections 7.40 through 7.59.
What actions can FDA take against firms that market adulterated or
misbranded cosmetics?
FDA may take regulatory action if it has information to support that a cos-
metic is adulterated or misbranded. The agency can pursue action through
the Department of Justice in the federal court system to remove adulterated
and misbranded cosmetics from the market. To prevent further shipment of an
adulterated or misbranded product, the agency may request a federal district
court to issue a restraining order against the manufacturer or distributor of
the violative cosmetic. Violative cosmetics may be subject to seizure. FDA
also may initiate criminal action against a person violating the law.
In addition, FDA works closely with the US Customs Service to monitor
imports. Under section 801(a) of the FD&C Act, imported cosmetics are
subject to review by FDA at the time of entry through US Customs. Products
that do not comply with FDA laws and regulations are subject to refusal of
admission into the United States. Violative products must be brought into
compliance (if feasible), destroyed, or re-exported.
FDA takes regulatory action based upon agency priorities, consistent with
public health concerns and available resources.
Can FDA inspect cosmetic manufacturers?
FDA can and does inspect cosmetic manufacturing facilities to assure cos-
metic product safety and determine whether cosmetics are adulterated or
misbranded under the FD&C Act or FPLA.
Does FDA test cosmetics?
The FD&C Act does not subject cosmetics to FDA pre-market approval in
order to be marketed legally. However, FDA collects samples for examination
and analysis as part of its plant inspections, import inspections, and follow-
up to complaints of adverse reactions. FDA may also conduct research on
cosmetic products and ingredients to address safety concerns.
25
The agency does not function as a private testing laboratory, and in order to
avoid even the perception of conflict of interest, does not recommend pri-
vate laboratories to consumers or manufacturers for sample analysis. Testing
laboratories are listed in your telephone directory.
Must cosmetic manufacturers register with FDA?
Manufacturers are not required to register their cosmetic establishments, file
data on ingredients, or report cosmetic-related injuries to FDA. However,
companies are encouraged to register their establishments and file Cosmetic
Product Ingredient Statements with FDA’s Voluntary Cosmetic Registration
Program (VCRP).
Is It a Cosmetic, a Drug, or Both?

The legal difference between a cosmetic and a drug is determined by a
product’s intended use. Different laws and regulations apply to each type of
product. Firms sometimes violate the law by marketing a cosmetic with a
drug claim, or by marketing a drug as if it were a cosmetic, without adhering
to requirements for drugs.
How does the law define a cosmetic?
The Food, Drug, and Cosmetic Act (FD&C Act) defines cosmetics by their
intended use, as “articles intended to be rubbed, poured, sprinkled, or
sprayed on, introduced into, or otherwise applied to the human body…for
cleansing, beautifying, promoting attractiveness, or altering the appearance”
[FD&C Act, sec. 201(i)]. Among the products included in this definition
are skin moisturizers, perfumes, lipsticks, fingernail polishes, eye and facial
makeup preparations, shampoos, permanent waves, hair colors, toothpastes,
and deodorants, as well as any material intended for use as a component of
a cosmetic product.
How does the law define a drug?
The FD&C Act defines drugs by their intended use, as “(A) articles intended
for use in the diagnosis, cure, mitigation, treatment, or prevention of disease,
and (B) articles (other than food) intended to affect the structure or any func-
tion of the body of man or other animals” [FD&C Act, sec. 201(g)(1)].
How can a product be both a cosmetic and a drug?
Some products meet the definitions of both cosmetics and drugs. This in-
tersection may happen when a product has two intended uses. For example,
a shampoo is a cosmetic because its intended use is to cleanse the hair. An
antidandruff treatment is a drug because its intended use is to treat dandruff.
Consequently, an antidandruff shampoo is both a cosmetic and a drug. Among
26
other cosmetic/drug combinations are toothpastes that contain fluoride, de-

odorants that are also antiperspirants, and moisturizers and makeup marketed
with sun-protection claims. Such products must comply with the requirements
for both cosmetics and drugs.
What about “cosmeceuticals”?
The FD&C Act does not recognize any such category as “cosmeceuticals.”
A product can be a drug, a cosmetic, or a combination of both, but the term
“cosmeceutical” has no meaning under the law.
How is a product’s intended use established?
Intended use may be established in a number of ways. Among them are:
• Claims stated on the product labeling, in advertising, on the In-
ternet, or in other promotional materials. Certain claims may cause
a product to be considered a drug, even if the product is marketed as if
it were a cosmetic. Such claims establish the product as a drug because
the intended use is to treat or prevent disease or otherwise affect the
structure or functions of the human body. Some examples are claims that
products will restore hair growth, reduce cellulite, treat varicose veins,
or revitalize cells.
• Consumer perception, which may be established through the
product’s reputation. For products in this position the consumer would
be asked why she is buying it and what she expects it to do.
• Ingredients that may cause a product to be considered a drug
because they have a well known (to the public and industry)
therapeutic use. An example is fluoride in toothpaste.
This principle also holds true for essential oils in fragrance products. A fra-
grance marketed for promoting attractiveness is a cosmetic. But a fragrance
marketed with certain “aromatherapy” claims, such as assertions that the
scent will help the consumer sleep or quit smoking, meets the definition of
a drug because of its intended use.
How are the laws and regulations different for cosmetics and
drugs?
The following information is not a complete treatment of cosmetic or drug
laws and regulations. It is intended only to alert you to some important differ-
ences between the laws and regulations for cosmetics and drugs in the areas of
approval, good manufacturing practice, registration, and labeling. You should
direct questions regarding laws and regulations for drugs to CDER.
27
How approval requirements are different

FDA does not have a premarket approval system for cosmetic products or
ingredients, with the important exception of color additives. Drugs, however,
are subject to FDA approval. Generally, drugs must either receive premar-
ket approval by FDA or conform to final regulations specifying conditions
whereby they are generally recognized as safe and effective, and not mis-
branded. Currently, certain—but not all—over-the-counter (OTC) drugs
(that is, non-prescription drugs) that were marketed before the beginning
of the OTC Drug Review (May 11, 1972) may be marketed without specific
approval pending publication of final regulations under the ongoing OTC
Drug Review. Once a regulation covering a specific class of OTC drugs is
final, those drugs must either
• Be the subject of an approved New Drug Application (NDA) [FD&C
Act, sec. 505(a) and (b)], or
• Comply with the appropriate monograph, or rule, for an OTC drug.
What do these terms mean?
An NDA is the vehicle through which drug sponsors formally propose that
FDA approve a new pharmaceutical for sale and marketing in the United
States. FDA only approves an NDA after determining, for example, that the
data are adequate to show the drug’s safety and effectiveness for its proposed
use and that its benefits outweigh the risks. The NDA system is also used
for new ingredients entering the OTC marketplace for the first time. For
example, the newer OTC products (previously available only by prescription)
are first approved through the NDA system and their “switch” to OTC status
is approved via the NDA system.
FDA has published monographs, or rules, for a number of OTC drug cat-
egories. These monographs, which are published in the Federal Register,
state requirements for categories of non-prescription drugs, such as what
ingredients may be used and for what intended use. Among the many non-
prescription drug categories covered by OTC monographs are
• acne medications
• treatments for dandruff, seborrheic dermatitis, and psoriasis
• sunscreens
A note on “new drugs”
Despite the word “new,” a “new drug” may have been in use for many years. If
a product is intended for use as a drug, no matter how ancient or “traditional”
its use may be, once the agency has made a final determination on the status
of an OTC drug product it must have an approved NDA or comply with the
28
appropriate OTC monograph to be marketed legally in interstate commerce.

Certain OTC drugs may remain on the market without NDA approval pend-
ing final regulations covering the appropriate class of drugs.
Where to learn more about NDAs and OTC monographs
If you have questions about NDAs and OTC monographs, you should address
them to CDER. The CDER Handbook provides an introduction to the drug
approval and OTC monograph processes. Other resources, also available on
CDER’s Web site, provide additional information on these subjects.
How good manufacturing practice requirements are different

Good manufacturing practice (GMP) is an important factor in assuring that
your cosmetic products are neither adulterated nor misbranded. However,
no regulations set forth specific GMP requirements for cosmetics. In con-
trast, the law requires strict adherence to GMP requirements for drugs, and
there are regulations specifying minimum current GMP requirements for
drugs [Title 21 of the Code of Federal Regulations (CFR), parts 210 and
211]. Failure to follow GMP requirements causes a drug to be adulterated
[FD&C Act, sec. 501(a)(2)(B)].
How registration requirements are different

FDA maintains the Voluntary Cosmetic Registration Program, or VCRP,
for cosmetic establishments and formulations [21 CFR 710 and 720]. As its
name indicates, this program is voluntary. In contrast, it is mandatory for
drug firms to register their establishments and list their drug products with
FDA [FD&C Act, sec. 510; 21 CFR 207].
How labeling requirements are different

A cosmetic product must be labeled according to cosmetic labeling regula-
tions. See the Cosmetic Labeling Manual for guidance on cosmetic labeling.
OTC drugs must be labeled according to OTC drug regulations, including
the “Drug Facts” labeling, as described in 21 CFR 201.63. Combination
OTC drug/cosmetic products must have combination OTC drug/cosmetic
labeling. For example, the drug ingredients must be listed alphabetically
as “Active Ingredients,” followed by cosmetic ingredients, listed in order of
predominance as “Inactive Ingredients.”
29
The Personal Care Products Council

In order to develop a system that meets the above criteria, The Personal Care
Products Council has been established by our industry to work with the FDA (Food
and Drug Administration), members of our industry, consumers and other inter-
ested individuals. An understanding of the function of the FDA, The Personal Care
Products Council and the responsibility of cosmetic companies, and raw material
suppliers is key to understanding our industry.
Table 3.2 outlines the function of the Personal Care Products Council and is
taken from their Web site, www.ctfa.org.
Table 3.2. The Personal Care Products Council1
The following information taken from www.ctfa.org is important to the un-

derstanding of the function of this key organization.
The Personal Care Products Council (formerly the Cosmetic, Toiletry
and Fragrance Association) is the leading national trade association for
the cosmetic and personal care products industry and represents the most
innovative names in beauty today.
For more than 600 member companies, we are the voice on scientific,
legal, regulatory, legislative and international issues for the personal care
product industry. We are a leading and trusted source of information
for and about the industry and a vocal advocate for consumer safety and
continued access to new, innovative products.
About the Personal Care Products Industry

Every day, millions of consumers around the world rely on personal care
products to live better, healthier lives. From moisturizers, lipsticks and
fragrances to sunscreens, soaps and anti-cavity toothpastes, these products
are essential to today’s consumer lifestyles. The personal care products
industry is a global industry with more than $250 billion in annual retail
sales.
Committed to Safety and Science

Product safety is the top priority of the personal care products industry.
We work diligently with our members to maintain the highest standards of
safety rooted in science and cutting-edge research. Through self-regulation,
the Council works to uphold and often surpass the most stringent US
consumer product safety standards. The Council has adopted a Consumer
Commitment Code to formalize many existing product safety practices and
to demonstrate its members’ commitment to safety. The linchpin of our
30
self-regulatory programs is the Cosmetic Ingredient Review (CIR) Expert

Panel, an independent, nonprofit panel of world-renowned scientists and
physicians established in 1976 to assess the safety of ingredients used in
cosmetics in the United States with the support of the US Food and Drug
Administration (FDA) and the Consumer Federation of America. Recog-
nizing the enormous expense and inefficiency of duplicate safety testing
on ingredients by member companies, the industry gathers worldwide
published and unpublished safety data for review by the independent
expert panel.
Providing In-Depth Information

We recognize and value our position as a trusted, relied upon source of
information about the global beauty industry. On any given day, beauty, trade
and mainstream media depend on our organization for credible, accurate
information about the personal care products industry and its products.
For example, our website, www.cosmeticsinfo.org, provides in-depth
information on ingredient safety and the safety assessment processes used
on cosmetics and personal care product ingredients.
Advocating for Consumer Safety

We are an active, vocal advocate for consumer safety. We work with the
US FDA and federal, state, and local leaders to ensure quality and safety
standards that protect the health of consumers and the environment.
Our goal is to strengthen voluntary industry self-regulatory programs and
promote uniform national regulatory standards.
Pursuing Harmonized Global Regulatory Standards

The Council works to harmonize global regulatory practices for consumer
products; to eliminate trade barriers; and to ensure a level playing field
for all our member companies while instilling consumer confidence in
product safety.
The Mission—INCI Names

In the early 1970s, the US cosmetics industry became concerned about gov-
ernment regulation. To demonstrate its capability for self-regulation, it instituted
programs to encourage voluntary registration of cosmetic formulations and to scien-
tifically review the safety and efficacy of cosmetic ingredients. Naming of cosmetic
ingredients is one of the most important functions of the Personal Care Products
Council. Table 3.3 outlines some of the rules for nomenclature.
31
*Table 3.3. Inventory of Ingredients—Nomenclature Conventions*
Conventions used for establishing INCI names are as follows:

1. In order to facilitate use and clarity, INCI names have been designed to require
a minimum of punctuation and capitalization.
2. Wherever new nomenclature has been adopted, every effort has been made to
use the shortest name consistent with these rules.
3. Simple chemical names are used wherever possible.
4. Recognized chemical abbreviations are used where applicable. A list of the
abbreviations used in the Inventory may be found under the section “Abbrevia-
tions”.
5. Traditional stems are retained as combining forms when consistent with other
systems (see rule 17).
6. Abbreviations are utilized for simplifying the nomenclature of families of
complex ingredients when applicable (see abbreviation list under the section
“Abbreviations”).
7. Compounds that are related or are similar to materials described in recognized
sources are named, whenever possible, by analogy to the listed names.
8. Singly substituted derivatives do not usually include the prefix “mono”. This
term is used only when required to prevent ambiguity. The absence of a suit-
able prefix implies “mono”, e.g. Glyceryl stearate.
9. The term “Glyceride” has been utilized to describe a monoglyceride. Mixtures
of mono-, di- and triglycerides are referred to as “Glycerides”. Triglycerides are
assigned specific nomenclature, e.g. Tristearin.
10. Multiple substitution is routinely described with the appropriate prefix such as
“di-”, “tri-” or “tetra-”, e.g. Glyceryl distearate.
11. Names of ingredients, other than colors, that contain terminal numbers are
generally hyphenated. Derivatives of hyphenated materials retain the original
hyphen, e.g. Laureth-3, Laureth-3 phosphate.
12. Hydration states are not usually expressed.
13. Straight-chain alkyl groups are described by their common stem names (see
rule 17).
14. Materials containing mixtures of even-carbon chain length fractions are named
by the appropriate commonly used fatty stem term, e.g. Cetearyl alcohol (C16
and C18). Materials containing mixtures of even- and odd-carbon chain length
fractions are designated by alternative nomenclature, e.g. C12-15 alcohols
(C12, C13, C14 and C15).
15. Branched-chain alkyl groups are usually described by the prefix “iso” followed
by the common stem name for the comparable straight-chain group (e.g.
Isostearyl alcohol, Isocetyl alcohol)—see also rule 17. The major exception
to this rule is the nomenclature for the 2-alkyl of Guerbet alcohols. These are
named by standard chemical rules (e.g., Ethylhexanol, Octydodecanol, De-
cyltetradecanol). Derivatives are named accordingly (e.g., Ethylhexyl myristate,
Cetyl ethylhexanoate, Diethylhexylamine, Triethylhexanoin, Butyloctanoic acid).
*European Commission—Enterprise and Industry Directorate General Consumer goods—

Cosmetics, 24/02/06
32
16. The following table has been included to clarify the nomenclature for deriva-
tives of caproic, caprylic and capric acids.
Chain length Stem name Acid Ester
C6 Capro Caproic Caproate
C8 Capryl Caprylic Caprylate
C10 Capr Capric Caprate
Chain length Acyl Alkyl Ampho

C6 Caprooyl Caproyl Caproo
C8 Capryloyl Caprylyl Caprylo
C10 Caproyl Capryl Capro
17. The following table describes the nomenclature applied to straight-chain acids
and alcohols. Branched-chain acids and alcohols utilize the names listed in
this table preceded by the term “iso” (e.g., Isostearic acid). Guerbet alcohols,
however, are designated by specific names (e.g., Octyldodecanol). (See also
rule 15).
Saturated:
Acid Alcohol
C6 Caproic Hexyl
C7 Heptanoic Heptyl
C8 Caprylic Caprylyl
C9 Pelargonic Nnyl
C10 Capric Decyl
C11 Undecanoic Undecyl
C12 Lauric Lauryl
C13 Tridecanoic Tridecyl
C14 Myristic Myristil
C15 Pentadecanoic Pentadecyl
C16 Palmitic Cetyl
C17 Margaric Heptadecyl
C18 Stearic Stearyl
C20 Arachidic Arachidyl
C22 Behenic Behenyl
Unsaturated:
C11 Undecylenic Undecylenyl
C16 Palmitoleic Palmitoeyl
C18 Oleic Oleyl
C18 Linoleic Linoleyl
C18 Linolenic Linolenyl
C20 Arachidonic Arachidonyl
C22 Cetoleic Cetoleyl
C22 Erucic Erucyl
18. The nomenclature for ingredients consisting of mixtures of similar materials
(e.g., fatty acids, fatty alcohols) is determined on the basis of the chemical
identity of the raw material as purchased. Mixtures that reflect the original
33
istribution of components due to their natural source (e.g., coconut) are

d
named utilizing the source stem (e.g., coconut alcohol). If the original natural
distribution has been significantly cut or enriched, the mixture is named on the
basis of the predominant component.
19. Names of lanolin derivatives usually contain the stem “lan”, e.g.. Laneth-60.
20. Because of the existing widespread use of these denominations, alkanol-
amides are named from the parent alkyl amide and the appropriate abbrevia-
tion for the amine used, e.g., Cocamide MEA.
21. The dimethyl term is omitted and is assumed in all alkyl dimethyl amine oxide
names (e.g., Stearamine oxide). Tertiary amine oxides with different substituent
groups are named completely (e.g., Dihydroxyethyl stearamine oxide).
22. Quaternary, ammonium salts usually have the suffix “-ium” in the stem of the
cation. The term “monium” describes a monomethyl-substituted quaternary
nitrogen; “dimonium” describes a dimethyl-subsituted quaternary nitrogen;
“trimonium” describes a trimethyl-substituted quaternary nitrogen.
23. The terms quaternium/polyquaternium are used to describe complex quaterna-
ry ammonium salts that do not have a common name or that cannot be named
by analogy to established names (e.g., Quaternium-82, Polyquaternium-20).
24. The term “ampho” has been used as a combining term in the nomenclature
for amphoteric surfactants derived from imidazoline intermediates. In naming
these compounds, this stem is combined with the appropriate stem names for
the substituent groupings (e.g., Sodium Cocoamphoacetate).
25. Common fatty stem terms are used to designate the alkyl portion of alkyl imi-
dazoline compounds (e.g., Lauryl Hydroxyethyl Imidazoline) even though one
carbon atom of the fatty radical becomes a member of the heterocyclic ring
during the materials’ manufacture.
26. Biological materials are named by specific terms (e.g., Hyaluronic Acid, Hy-
drogenated Menhaden Oil) when the material has been isolated, purified and
chemically characterized. Alternative nomenclature for biologicals is utilized
to name materials in accordance with the extent of their processing. They may
have INCI names based on: (a) the Latin name of the genus, or (b) primarily on
designations from Pharmacopoeias, followed by the part used if pertinent, and
the type of preparation if pertinent (e.g., extract, oil, powder, etc.). For mam-
malian derived ingredients, usually (c) the INCI names are based on the English
name of the part used, if pertinent (e.g., connective tissue, spleen, stomach,
etc.) and the type of preparation, if pertinent (e.g. extract, oil).
Examples of INCI names for biologicals are (a) Brevoortia Oil; (b) Faex Extract;
(c) Connective Tissue Extract.
27. Cosmetic colorants have INCI names according to the nomenclature used in
Annex IV to Directive 76/768/EEC.
28. Hair dye ingredients are named according to chemical structure. In the event
that chemical names are very complex, a colour/number combination is used
prefixed by the letters “‘HC”.
29. Denatured alcohols are designated by the INCI name “Alcohol denat.”. Alcohol
denat. is ethyl alcohol that is denatured with one or more denaturing agents in
accordance with the national legislation of each Community Member State.
34
30. Materials derived from plants are known as botanicals. In general, these
ingredients have not undergone chemical modifications and include plant
derived ingredients such as extracts, juices, waters, distillates, powders, oils,
unsaponifiables, etc. They have INCI names based on the international Linné
designated nomenclature of the genus and the species, followed by the plant
part, if pertinent or applicable (e.g., leaf, fruit, bark, etc.), and the type of prepa-
ration (e.g., extract, oil, powder, etc.). Chemical derivatives of botanicals follow
the nomenclature rules for chemicals (e.g., Cocoglyderides, Hydrogenated
Castor Oil, Hydrogenated Palm Acid, Olive Acid, Palm Alcohol, Soyamide DEA,
Sulfated Olive Oil, etc.).
The following references are used to establish the Linné-derived for botanicals:
(a) The primary referece is Penso, G., Index Plantarum Medicinalium Totius
Mundi Eorumque Synonymorum, O.E.M.F. Milano (1983—ISBN 88-7076-027-8.
(b) When the genus and species is not identified in the text cited in (a), a variety
of secondary sources are utilized including the following, in order of prior-
ity: (1) Steinmetz, E.F., Codex vegetabilis, Amsterdam (1957); (2) Hoppe, H.A.,
Drogenkunde, 8th Edition, Walter de Gruyter, Berlin, Volume 1 (1957—ISBN
3-11-00-8)¸Volume 2 (1977 – ISBN 3-11-006660-2); (3) Mabberley, D.J., The
Plant Book—A portable dictionary of higher plants, Cambridge 1992—ISBN N°
0-521-34060-8; (4) Hoppe H.A., Levring T., Tnaka Y., Marine Algae in Pharma-
ceutical Science, Walter de Gruyter, Berlin, New York, 1979.
31. Name/number combinations are used as INCI names for cosmetic ingredients
only where the complexity and/or similarity of ingredients precludes assign-
ment of reasonable nomenclature by any other means. In all cases where arbi-
trary numbers are used, these numbers are preceded by names suggestive of
the structure or the composition of the material. Each name/number combina-
tion represents a specific ingredient that is listed in the Inventory. The following
name/number series of combinations have been used:
(a) Benzophenone
This term is used for all benzophenon derivatives
(e.g., Benzophenone-2).
(b) HC color
See rule 28.
(c) Quaternium/Polyquaternium
See rule 23.
(d) Hydrofluorocarbon/Hydrochlorofluorocarbon
These terms are used for hydrohalocarbon aerosol propellants
(e.g.Hydrofluorocarbon 152a, Hydrochloroflurocarbon 142b).
(e) Polysilicone
common names or established conventions for silicone compounds (e.g.,
Poylsilicone-1)
(f) Polyacrylate
see rule 49.
(g) Polyester-
see rule 49.
(h) Polyether-
see rule 49.
(i) Polyurethane-
see rule 49.
35
32. Commercial raw materials are often deliberate mixtures of several compo-
nents. The mixtures do not appear as such and must be identified by listing the
individual components (e.g., Kathon CG: Aqua, Chloromethylisothiazolinone,
Methylisothiazolinone, Magnesium chloride, Magnesium nitrate).
33. The INCI names for extracts represent the “material extracted” and do not
include reference to the extracting solvents and/or other diluents that may be
present in these materials.
34. Solvents and/or diluents contained in commercially available raw materials
such as surfactants, polymers and resins are not normally identified as part of
the INCI name.
35. Polyethylene glycol (polyoxy-1, 2-ethanediyl) is abbreviated to the acronym
“PEG”.
Polyethylene glycol homopolymers are named as PEG-X, where X is the aver-
age number of ethylene oxide monomer units, e.g., PEG-10.
Ethoxylated alcohols are named by combining the conventional alcoholic stem
name with the suffix “eth” followed by the average number of ethylene oxide
monomer units, e.g. Laureth-10.
Esters of polyethylene glycol homopolymers are named as PEG derivatives,
e.g., PEG-10 stearate.
Other ethoxylated substances are named accordingly, e.g., PEG-6 cocamide.
Because names based on the approximate molecular weight of the ethylene
oxide polymer are also in common use, the following table is provided to allow
easy conversion between the two systems:
Approximate Average Number
Molecular Weight of Monomer Units
100 2
200 4
300 6
400 8
450 9
500 10
600 12
1000 20
1540 32
1800 36
2000 40
3000 60
4000 75
6000 150
8000 180
36. Polypropylene glycol (polyoxy-1, 2-propanediyl) is abbreviated to the acronym
“PPG”. Polypropylene glycol homopolymers are named as PPG-X, where X is
the average number of propylene oxide monomer units, e.g., PPG-10.
Esters and ethers of polypropylene glycol homopolymers are named as PPG
derivatives, e.g., PPG-10 stearate, PPG-10 lauryl ether.
Other propoxylated substances are named accordingly.
36
37. PEG and PPG polymers or their derivatives in which one of the terminal primary
alcohol groups (-CH2OH) has been oxidized to a carboxylic acid (-COOH) are
named by adding the term “carboxylic acid” or “carboxylate” to the parent
name of the original polymer, e.g. PEG-10 carboxylic acid, Coceth-7 carboxylic
acid, Ammonium laureth-8 carboxylate.
38. The term “Pareth” applies to ethoxylated parffinic alcohols containing both
even- and odd-carbon chain length fractions.
39. The term “Acrylates” is used to describe linear, non-cross linked copolymers
that contain combinations of acrylic acid, methacrylic acid and their methyl,
ethyl, propyl or butyl esters. Similarly, the term “Crotonate(s)” is used to
describe the copolymers that contain combinations of crotonic acid and its
methyl, ethyl, propyl or butyl esters.
40. The name “Carbomer” is used to describe high molecular weight cross-linked
homopolymers of acrylic acid. The cross-linking agent(s) is (are) identified in
the ingredient entry definition. (See also rule 41)
41. The term “cross-polymer” is used to describe polymers other than Carbomer
that are cross-linked. (See also rule 40)
42. The term “Poloxamer” denotes a symmetrical block copolymer formed by
ethoxylation of polypropylene glycol. Substances with differing degrees of po-
lymerization are further identified by a code number derived from the molecular
weight of the polymer.
43. The term “Meroxapol” denotes a symmetrical clock copolymer formed by the
propoxylation of polyethlene glycol. Substances with differing degrees of po-
lymerization are further identified by a code number derived from the molecular
weight of the polymer.
44. The term “Poloxamine” denotes a symmetrical block copolymer formed by
successively propoxylating then ethoxylating ethylene diamine. Substances
with differing degrees of polymerization are further identified by a code number
derived from the molecular weight of the polymer.
45. Copolymers of ethylene glycol and propylene glycol which do not form sym-
metrical block copolymers are named as PEG/PPG-X/Y derivatives where X
and Y are the average number of ethylene oxide and propylene oxide monomer
units respectively.
46. The term “Alkoxyno-n” means an ethoxylated alkyl phenol where n indicates
the average number of ethylene oxide units.
When the name is: the alkyl is:
octoxynol tetramethylbutyl
nonoxynol nonyl
dodoxynol dodecyl
pentadoxynol pentadecyl
47. Biotechnological materials are substances derived by the action of micro-
organisms, such as bacteria or yeasts, on a substrate to produce materials by
fermentation, metabolism, hydrolysis, lysis or other processes. The process
may involve the use of nutrients or other materials such as enzymes. The
resulting product is referred to as a “culture” or “ferment”. The ferment can be
further processed by extraction, filtration, and/or other procedures to yield the
final product.
37
The conventions used to provide INCI names for biotechnological materials are
as follows:
(a) When the end product produced from a given “ferment” or “culture” has
a common or usual name, such name may be used, e.g., Yogurt, Gellan
Gum or Xanthan Gum.
(b) When the end product does not have a common or usual name, the prod-
uct will be named using the genus of the microorganism, followed by a
slash and the name of the substrate (if applicable), followed by the work
“ferment”. Substrates will be identified by their common, usual, or other
technical name, e.g., Lactococcus/Carrot Ferment. On a case-by-case
basis, the genus and species name of the microorganism may be used
when the used of the genus only may be misleading and the identification
of the species is needed for clarity, e.g., Candida bombicola Ferment.
(c) If the selected components of the ferment have been isolated and puri-
fied to a significant extent and analytical evidence is provided, the name
for one or more of the components may be used, e.g., Glycosphingolip-
ids, Beta-Glucan or Dextran.
48. The term “Ceramide” as part of an INCI name will be assigned to those classes
and structures of natural lipids derived from skin as reported by Wertz P.W.,
Miethke M.C., Long S.A., Strauss J.M. and Downing D.T. in “The composition of
ceramides from human stratum corneum and from comedones”, The Journal
of Investigative Dermatology, 84, 410-412 (1985).
A synthetic N-acylated sphingoid base that is identical to any one of the many
constituents of the natural ceramides, as reported by Wertz, will be assigned
an INCI labeling name using the term ceramide followed by a number (e.g.,
Ceramide 3) or a number and Roman numeral (e.g., Ceramide 6II). The term ce-
ramide as part of the INCI name will only be assigned to a synthetic N-acylated
sphingoid base that contains, as the predominant component, the erythro
isomer of at least one of the many natural ceramides described by Wertz. A
predominant component is one that is present at the highest concentration in
relation to other synthetic materials of similar structure and related composi-
tion present in a mixture.
Synthetic N-acylated sphingoid bases that do not have the erythro configura-
tion, or otherwise are not constituents of natural ceramides as described by
Wertz, will not be named using the term ceramide. In such cases, a chemical
or other appropriate name, to be determined by the International Nomenclature
Committee (INC) on a case-by-case basis, will be assigned as the INCI labeling
name. The INC may accept a signed statement by a person requesting the
assignment of an INCI name that a synthetic N-acylated sphingoid base is the
erythro isomer and otherwise conforms in composition to the above criteria.
49. The term “Aminoacrylates” refers to simple aminoacrylates, in which the
substituted alkyl groups attached to amino nitrogen range from C1-4, and acry-
lates conforms to the definition as described in rule 33.
50. Synthetic peptides consisting of 2–10 amino acid residues are named using
the appropriate prefix, di-, tri-, tetra-, etc., followed by the term peptide and an
arbitrary number, e.g., Dipeptide-2.
Synthetic peptides consisting of 11–100 amino acids are designated by the
term oligopeptide, followed by an arbitrary number.
38
Synthetic peptides consisting of more than 100 amino acids are designated by
the term polypeptide, followed by an arbitrary number.
The amino acid residues composing the peptide are listed alphabetically in the
entry definition in Section 1.
The amino acid residues may include the following:
Alanine Glutamine Phenylalanine
Arginine Glycine Proline
Asparagine Histidine Serine
Aspartic Acid Isoleucine Threonine
Cysteine Leucine Tryptophan
Cystine Lysine Tyrosine
Glutamic Acid Methionine Valine
51. Polymer nomenclature—Polymeric materials are named according to the name
in common usage if it is well known, or by the structure if well defined. If no
common name exists, and the structure is not well defined, the polymers are
named according to their source, as described below. Homopolymers (consist-
ing of one constituent monomer) are named by placing the term ‘poly’ before
the constituent monomer, e.g., Polyisobutene.
Copolymers and Crosspolymers (consisting of two or more constituent mono-
mers) are named by listing the monomers separated by a slash (/) followed by
the work “Copolymer” or “Crosspolymer”, respectively, e.g., Acrylates/Acryl-
amide Copolymer, Acrylates/VA Crosspolymer.
Copolymers consisting of four or more monomers may be given an INCI name
according to their class followed by an arbitrary number, e.g., Polyester-1, with
the monomers listed in the entry definition of the material. Such nomenclature
is granted at the discretion of the INC, with a purpose of shortening lengthy
INCI names.
Thus far, the only classes of polymers to be created for this type of nomencla-
ture are Polyesters, Polyacrylates and Polyurethanes. More classes may be
added in the future, if the need arises.
Sources For Ingredient Nomenclature

Originally Published in Cosm Toil 110 (5) 29-31 (1995)
The CTFA did not arbitrarily create ingredient names for the INCI nomencla-
ture system. It relied upon information supplied by chemical vendors and other
existing sources of chemical identification.
To prepare a cosmetic product’s ingredient listing, chemists should look to the
following sources to find the appropriate nomenclature:
1. US Code of Federal Regulations (21 CFR 701.30) for list of ingredients named
by the FDA
2. International Cosmetic Ingredient Dictionary for INCI and
Colour Index names
3. US Pharmacopeia (USP)
39
4. National Formulary (NF)

5. Food Chemicals Codex (FCC)
6. USAN and the USP Dictionary of Drug Names
Finally, if suitable nomenclature is not found in any of these sources, a techni-
cal name or description, or a name that is generally recognizable by consumers
may be employed.
Nomenclature Systems
Silicones: Not all cosmetic ingredients are based on fatty acid chemistry.
Silicon-based ingredients, common in personal-care products for lubrication, mois-
turization and conditioning, have their own special nomenclature. As an example,
the structure of dimethicone (Figure 3.1) would be hard to deduce from its INCI
name alone. Dimethicone (or dimethyl-polysiloxane) is a mixture of fully methy-
lated linear siloxane polymers end-blocked by trimethylsiloxy units. The industry
uses literally hundreds of other silicon derivatives based on this chemistry. These
include dimethicone copolyol (dimethicone with polyoxyethylene groups added
to improve water solubility) and cyclomethicone (cyclic dimethyl polysiloxane),
known for its lubricity and volatility.
Figure 3.1. CTFA Form TN
Ethanol: Alcohols are another cosmetic raw material with specialized nomen-
clature requirements. Chemists unfamiliar with the INCI system might presume
that ethanol—two simple carbon units and a hydroxyl group—would be one of
the easiest ingredients to name. Wrong! Because the ethanol employed in most
cosmetic products contains some form of denaturant to deter human consumption,
naming them requires specialization.
In fact, the International Cosmetic Ingredient Dictionary does not show “ethanol”
per se. Instead, it displays a list of “specially denatured alcohols” (SDA), each with
an abbreviation to specify the denaturant. Ethanol denatured with t-butyl alcohol
and sucrose octaacetate is SDA 40-A, but ethanol with methyl alcohol is SDA 3-A.
In all, the fifth edition of the dictionary lists 26 denatured ethyl alcohols. In the
European Union, “alcohol denat” refers to denatured ethanol using an additive
approved by the appropriate member states.
Colorants: INCI colorant nomenclature depends upon the regulatory status
of the subject material. Most synthetic pigments used in cosmetics are regulated in
the United States by the FDA. These, known as certified colors, have difficult and
unwieldy chemical names. Fortunately, INCI classification abbreviates colorants
according to their approved usage in either the FD&C (Food, Drug and Cosmetic),
40
D&C (Drug and Cosmetic) or Ext. D&C (External Drug and Cosmetic) certifica-
tion. Examples include FD&C blue no. 1 (for which common alternate names are
brilliant blue or food blue 2), D&C green no. 5 (alizarine cyanine green) and Ext.
D&C yellow no. 7 (naphthol yellow S).
In the EU, colorants are identified in the Colour Index (CI) by an internation-
ally recognized 5-digit code. The CI nomenclature is now being listed by CTFA as
an alternate INCI name. Thus, FD&C blue no. 1 is also CI 42090.
Some classes of colorant, not requiring special certification, are identified dif-
ferently. Two common examples are the iron oxides (such as cosmetic black and
cosmetic brown) and the ultramarine colors (ultramarine blue, pink and green).
Color-imparting cosmetics frequently use these insoluble pigments.
Basic dyes are primarily used as permanent or semipermanent hair colorants.
Examples include basic blue 9, also known as 3,7- bis (dimethylamino)phenothiazin-
5-ium chloride and basic brown 16, or [8-[(p-aminophenyl) azo]-7-hydroxy-2-
napthyl]trimethylammonium chloride.
Other ingredients: Though there appears to be an endless number of chemical
designations and abbreviations, the INCI system also uses many easily recogniz-
able names for natural and natural-derived ingredients. These include beeswax,
lanolin, menthol and a host of other animal-, vegetable- and mineral-derived
components.
The manner in which INCI names are assigned to so-called natural materials
depends upon their composition. Materials of biological origin, such as “hyaluronic
acid,” are named by specific terms once they have been isolated and purified.
When the exact components in a mixture can not be reasonably classified, as
with certain plant extracts, the source may be used to name the material. “Aloe
vera,” for example, identifies the material extracted from the plant of the same
name. Other noteworthy examples include keratin protein, vegetable gums, and
various mineral waxes. Such familiar terms ease the obvious difficulty of assigning
IUPAC names to materials that are mixtures of many compounds.
Fragrances are designated by the comparatively mundane and non-descriptive
qualifier “fragrance,” though they may be elaborate concoctions of exotic elements
like Siberian pine needles, whale musk and rose petal extract. No further chemical
identification is required. However, in circumstances where specific aroma chemi-
cals are cited on ingredient statements, the INCI nomenclature should be used.
For example, “chamomile” is the name given to the fragrance oil extracted from
the plant of the same name.
In a system this complex, there are bound to be cases that just don’t make
sense scientifically. What is the structural reason for assigning the names carbomer
or poloxamer to these common cosmetic thickeners? To confound matters, if an
ingredient is considered to be proprietary or a trade secret, its vendor can petition
the FDA to allow that material to be listed as simply “other ingredients” on label-
ing for the US market. In addition, if an incidental material is present that has no
function or effect on the formula, or if it is present at an insignificant level, it need
not be declared on the ingredient listing.
41
Water, perhaps the most common of all cosmetic ingredients, can only be
legally identified as “water.” Despite the efforts of many companies, misnomers
such as “deionized,” “distilled,” “glacier” and “fresh mountain stream” water are
not accepted terminology.
INCI Name Assignment Procedures

INCI names are assigned by The Personal Care Products Council, formerly
CTFA International Nomenclature Committee (INC), comprised of industry experts
that meet approximately quarterly. In order to have an INCI name assigned to an
ingredient, the supplier must submit data about the ingredient on CTFA Form
TN. This form, available atwww.ctfa-buyersguide.org, asks for such information as
chemical structure, Chemical Abstracts Service (CAS) number, and manufacturing
method. There is currently a fee of $200.00 to register a new product.
Because INCI names are assigned to ingredients based upon the written in-
formation provided by the ingredient’s supplier, it is the supplier’s responsibility to
ensure that the information submitted is complete and accurate.
Once Form TN is received by CTFA, a preliminary literature search is per-
formed on the ingredient, and the submitting firm is contacted for any deficiencies
in the application.
The Form TN is then reviewed at the next INC meeting. The INC either as-
signs an INCI name, or finds that additional information is still required about the
ingredient.
After the meeting, the submitter is informed officially by CTFA of the INC’s
decision.
Companies wishing to change an INCI name must send a written request to the
INC. Such requests must include supporting information, including the rationale
for the change, alternate nomenclature, information on the structure or composi-
tion of the material, and analytical data, if applicable.
Labeling with INCI Names

Some specific conventions for INCI names exist that must be observed when
ingredient labeling. Two of the most important are discussed below.
Solvents and diluents: Solvents and diluents in raw materials such as surfactants
and polymers are not identified as part of the INCI name. However, diluents and/
or solvents must be listed on the package label in their proper order of predomi-
nance with respect to all other ingredients in the formulation. Information on the
concentration of solvents and/or diluents contained in such raw materials must be
obtained from the supplier.
Incidental ingredients: Incidental ingredients contained in cosmetic raw
materials are not included in the INCI name. Incidental ingredients include an-
tioxidants, preservatives or processing aids that are present for a specific function
in a raw material, but are not intended to have a technical or functional effect in
the finished cosmetic product, and are present at insignificant levels in the finished
cosmetic product.
42
Additional Information
The CTFA has published additional information on the labeling requirements
for products marketed in the United States1 and on the regulatory status of colorants
in the United States and many other countries.2
INCI Information Sources

In the United States:
The Personal Care Products Council
1101 17th Street, N.W., Suite 300
Washington, DC 20036 USA
Phone: 202-331-1770
Fax: 202-331-1969
In the EU:
COLIPA, The European Cosmetic, Toiletry and Perfumery Association
Rue du Congrès 5-7
B-1000 Bruxelles
Belgium
Phone: 011-32-2-227-6610
Fax: 011-32-2-227-6627
Conclusion
The ability to provide timely, accurate, meaningful and consumer friendly
names for cosmetic products remains a challenge. Consumer friendly is a key
concept. One recent Internet article states consumers should avoid sodium ether
sulfate because it contains ether, which will put the user asleep. As long as this
type of “knowledge” is disseminated, we in our industry will all have the challenge
of explaining consumer confusion.
Published in February 2001 Cosmetics and Toiletries magazine.
References
1. CTFA International Color Handbook, Second Edition, The Cosmetic, Toiletry, and
Fragrance Association, Washington, DC: (1992)
2. CTFA International Regulatory Resource Manual, Fourth Edition, The Cosmetic,
Toiletry, and Fragrance Association, Washington, DC: (1995)
Chapter 4
INCI Names: International

Harmonization
This chapter discusses differences between INCI names in the
US Japan and the EU as well as some regulation differences.
key words: nomenclature, INCI, International Nomenclature

Cosmetic Ingredient, regulation, EU, labeling
I n Chapter 3 “Cosmetic Ingredient Nomenclature”, the FDA, the Personal Care

Product Council and the process of naming cosmetic ingredients was discussed.
This chapter focuses on the harmonization and exceptions that exist between the
United States, the European Union and Japan.
INCI (International Nomenclature Cosmetic Ingredient) names are the labeling
names that must be used on finished cosmetic product labels in the United States
(US), the countries of the European Union (EU) and many other countries. The
names are listed in the International Cosmetic Ingredient Dictionary and Handbook1
(the Dictionary), published biannually in the US. The Dictionary also contains
information on the chemistry of the INCI named ingredient, including chemical
structure, cosmetic function, chemical synonyms and regulatory information.
Differences between the US and the EU

For the most part, INCI names are the same in the US and the EU markets.
However, a few notable exceptions do exist. National laws and regulations dictate
these differences.
The types of ingredients most frequently affected are:
• Colorants;
• Botanicals;
• Denatured alcohol;
• EU trivial names;
• Fragrance and flavor.
The differences for each of these ingredient types are discussed below.
Colorants that are not hair dyes: Colorants (excluding hair dyes) approved for
use in the US are listed in Title 21 of the US Code of Federal Regulations, Parts
73, 74 and 82. The INCI names for these colorants are found in the Dictionary in
Section 3 under one of three headings: Color Additives—Batch Certified by the US
Food and Drug Administration; Color Additives—Exempt from Batch Certification
by the US Food and Drug Administration; Color Additives Lakes—Batch Certified
43
44
INCI Names: International Harmonization Beginning Cosmetic Chemistry
by the US Food and Drug Administration. Batch certification is the US Food and
Drug Administration’s (FDA) method of verifying that each individual batch of
organic color additives meets the standards and specifications found in Title 21 of
the US Code of Federal Regulations, Part 74. Colorants can be classified as either
organic or inorganic, depending on their chemistry. A “lake” is the insoluble form
of an organic colorant.
Table 4.1. Examples of abbreviated INCI names for batch certified colorants
INCI Name Unabbreviated FDA Batch certification name

Red 6 D&C Red No. 6
Ext. Violet 2 Ext. D&C Violet No. 2
Red 40 Lake FD&C Red No. 40 Aluminum Lake
The INCI names for US color additives that are subject to batch certification
are abbreviated labeling names. As such, the cosmetic product manufacturer may
choose to omit from the product label such terms as “FD&C” (Food, Drug and Cos-
metic), “D&C” (Drug and Cosmetic), “No.”(Number) and the laking agent. Table
4.1 shows examples of abbreviated INCI names for batch certified colorants.
Colorants approved for use in the EU may be found in Annex IV of the European
Commission Cosmetic Directive (Dir. 76/768/EEC—June 1991, with additional
Commission Directives).
With a few exceptions, colorants are listed in Annex IV by the Colour Index
(CI) numbers. The INCI labeling name for lakes and salts of EU colorants, not
otherwise prohibited in Annex II or regulated by Annex V (Dir. 76/768/EEC—June
1991), is the same CI number as the colorant found in Annex IV, without reference
to the laking agent or salt. These INCI names may be found in the Dictionary in
Section 3 under the heading Color Additives—Approved in the EU.
Industry has proposed that a dual declaration of colorants with both the US name
and the EU name be allowed on labels of cosmetic products intended for sale in
both the US and the EU markets. Examples of harmonized names are as follows:
Green 3 (CI 42053)
Ultramarines (CI 77007)
Although the FDA has indicated a willingness to accept this approach as an
interim step while it considers the question of harmonized ingredient labeling,
CTFA has been informed that certain EU member states have refused to accept
this approach.
Persons using harmonized INCI labeling names on products intended for both
the US and the EU markets must ensure that the colorants conform with regulatory
requirements for the US and the EU.
Colorants that are hair dyes: US laws and regulations do not require batch
certification of organic colorants used in hair dyes. There are certain labeling
45
requirements, however, for these so-called “coal-tar” dyes, a term relating to their
original source in the 19th century.
The INCI names for hair colorants in the US and EU are equivalent, and with
few exceptions are based on the chemical structure of the ingredient. For a simple
structure, the chemical name of the colorant is used. When the chemical structure
is very complex, a combination of letters and numbers may be assigned with the
prefix “HC”. In addition, the names of colorants as listed in the Colour Index may
be used. Examples of INCI names of hair colorants include:
HC Blue No. 4
Acid Red 14
2-Amino-5-Nitrophenol
These INCI names may be found in the Dictionary in Section 3 under the
heading Color Additives—Hair.
Botanicals: Cosmetic ingredients physically derived from plants are known as
botanicals. Generally, these ingredients have not undergone significant chemical
modification and include preparations such as extracts, juices, distillates, powders
and oils.
In the US, INCI names for botanicals include the Latin binomial (genus and
species names), the common name of the plant (if applicable), the plant part, and
the type of preparation; for example, Avena Sativa (Oat) Kernel Extract.
In the EU, the INCI names for botanicals currently list only the Latin binomial;
for example, Avena Sativa.
The harmonized INCI name for both markets in this case would simply be the
US INCI name, Avena Sativa (Oat) Kernel Extract.
It should be noted that at the time this chapter was written, a proposed update
to the EU inventory of cosmetic ingredients lists the plant parts and preparations
for the labeling of botanicals. Readers are advised to check the EU regulations for
the status of this proposal.
Denatured alcohol: Alcohol Denat. is the established INCI labeling name for
ethyl alcohol that is denatured (rendered non-potable) in accordance with national
regulations in the EU member states and in the US.
In the US, the names and formula specifications for specially denatured (SD)
alcohols are listed in the US Department of the Treasury Regulations under Title
27, US Code of Federal Regulations, Parts 20 and 21.
For the US market, labelers may use either the SD Alcohol name or Alcohol
Denat. on product labels. For products intended to be marketed in the US and
the EU, the name Alcohol Denat. should be used.
EU trivial names: In the EU, “trivial” names are listed in the EU Inventory
of Cosmetic Ingredients, and are included in the Dictionary as well. These names
represent common names that should be easily recognized by consumers in the EU,
where 11 different languages are spoken. The trivial names are based primarily on
designations taken from the European Pharmacopeia2. Examples of such labeling
names harmonized for the US and the EU markets are as follows:
46
Water (aqua)
Beeswax (Cera alba)
Sea Salt (Maris Sal)
Fragrance and Flavor: The terms Fragrance and Parfum are used as INCI
labeling names in the US and the EU, respectively. These names are used to iden-
tify that a product contains a material or combination of materials to produce or
to mask a particular odor.
The terms Flavor and Aroma are used as INCI labeling names in the US and
the EU, respectively. These names are used to identify that a product contains a
material or a combination of materials to produce or to mask a particular flavor.
International Harmonization
The information below is taken from the www.ctfa.org site and is designed to
provide basic information on the relationship between US regulations and those
experienced in other parts of the world. The harmonization of the regulations is
both complex and ever changing. This information is offered for basic understand-
ing however the reader is cautioned to review any changes and to get the advice
of an expert when attempting to act on this information.
The United States and European Union: Strictly Regulating Cosmetic Safety
The United States (US) and European Union (EU) both work to ensure the safety
of cosmetics for consumers through rigorous regulation. In the United States, the
cosmetics industry is regulated by the US Food and Drug Administration (FDA),
which has been granted broad regulatory authority under the federal Food, Drug
and Cosmetic Act, enacted in 1938. The 27 European Union Member States have
transposed the European Union Cosmetics Directive, enacted in 1976, into national
law. Each Member State has health authorities, which then regulate cosmetics
within their respective national boundaries according to the law.
In both the US and the EU, cosmetics manufacturers ensure product safety
prior to marketing, list all ingredients on the product label and comply with any
restrictions that are established for cosmetic ingredients and products. Any potential
risk from a product is assessed as part of its safety evaluation.
In the US, the Cosmetic Ingredient Review (CIR) Expert Panel conducts
independent safety reviews of ingredients as a part of the cosmetic safety process,
with the results published in the International Journal of Toxicology and on the CIR
website. The EU Scientific Committee on Consumer Products (SCCP) is responsible
for reviewing all special and active cosmetic ingredients and assessing conditions
for safe use. The results are subsequently published on the SCCP website.
In the US, cosmetic and personal care products companies work with leading
scientific and medical experts every day and invest millions of dollars in sophisticated
laboratory equipment and facilities to ensure cosmetic product safety. In addition to
this strong commitment to safety, federal law requires that every cosmetic product
be substantiated for safety before it goes to market. The FDA statistics confirm that
cosmetics are one of the safest product categories used by Americans today.
47
The US and EU have slightly different ways of regulating the cosmetic and
personal care industry, but both systems provide consumers with a high degree
of safety. Some argue that cosmetics are more strictly regulated in the EU, citing
recent actions taken in the EU to red flag or ban certain chemicals from use in
cosmetics. However, an examination of Annex II of the EU Cosmetics Directive, a
list of 1,300 banned ingredients, reveals that a large number of those chemicals are
not used and never have been used in cosmetics in the US or Europe. For example,
the EU list includes substances such as jet aircraft fuel, various petroleum refinery
byproducts and carbon monoxide.
Another difference between the EU and US systems of regulating cosmetics
is that the EU allows the marketing of cosmetic products with certain medicinal
effects, while the United States has required extra regulatory hurdles because
they are classified as drugs. Some of the substances include sunscreens, anti-caries
toothpaste and lip balms. Even though color additives are not classified as over-
the-counter (OTC) drug actives, they are also subject to more regulatory scrutiny
in the US than they are in Europe.
Cosmetic Regulation in Japan

The Japanese government regulates the cosmetics industry through its Ministry
of Health, Labor and Welfare according to the Pharmaceutical Affairs Law (Law
No. 145) established August 10, 1960. Japan has adopted a list of prohibited in-
gredients, a list of restricted ingredients, a positive list of UV filters and a positive
list of preservatives.
Other than these restrictions, the burden of ensuring product safety has been
shifted to cosmetic manufacturers. As such, any ingredient that can be shown to be
safe may be used in a cosmetic product. Until recently, a manufacturer or importer
of cosmetics was required to obtain a pre-market approval and license from the
Ministry of Health, Labor and Welfare. Since 2001, however, Japanese cosmetics
companies are required only to provide notification of the product’s brand prior to
manufacturing or importing.
Japan is an excellent example of a nation where costly pre-market registration
procedures were replaced with manufacturer responsibility for product safety and
with post-market surveillance (similar to the systems in the US and EU) without
compromising consumer safety.
Original: Japanese
Provisional Translation
Standards for Cosmetics
(Ministry of Health and Welfare Notification No.331 of 2000)
In accordance with the provisions of Article 42, Paragraph 2 of the Pharmaceu-

tical Affairs Law (Law No.145 of 1960), the Standards for Cosmetics are hereby
established as follows and shall be applied from April 1, 2001, and the Quality
Standards for Cosmetics (Ministry of Health and Welfare Notification No.321 of
August 1967) and the Japanese Standards for Cosmetic Ingredients (Ministry of
48
Health and Welfare Notification No.322 of August 1967) shall be abolished on

March 31, 2001; provided, however, that any medical drug ingredients which are
also cosmetic ingredients that have actually been approved pursuant to Article 14,
Paragraph 1 of the said law at the time of application of this notification or which
are also cosmetic ingredients listed in the Appendix of the Ministry of Health and
Welfare Notification No.15 of February 1961 (Re: Designation of Cosmetic In-
gredients that must be Approved for Each Item in Accordance with the Provisions
of Article 14, Paragraph 1 of the Pharmaceutical Affairs Law) may, regardless of
the provisions of section 2 below, be used as cosmetic ingredients only if used in
the amount for which the cosmetic ingredient was approved or the amount of the
cosmetic ingredient as listed in the said Appendix, as the case may be; and provided
further, that any cosmetics manufactured or imported on or before March 31, 2001,
shall be treated as though this notification were not established.
Standards for Cosmetics

General provisions
1. Ingredients of cosmetics, including any impurities contained therein, shall not
contain anything that may cause infection or that otherwise makes the use of
the cosmetics a potential health hazard.
2. Prohibition of inclusion of ingredients other than preservatives, UV absorbers
and tar colors
Cosmetics shall not contain any medical drug ingredients (excluding those
used only as additives and those listed in Appendix 4.2-1 through 4.4), or any
ingredients that do not meet the Standards for Biological Materials (Ministry
of Health, Labour and Welfare Notification No.210 of 2003), Class I Specified
Chemical Substances provided in the Law Concerning the Evaluation of Chemi-
cal Substances and Regulation of Their Manufacture, etc. Article 2, Paragraph
2 (Law No.117 of 1973), or Class II Specified Substances provided in the same
law Article 2, paragraph 3 or the materials that are determined by the Minister
of Health, Labour and Welfare and have property similar to these substances,
or any of the materials listed in Appendix 4.1.
3. Limitation on inclusion of ingredients other than preservatives, UV absorbers
and tar colors
If any of the materials listed in the section of ingredient names of Appendix 4.2
is incorporated in a cosmetic, the amount of such ingredient contained shall
be under the values in the column of maximum amount of ingredient per 100
g of the said Appendix.
4. Limitation on inclusion of preservatives, UV absorbers and tar colors
Any and all preservatives (meaning materials incorporated in cosmetics for the
purpose of inhibiting growth of microorganisms in such cosmetics) incorporated
in cosmetics shall be among those listed in Appendix 4.3.
Any and all UV absorbers (meaning materials that specifically absorb ultraviolet
rays and that re incorporated in cosmetics for the purpose of protecting skin
49
or hair from adverse effects of ultraviolet rays) incorporated in cosmetics shall

be among those listed in Appendix 4.4.
The provisions of Article 3 of the Ministerial Ordinance for the Designation
of Tar Colors That May Be Used in Medical Drugs, Etc. (Ministry of Health
and Welfare Ordinance No.30 of 1966) shall be applied mutatis mutandis to tar
colors incorporated in cosmetics; provided, however, that Red No.219 and Yel-
low No.204 may be incorporated only in cosmetics applied to hair and nails.
Appendix 4.1
1. 6-Acetoxy-2,4-dimethyl-m-dioxane
2. Antihistamines except those of aminoether type (such as diphenhydramine)
3. Hormones and those derivatives except estradiol, estrone and ethinylestradiol
4. Vinyl chloride monomer
5. Methylene chloride
6. Bismuth compounds other than bismuth oxychloride
7. Hydrogen peroxide
8. Cadmium compounds
9. Sodium perborate
10. Chloroform
11. Progrenolone acetate
12. Dichlorophene
13. Mercury and its compounds
14. Strontium compounds
15. Sulfamide and its derivatives
16. Selenium compounds
17. Nitrofuran type compounds
18. Hydroquinone monobenzylether
19. Halogenated salicylanilide
20. Vitamin L1 and Vitamin L2
21. Bithionol
22. Pilocalpine
23. Pyrogallol
24. Inorganic fluorine compounds
25. Pregnanediol
26. Local anesthetics such as procaine
27. Hexachlorophen
28. Boric acid
29. Formalin
30. Methyl alcohol
50
Appendix 4.2
1. The ingredients restricted in all types of cosmetics

Maximum amount of
Ingredient name ingredient per 100 g
Aluminum chlorhydroxy allantoinate 1.0 g
Cantharides tincture, ginger tincture or capsicum tincture 1.0 g as total
Phenyl salicylate 1.0 g
Polyoxyethylene laurylether (8-10E.O.) 2.0 g
2. The ingredients restricted according to types or intended purposes of cosmetics

Maximum amount of
Aerosol agents
Prohibited
Zirconium
Cosmetics to be washed away immediately after use such
as soap or shampoo 0.50 g
Thiram
Cosmetics other than those washed away immediately
after use such as soap or shampoo
Undecylenic acid monoethanolamide Prohibited
Thiram 0.30g
Zinc p-phenolsulfonate 2.0 g
2-(2-Hydroxy-5-methylphenyl) benzotriazole 7.0 g
Sodium lauroyl sarcosinate Prohibited
Cosmetics used in cephalic, mucosa part or the oral
cavity, and cosmetics used in other parts, containing
lower aliphatic monoalcohols (exclude those contain-
ing the said alcohols added to dissolve ingredients in 20000 IU as total
the said cosmetics)
Estradiol, estrone and ethinylestradiol
Cosmetics other than those used in cephalic, mucosa part
or the oral cavity, containing no lower aliphatic monoalco-
hols (include those containing the said alcohols added to 50000 IU as total
dissolve ingredients in the said cosmetics )
Estradiol, estrone and ethinylestradiol
Cosmetics used in only cephalic part
0.010 g
Aminoether type antihistamines
Cosmetics other than those used only in cephalic part
Prohibited
Aminoether type antihistamines
Toothpaste
0.50 g
Sodium lauroyl sarcosinate
51
Compounds to be used with the purpose of emulsifying 0.76 g ( limited not to

beewax or white beewax greater than 1/2 amount
Sodium pyroborate of beewax and white
beewax)
Compounds to be used for purposes other than
emulsifying beewax or white beewax Prohibited
Sodium pyroborate
3. The ingredients restricted according to types of cosmetics (*)

Maximum amount (g) of ingredient per 100 g
Cosmetics not Cosmetics
Cosmetics not used used for mucosa that may
for mucosa and to and not to be be used for
Ingredient name be washed away washed away mucosa
Thioctic acid 0.01 0.01
Ubidecarenone 0.03 0.03
(*)Blank indicates that it is prohibited to be used.
Appendix 4.3

Maximum amount (g) of
Benzoic acid 0.2
Benzoate 1.0 as total
Alkyldiaminoethylglycine hydrochloride 0.20
Photosensitizing dyes 0.0020 as total
Chlorcresol 0.50
Chlorobutanol 0.10
Salicylic acid 0.20
Salicylate 1.0 as total
Sorbic acid and sorbate 0.50 as total
Dehydroacetic acid and dehydroacetate 0.50 as total
Trichlorohydroxydiphenylether (Triclosan) 0.10
p-Oxybenzoic acid esters and their sodium salts 1.0 as total
Phenoxyethanol 1.0
Phenol 0.10
Sodium lauryldiaminoethylglycine 0.030
Resorcin 0.10
52
Appendix 4.3 continued
2. The ingredients restricted according to types of cosmetics (*1)

Maximum amount (g) of ingredient per 100g
Cosmetics
Cosmetics not used Cosmetics
not used for for mucosa that
mucosa and and not to may be
to be washed be washed used for
Ingredient name away away mucosa
Zinc, ammonia and silver substituted
1.0 1.0
zeolite(*4)
Pantothenyl ethylether benzoate ** 0.30 0.30
Isopropylmethylphenol ** 0.10 0.10
Cetylpyridinium chloride 5.0 1.0 0.010
Benzalkonium chloride ** 0.050 0.050
Benzethonium chloride 0.50 0.20
Chlorhexidine hydrochloride 0.10 0.10 0.0010
o-Phenyl phenol ** 0.30 0.30
Sodium o-phenylphenate 0.15 0.15
Silver-Copper Zeolite(*5) 0.5 0.5
Chlorhexidine gluconate ** 0.050 0.050
Cresol 0.010 0.010
Chloramine T 0.30 0.10
Chlorxylenol 0.30 0.20 0.20
Chlorphenesin 0.30 0.30
Chlorhexidine 0.10 0.050 0.050
1,3-Dimethylol-5, 5-dimethylhydantoin 0.30
Alkylisoquinolinium bromide ** 0.050 0.050
Thianthol 0.80 0.80
Thymol 0.050 0.050 **(*2)
Trichlorocarbanilide ** 0.30 0.30
p-Chlorphenol 0.25 0.25
Halocarban ** 0.30 0.30
Hinokitiol ** 0.10 0.050
Zinc pyrithione 0.10 0.010 0.010
Iodopropynyl butylcarbamate(*6) 0.02 0.02 0.02
Polyaminopropyl biguanide 0.1 0.1 0.1
Methyl isothiazolinone 0.01 0.01
53
Methylchloro isothiazolinone and

0.10
methyl isothiazolinone solution(*3)
N,N”-Methylenebis[N’-(3-hydroxym-
0.30
ethyl-2,5-dioxo-4-imidazolidinyl)urea]
p-Dimethylaminostyryl heptyl methyl
0.0015 0.0015
thiazolium iodide
(*1) Blank indicates that it is prohibited to be used, and ** indicates that there is no upper limit for the
amount of ingredient.
(*2) It can be contained in cosmetics used for mucosa and only for oral cavity.
(*3) It indicates the aqueous solution containing 1.0–1.3% of 5-chloro-2-methyl-4- isothiazolin-3-one
and 0.30–0.42% of 2-methyl-4-isothiazolin-3-one.
(*4) It indicates the compound containing 0.2–4.0% as silver and 5.0–15.0% as zinc when it is exposed
to strong heat.
(*5) It indicates the compound containing 2.7–3.7% as silver and 4.9–6.3% as copper when it is
exposed to strong heat.
(*6) It is prohibited to be contained in aerosol agents.
Appendix 4.4

Maximum amount (g) of
Ingredient name ingredient per 100g
Homomenthyl salicylate 10
2-Cyano-3,3-diphenyl prop-2-enoic acid 2-ethylhexyl ester
10
(octocrylene)
Glyceryl mono-2-ethylhexanoate di-p-methoxycinnamate 10
p-Aminobenzoic acid and its esters 4.0 as total
4-tert-Butyl-4’-methoxy dibenzoylmethane 10
2. The ingredients restricted according to types of cosmetics (*1)

Cosmetics
Cosmetics not used
not used for for mucosa Cosmetics
mucosa and and not to that may
to be washed be washed be used for
4- (2-β-glucopyranosiloxy)
5.0 5.0
propoxy-2-hydroxybenzophenone
Octyl salicylate 10 10 5.0
Methyl-2, 5-diisopropylcinnamate 10 10
2-[4-(diethylamino)-2-
hydroxybenzyl] benzoic acid 10.0 10.0
hexylester
54
Appendix 4.4 continued

Cosmetics
Cosmetics not used
not used for for mucosa Cosmetics
mucosa and and not to that may
to be washed be washed be used for
Cinoxate ** 5.0 5.0
Dihydroxydimethoxybenzophenone 10 10
Sodium dihydroxydimethoxybenzo-
10 10
phenone disulfonate
Dihydroxybenzophenone 10 10
Dimethicodiethyl-benzal malonate 10.0 10.0 10.0
1- (3, 4-dimethoxyphenyl)-4,
7.0 7.0
4-dimethyl-1, 3-pentanedione
Dimethoxybenzylidenedioxo-imida-
3.0 3.0
zolidine 2-ethylhexyl propionate
Tetrahydroxybenzophenone 10 10 0.050
Terephthalylidene dicamphor
10 10
sulfonic acid
2,4,6-Tris [4-(2-ethylhexyloxycarbo-
5.0 5.0
nyl) anilino] -1,3,5-triazine
Methylbis(trimethylsiloxy)silyl iso-
7.5 7.5 2.5
pentyl trimethoxycinnamonate
Drometrizole trisiloxane 15.0 15.0
Amyl p-dimethylaminobenzoate 10 10
2-Ethylhexyl
10 10 7.0
p-dimethylaminobenzoate
Isopropyl p-methoxycinnamate
and diisopropyl cinnamate ester 10 10
mixture(*2)
2-Ethylhexyl p-methoxycinnamate 20 20 8.0
2,4-Bis-[{4-(2-ethylhexyloxy)-
2-hydroxy}-phenyl]-6- 3.0 3.0
(4-methoxyphenyl)-1,3,5-triazine
2-Hydroxy-4-
** 5.0 5.0
methoxybenzophenone
Hydroxymethoxybenzophenone
10(*3) 10(*3) 0.10(*3)
sulfonate and its trihydrate
55
Sodium
hydroxymethoxybenzophenone 10 10 1.0
sulfonate
Phenylbenzimidazole sulfonic acid 3.0 3.0
Ferulic acid 10 10
2,2’-methylenebis(6-(2H-
benzotriazole-2-yl)-4-(1,1,3, 10.0 10.0
3-tetramethylbutyl)phenol
(*1) Blank indicates that it is prohibited to be used, and ** indicates that there is no upper limit for the
amount of ingredient.
(*2) It indicates the compound containing 72.0–79.0% of isopropyl p-methoxycinnamate, 15.0–21.0% of
ethyl 2,4-diisopropyl cinnamate and 3.0 - 9.0% of methyl 2,4-diisopropyl cinnamate.
(*3) It is calculated as the total amount of hydroxymethoxybenzophenone sulfonate.
Published February 2001 Cosmetics and Toiletries magazine.
References
1. J
A Wenninger, RC Canterbery and GN McEwen Jr, eds, International Cosmetic
Ingredient Dictionary and Handbook, Seventh Edition The Cosmetic, Toiletry, and
Fragrance Association, Washington, DC (2000)
2. E
uropean Pharmacopeia, 2nd ed, prepared by the Council of Europe, Sainte-Ruffine:
Maissonneure (1983)
Chapter 5
Material Safety Data

Sheets
Usefulness to the cosmetic chemist.
key words: safety information, regulatory, MSDS
A s a cosmetic chemist you deal with dozens (if not hundreds or thousands) of
chemicals that are potentially hazardous. Therefore, you should know how to
find information to help ensure the safe handling of such materials. In the United
States, the document known as the Material Safety Data Sheet (MSDS) is an im-
portant information source. MSDSs must be made available to employees whose
work requires handling of chemical raw materials and finished products.
An MSDS, as defined in the US Code of Federal Regulations1, seeks “…to en-
sure that the hazards of all chemicals produced or imported are evaluated, and the
information concerning their hazards is transmitted to employers and employees.”
Practically speaking, this means that an MSDS should communicate basic safety
information to individuals who might come in contact with the material as a result
of their occupations. Federal law establishes the required details and specifies the
appropriate procedures.
Federal law, specifically Section 18 of the Williams-Steiger Occupational Safety
and Health Act of 1970, requires that suppliers of chemical raw materials and
finished products make an MSDS available to any worker(s) who might come in
contact with their products1. This statute applies equally for samples provided to
formulating chemists for evaluation and for production quantities. Since certain
finished products may contain potentially hazardous materials, manufacturers of
such products are also required to make MSDSs available to individuals who may
be exposed to these products in the workplace.
Individual states can also petition the federal government, under the auspices
of the Occupational Safety and Hazards Administration (OSHA) regarding accep-
tance/implementation of their own regulations. If the state requirements do not
meet federal standards, state law will be pre-empted by federal law. OSHA enforces
these regulations for the federal government. At the state level, each individual
state’s Department of Labor is responsible.
One of the primary purposes of an MSDS is to protect employees who come
in contact with potentially dangerous materials. For this protection to be effective,
employees must know where MSDSs are stored. They must also know how to use
them and have access to this information in the work area. Because these safety
57
58
Material Safety Data Sheets Beginning Cosmetic Chemistry
precautions apply equally to all employees who deal with chemicals, MSDSs must
be available to both compounding and production personnel in addition to R&D
scientists. As we will discuss later, MSDSs provide basic information that can be
used in a crisis to help minimize risks resulting from chemical exposure.
Beyond the immediate workplace, any employees who come in contact with
materials that are regulated by MSDSs in the course of their job are entitled to
receive an MSDS upon request. For example, a truck driver who transports such
materials, or finished products made with these materials, has a right to request
material safety information.
Most manufacturers have made MSDSs for all of their products available to
anyone who searches their sites on the Internet. This posting makes it convenient
for people to have access and also limits the liability of producers who might be
accused of being too secretive with safety information.
As a cosmetic chemist, you should be familiar with the basic elements of a typi-
cal MSDS for two reasons: for your own safety and because you might be required
to prepare such a document. The following discussion provides a brief overview of
the critical sections and subsections of a typical form.
Critical Sections of an MSDS

Product and company identification: Typically, the first section identifies the
company supplying the material in question. It also provides an emergency contact
telephone number. The chemical itself may be identified in a variety of ways: trade
name, chemical family, INCI name, CAS number, and RTECS number. Additional
details about the material’s composition can also be supplied, including information
related to components of the material (if it is a compound), percentage of active
ingredients and contaminants.
Specific data about the physical and chemical properties of the material may be
expressed, as well: molecular formula, boiling and freezing points, vapor pressure,
specific gravity, and solvency.
Hazards identification: This section provides information regarding known
health effects of the material, such as whether or not it is considered to be car-
cinogenic. Since the risk of handling any given chemical differs with the degree
of exposure, the MSDS relates the known hazards at specific levels of exposure.
These exposure limits may be defined as concentration of the material in the air,
and are expressed as PEL (Permissible Exposure Limit) in OSHA standards and
as TLV (Threshold Limit Value) in ACGIH standards (American Conference of
Governmental Industrial Hygienists). Similarly, the toxicological data may be
expressed in terms of LD50 (the dosage required to kill 50% of a population of
laboratory animals). Other ratings for health and fire safety—such as CERCLA
and NFPA—may be included, as well.
First aid measures: This section offers counteractive measures to take in the
event of overexposure. For example, the MSDS may state that vomiting should
be induced in the case of ingestion. This section should also detail the routes of
entry that present a hazard (i.e., how the product may enter the body—inhalation,
skin contact, eye contact, or oral ingestion). While the information provided in
59
an MSDS is not intended to take the place of complete toxicological data, it does
provide basic information to assist in reacting to an emergency.
Regulatory Acronym
PCPC—Personal Care Products Council (formerly Cosmetic, Toiletry and
Fragrance Association or CTFA)
CAS—Chemical Abstracts Service
INCI—International Nomenclature Cosmetic Ingredient
RTECS—Registry of Toxic Effects of Chemical Substances
PEL—Permissible Exposure Limit
TLV—Threshold Limit Value
ACGIH—American Conference of Governmental Industrial Hygienists
CERCLA—Comprehensive Environmental Response, Compensation,
and Liability Act
NFPA—National Fire Protection Association
DOT—Department of Transportation
SARA—Search and Rescue Aid
TSCA—Toxic Substances Control Act
CFR—Code of Federal Regulations
OSHA—Occupational Safety and Health Act or Administration
Fire and explosion data: This section informs handlers of appropriate fire-
fighting measures. Flash point, auto-ignition temperature and preferred extinguish-
ing media (water, foam, carbon dioxide) can be included. The intent is to provide
enough information for fire fighters to assess the potential danger in a fire involving
the material, and to choose the best methods for controlling the fire.
Reactivity: This section is dedicated to the product’s reactivity comments on
the general stability and chemical reactivity of the material (e.g., if it is a powerful
reducing or oxidizing agent). It also lists hazardous decomposition and polymeriza-
tion products. This information may also be useful to fire fighters, and may help
you avoid hazardous mixtures of materials in your laboratory.
Accidental release measures: This section gives appropriate responses to a
chemical spill. Special precautions may be indicated, such as gloves and protective
goggles. If special respiratory equipment is required (e.g., mask or self-contained
breathing apparatus), this information will be disclosed, as well. Spill precautions
detail what to do to clean up spilled material safely, including environmentally
responsible disposal methods. Therefore, this section may include some form of
environmental impact rating for the material, such as aquatic toxicity, biodegrad-
ability, or other ecological data. At the very least, the MSDS will typically include a
statement that the user must comply with federal, state and local chemical disposal
regulations.
Transportation information: Transportation data may be required if US
Federal Department of Transportation (DOT) regulations affect how the product
is shipped.
60
Material Safety Data Sheets Beginning Cosmetic Chemistry
Regulatory information: Regulatory data, based on TSCA (Toxic Substances

Control Act), CERCLA, SARA (Search and Rescue Aid) and OSHA references,
may also apply.
International Requirements
While the information above is sufficient for the United States, it is important
to note some of the variations found around the world. The following is a brief
summary.
In 1988, Canada implemented a program called the Workplace Hazardous Mate-
rials Information System (WHMIS). It is controlled by Health Canada and features
standardized hazard symbols to quickly communicate safety information.
In the EU, compounds are required to be identified with Risk and Safety State-
ments. They have created a standard list of R-statements and S-statements which
are numerically coded and can be cross referenced. For example, if a material is
labeled with R: 44, it corresponds to the risk statement R44: Risk of explosion if
heated under confinement. Each label must contain these R/S statements.
Germany requires the extra inclusion of a classification of the water hazard of
a material. For example, WGK nwg is used for non-water polluting substances.
WGK 3 is for highly water polluting substances.
Preparing an MSDS
As a cosmetic formulator, you should know the types of information you will
need to prepare an MSDS. Although an MSDS does not have to disclose your
entire formulation, it must inform the user of known potential dangers. Certainly,
cosmetic products are designed to be safe for use by the general public; but, in
certain situations, product misuse may lead to hazardous conditions. For example,
while soaps, shampoos, hair conditioners and various types of makeup are relatively
innocuous, ingestion may cause health problems. Other products, such as relax-
ers, permanent waves and hairsprays, contain ingredients that may be caustic or
flammable. These considerations must be dealt with when evaluating the potential
hazards of your product.
Of course, since finished products are generally mixtures of many materials,
synergistic effects between two or more chemicals may enhance the toxicity or
other hazards. Therefore, your products should be evaluated as a whole as well as
by the hazards of the “most dangerous” ingredient. To this end, testing of the final
formula may be necessary.
For example, the precise mixture of alcohol, water and propellant will deter-
mine the flammability of an aerosol product. Therefore, flashpoint testing may
be required to determine its exact flammability, for storage and transport safety.
Other products, such as creams and lotions (which are complex mixtures of sur-
factants, oils, preservatives and fragrance), may require toxicity or irritation testing
to definitively determine their potential hazards. Although these factors should be
considered when deciding what testing to perform when preparing an MSDS, you
should always seek input from your management. Similar considerations apply if
61
you are a cosmetic chemist preparing an MSDS for a chemical produced by a raw
material supplier.
Conclusion
Whether you are preparing an MSDS for one of your own products or working
with MSDSs from chemical suppliers, a working knowledge of the information
contained within these documents is imperative. Now that you understand what
an MSDS is, you know why it is so important to chemists and other employees who
come in contact with raw materials and finished products.
Acknowledgement: The authors would like to thank Kathy Papademas of Alberto-Culver for her
assistance in researching this article.
Published in 1994 Cosmetics & Toiletries magazine.
References
1. Code of Federal Regulations, Title 29—Labor, Chapter XVII—OSHA, Dept of Labor
(Jan 2007)
Chapter 6
Building Effective Supplier

Relationships
Suppliers are your industry partners and are there to serve you
and to help you grow your business and theirs.
key words: vendors, suppliers, business relationships,

raw materials, samples
C osmetic scientists must be skilled in many areas related to product develop-

ment including formulation, claims support, packaging, process engineering
and regulatory issues. We have previously discussed the role of the chemist in the
cosmetic industry1. But another member of the cosmetic community must possess
equally diverse talents: the supplier.
Suppliers, or vendors, are responsible for providing the goods, services and
equipment used by cosmetic scientists to develop and produce new products.
These include chemical raw materials, fragrances, specialty chemicals, testing
services, analytical instrumentation, and mixing and processing equipment. Sup-
pliers’ staff includes the sales representatives who deal directly with finished goods
manufacturers, as well as other individuals who handle marketing, internal sales
and technical support functions.
It is important that the chemist understand the role of suppliers in order to
take advantage of this important resource. This chapter describes the interaction
between suppliers and cosmetic scientists.
The Role of the Supplier

A cosmetic scientist working for a finished goods manufacturer deals with sales
representatives from a variety of companies. These representatives are responsible
for ensuring that you, the customer, can order and receive the goods and services
offered by their company.
These goods and services include chemical raw materials (such as surfactants
and fragrances); other valuable commodities such as packaging, manufacturing and
filling equipment; and testing services. Suppliers assist their customers by fulfilling
requests for raw material samples, test data and various forms of technical support
including financial and business information.
63
64
Building Effective Supplier Relationships Beginning Cosmetic Chemistry
The Vendor View

Insights on how to deal with suppliers from their point of view was provided
for this chapter by Michael Mosquera of HallCrest Chemical.
1. Keep an open mind
Often the philosophies and attitudes of companies convey or imply that they
are experts in the field of product development and that no vendor can possibly
know more about formulation than they do. In fact, some vendor companies can be
larger and have more technology and resources available to them than the finished
goods companies. It is important not to let the Not Invented Here (NIH) attitude
preclude the cosmetic chemist from having an open mind and willingness to hear
about products, ideas and technologies that a vendor may have to offer.
2. Vendor recognition
Most cosmetic chemists will come to know the names and reputations of the
large and well known vendors whether it is through magazine ads, trade shows,
ongoing business or through entertainment venues. Therefore, the call for an ap-
pointment from an “unknown vendor” may be dismissed because their name isn’t
known. This call could be an opportunity for the cosmetic chemist to discover a
new product or raw material that could be beneficial not only for his or her project
but could be of interest to others within the company.
3. Looking outside the box
Another way for the cosmetic chemist to use the services of the vendor is to
perhaps ask for literature or information about products or technologies that the
vendors may sell into other markets or industries that could be adapted for the
cosmetic or personal care industries. Many of the large vendors have specialty
products, which they offer to the pharmaceutical or food industries that would be
safe and effective for a topical application. It doesn’t hurt to ask.
4. Joint research programs
Many successful new products have been developed as a result of a partner-
ship between a cosmetic company who had an idea or concept and a vendor who
had the technology, equipment or raw materials that helped make the concept a
reality. If you find a potential vendor partner for those special projects, it may be
beneficial to discuss this with your management.
5. Vendor contacts
The cosmetic chemists should look to develop their “social” science skills as
well. The “face to face” meeting with the vendor is the best way to ascertain the
potential of a supplier’s products and capabilities. Just asking to have them send
their brochure and literature will not always give you the real story about the
vendor, and you miss out on key information that could be useful for current or
future projects.
6. So many vendors, so little time
Good time management is essential in meeting your product development as-
signments. The same can be said for allocating time with vendors. Schedule your
vendor appointments to allow yourself enough time to spend with each one and
65
complete your daily work tasks. If you cannot keep the appointment, a telephone
call, e-mail or fax would be most welcome by the vendor who may be traveling
great distances to meet with you.
7. Vendor network
Vendor network footnote

Establishing your own network of vendors who you trust and consider experts in a particular area can
be a very important resource for the cosmetic chemist. For example: suppliers who have technical
knowledge and expertise in materials such as preservatives, surfactants, fragrances, silicones or
botanical extracts could be called upon when needed.
Depending on the size of your business, you may have a dedicated representative
from the suppliers you buy from or you may deal with a distributor. A distributor
is a smaller, independent company that provides representation in geographical
regions or to market segments where the larger suppliers may not have an adequate
presence. Distributors usually sell a broad range of products from several different
companies in areas where those companies choose not to have full-time represen-
tatives. For lists of suppliers and their distributors, please refer to the suggested
reading list at the end of this chapter.
The Sales Call

The primary contact between a chemist and a supplier occurs during personal
visits. In these meetings, the suppliers usually use the opportunity to introduce their
company and all of the technologies represented. Subsequent meetings generally
focus on providing information, which encourages use of their materials.
During these meetings, suppliers introduce new raw materials or technologies
that can lead to novel or improved products. These meetings can also spark ideas for
significant cost-saving projects, new claims or interesting product demonstrations.
Additionally, the supplier should be able to offer solutions to technical problems
the chemist might be having with formula stability or scale-up. For chemists, these
meetings should be used as a time to think creatively about how to incorporate the
materials that the supplier is offering.
Exploring a New Ingredient

Because suppliers would like chemists to use their materials, they are often
willing to provide free samples. Samples are given away with the expectation that
your company will ultimately buy their materials in large quantities. Depending on
the cost of the raw material, samples ranging from a few grams to a quart or more
may be offered free, or for only a small fee.
Of course, in some cases, such as when a consumer test is planned, a larger
sample is needed to test the raw material in your new formula. You may not get
that amount for free, but your supplier may be willing to negotiate a reduced cost
on the test ingredient to facilitate your product development. Remember, if the
product works and goes into full scale manufacture, your supplier will be selling
you a lot more of the new ingredient.
66
Suppliers will also give suggestions on use levels, processing tips and performance
expectations. The chemist’s job is to evaluate these suggestions so he or she can use
the best level of each ingredient to optimize desired product characteristics while
minimizing cost and other negative characteristics. For example, a compound may
provide excellent feel in a skin lotion but, when used in excessive amounts, lead
to formula instability.
The primary reason to get a sample of a new raw material is to test it in a for-
mula and see whether it actually does offer you cost, claim, manufacture and/or
quality improvements. The new material may improve a product’s performance.
For example, a novel surfactant could improve the foam quality or reduce irritation
of a bodywash product. The material may also provide a cost savings, as certain
ingredients work synergistically with others. If less of both can be used to achieve
the same results, that reduces the total formula costs.
New ingredients can solve stability problems in formulas, such as unwanted
color changes or emulsion instabilities. Some suppliers sell blends that can both
reduce overall formula costs and decrease production time. Some new ingredients
enable novel marketing claims to be made about a formula.
If chemists do not have the chance to try a supplier’s products, the ingredients
will have no chance to be used in a formulation. For this reason, salespeople strive
to give out samples. Unfortunately, not all raw materials have the same value to
all chemists. If a chemist is not diligent, he or she can end up with hundreds of
samples of raw materials that are never evaluated in formulations.
Sample Requests
When making a sample request, therefore, do so with a good idea of how the
material will be used. For example, if a supplier presents a material that could be
a good hair conditioning ingredient, keep notes. A benefit of taking notes is that
they provide your lab with a reminder of why a sample was requested in the first
place. Samples usually take a few days to arrive; an idea that came up during the
sales meeting with your supplier is often forgotten before it can be tested. Without
proper records related to who sent the sample and why it was requested, you could
end up with countless jars of material and no idea what to do with them.
Avoid getting samples just for the sake of getting samples or just to please a
salesperson. Excessive samples can start to clutter a lab and cause real problems
in disposal because some ingredients require special waste disposal methods. Too
many samples on hand also create problems for the chemists responsible for their
evaluation.
Evaluating a Sample
A chemist should have a system set up for evaluation of new material. True
evaluation requires comparison between the formula without the ingredient (control)
and the formula with the ingredient. One of the most thorough ways to evaluate a
material is by first creating a blank formula with defined characteristics.
For instance, if you are developing a shampoo, you should have a blank formula
ready for which you have measured as many of its characteristics that you can.
67
This list would include performance characteristics (like foam height and quality,
conditioning ability and combability) and physical characteristics (like viscosity
profile, pH, appearance and stability).
A great way to save yourself some time is to ask for the supplier to provide you
samples of a formulated product with and without their raw material. Suppliers typi-
cally have tech services labs that can create finished formulas. Your first evaluation
of the new ingredient can then be done without having to make formulas yourself.
If you see impressive enough results, then you continue with your development.
If not, you talk to the supplier and try something else.
Once the initial parameters are established, you can then add the new material
and determine exactly how it affects your formula. If a supplier presents a material
that is supposed to improve the foam height of a shampoo, you can test for yourself
to see if it actually does.
While it is always fun to try out new, experimental materials, certain things
must be kept in mind. Newly introduced raw materials may be more difficult for a
supplier to produce, which they—and you—could discover at scale-up. Addition-
ally, new materials can significantly increase the cost of your formula. The chemist
must strike a balance between performance improvement and cost-effectiveness.
Finally, new materials may require extra testing, such as inhalation or other safety
testing. This added expense is sometimes prohibitive to the use of a new material
in a product.
Technical Support
Suppliers provide valuable technical assistance by providing chemists with start-
ing formulations. By providing a place for the formulator to begin, these starting
formulations may help shorten the time required for new product development.
Many suppliers have detailed formularies that demonstrate how to use their
raw materials. However, the formulator should keep in mind that these starting
formulations are, as the name implies, starting points; they should not be treated
as finished products. While suppliers’ formulas can be useful, they may require
significant work before they can be produced for sale. At the very least, it is im-
portant for the formulator to understand which suppliers have the capability to
provide starting formulations.
Suppliers may even be able to provide prototypes of their starting formulations
for your evaluation. This service is important because the average scientist may have
contact with a dozen or more different vendors, each of whom may sell dozens of
different raw materials. It would be physically impossible for you to create a trial
formulation for every single raw material with which you come in contact. And if you
can’t evaluate a raw material in your formula, you probably will not purchase it.
Therefore, it is to the suppliers’ advantage to provide you with prepared samples
and concepts that use their ingredients. We suggest that you ask your vendors if
they can supply a prototype that demonstrates the chemicals they are promoting.
Even though the supplier’s formula may be a “rough draft,” it is easier for you to
evaluate someone else’s prototype than it is to take the time to create the product
from scratch.
68
Raw Material Specifications

Another important function of raw material suppliers is to assist scientists
with technical information that supports their product development process. At
minimum, this information includes the data presented on the Material Safety
Data Sheet (MSDS), the specification sheet and the Certificate of Analysis (also
known as the “C of A”). These documents provide the basic information required
for any ingredient.
Suppliers will have additional information regarding the composition of their
raw materials. Many subtle variations may occur in the manufacture of chemicals,
such as changes in feedstock or in production processes. Cosmetic manufacturers
understand these variations, and it is important that the raw material suppliers
convey the necessary information to the product development chemists so relevant
specifications can be developed. It may even be helpful for the suppliers to have
the product development team visit their production facility to see firsthand how
the ingredients under discussion are made.
Technical Testing
Suppliers assist in the product development processing by providing testing
services. For example, raw material suppliers can evaluate the stability or efficacy
of your formulations and fragrance suppliers can evaluate the consumer appeal
of your products. Suppliers that sell analytical instruments or processing equip-
ment may be willing to loan or lease their apparatus to you for testing before you
purchase it.
With technical service programs, suppliers may be able to conduct claims-
support testing for you as you start working on a new product. For example, they
may evaluate how well their ingredient moisturizes skin or conditions the hair. This
type of data is useful to cosmetic chemists because it provides direction for future
testing. You can ensure bias-free results during the testing by coding the samples
to keep their identity a secret. The supplier can then test the samples without
having an unconscious preference for the sample containing their material. They
may conduct this testing in their own technical applications laboratory or they may
contract with an outside service. In a few rare cases, you may solely rely on the
supplier’s data for your claim support, but in most situations the final product has
changed from your prototype samples.
It is desirable for the finished product manufacturer to conduct its own testing.
The need to retest arises because the supplier’s testing is commonly done in a generic
base formula that may differ in function from the one you are developing. In any
event, it is an unusual benefit for the formulator to have testing done at little or no
charge. The chemists should consult with the supplier to understand the limits of
their abilities and how much testing they are willing to fund.
Trend Monitoring and Idea Generation

Suppliers are a very good source of new ideas. Fragrance vendors constantly
monitor industry trends to insure their fragrances are consistent with consumer
desires and help inspire new product concepts. It is common practice for cosmetic
69
companies to invite fragrance vendors to present their trend data to chemists,

marketers and others involved in the new product development process.
Chemical suppliers are very skilled at identifying new claims and functions for
products because they understand the properties of their raw materials better than
anyone else. Many raw material suppliers do their own claims testing to determine
functions and performance of the raw materials. For example, protein suppliers may
identify that a certain type of protein is more substantive to hair and skin; they may
also have ideas on how to use this technology to support superior benefit claims.
With the push for more and more innovation, suppliers are particularly impor-
tant to partner with in the development of their new raw materials. If you share
information with them about what your consumer is seeking, you can help drive
their raw material development. This cooperation may ultimately lead to a product
that benefits both parties.
The salespeople who visit you also visit other companies in the industry. They
are often the first to know whether a competitor company is being bought or
sold. They pick up on the concerns of their customers and the trends in research.
They become experts at knowing about solving problems. If appropriate, they will
share possible solutions to your problems that other companies have employed.
Finally, suppliers also keep an eye on the comings and goings of people around
the industry. They can be a good source of information related to job openings
and job candidates.
Use your suppliers’ wealth of knowledge to generate new ideas for products
and claims.
The Supplier and the Purchasing Department

While suppliers work with the chemists at a company, they will also be involved
with the purchasing department. Typically, a salesperson will first present a new
material to a chemist. Once it is used in a formula, the purchasing department
works out the price details. Often the suppliers are reluctant to provide chemists
with exact prices because they are negotiated with the purchasing department and
prices can change depending on yearly volumes. Chemists should, however, have
a rough idea of how much an ingredient will cost because relative cost will affect
the amount used in a formula. Keep in mind, however, that the price the supplier
initially provides is not typically the price your company will pay when full-scale
production proceeds.
Potential Issues
Confidentiality: As in all industries, ideas for new products and claims in the
cosmetic industry are well-kept secrets. If information on a new idea leaks out to
a competitor, your company may lose a critical competitive edge. It is critical that
the information exchanged between the finished goods manufacturers and their
suppliers be kept confidential. To insure that this kind of information remains pro-
prietary, legal documents known as confidentiality agreements (also called secrecy
or nondisclosure agreements) are used. The confidentiality agreement protects
both you and your suppliers. We encourage you to consult with your management
regarding your company’s policy toward secrecy agreements.
70
Entertainment: One of the nice fringe benefits of the cosmetic industry is

the entertainment you may receive from your suppliers. Suppliers may offer to
take you to lunch or dinner to give you more time to discuss business. This outing
provides a more relaxed atmosphere for exchanging information and ideas. Other
social events (such as dinners and golf outings) are commonly attended by chemists
and other scientists in this industry. While it is not wrong to engage in this kind of
extracurricular contact, many companies have strict regulations about how much
contact their employees may have with suppliers. As always, discuss this with your
management and be familiar with your company policies. Be careful that you are
not violating any policies your company may have regarding accepting entertain-
ment from suppliers.
Building Effective Working Relationships

In closing, we urge you to use a little common sense and decency when dealing
with your suppliers. These people are there to serve you and to help you grow your
business and theirs. You will find that your working relationships are much more
effective when you deal with suppliers courteously and professionally. Suppliers are
your business partners and should be treated accordingly. If you receive a phone call
or a note from them, return their message at your earliest convenience. It makes
their job much easier and helps establish goodwill.
Similarly, use their resources wisely. If you find a supplier that is willing to do
development work or testing for you, only use their services when it has a good
chance of building business for both of you. If you squander too much of the sup-
pliers’ resources on insignificant projects, they may be less likely to work closely
with you in the future. As a product development scientist you should value the
role of the supplier in the cosmetic industry.
Acknowledgement: The authors thank Michael Mosquera of HallCrest Chemical for his help with
this chapter.
Published in 2001 Cosmetics & Toiletries magazine
References
1. R Schueller and P Romanowski, The Role of the Scientist in the Cosmetic Industry,
Cosmet Toil 111(8) 35–9 (1996)
Suggested reading
Cosmetics & Toiletries magazine’s Cosmetic Bench Reference, Allured Publish-
ing, Carol Stream, IL
Soap & Cosmetics 2000 Blue Book, vol. 75, No. 12, Chemical Week Associates,
NY (December 2000)
CTFA International Buyers Guide 2000, Published by CTFA, Washington
(2000)
www.TheCosmeticSite.com
www.CTFA.org (Membership privileges are needed to access some parts of
the site)
www.Cosmeticindex.com
II. Basic Cosmetic Science:
Biology of Hair and
Skin; Chemistry of Raw
Materials

Chapter 7
Inside the Hair:

An Advanced Hair
Biology Model
In this survey, various writers describe a model of the inside of a
hair strand.
key words: hair and hair care, hair structure, cuticle, cortex, lipids
G ive me a head with hair. Long beautiful hair. Shining, gleaming, streaming,
flaxen, waxen—Hair!
These lyrics from the popular Broadway musical Hair are humorous, but they
do raise a very serious question: what exactly is hair? Simply put, the answer is that
hair is protein. This simple answer, however, does not even begin to explain the
complexity and sophistication of the hair fiber.
Science is like that sometimes; it starts with a simplistic model that evolves to
explain more subtle and complex details. For example, consider how the conception
of the atom has evolved over time. The ancient Greeks originally described atoms
as simple, tiny, indivisible particles. This notion was expanded on by Bohr’s theory
that atoms were more like miniature solar systems with electron “planets” revolving
around a “solar” nucleus. Other theories have evolved to the point where atomic
structure now is viewed as an electron density cloud swirling around a diverse col-
lection of subatomic particles.
The concept of hair biology has gone through a similar evolution. The sim-
plistic view that “hair is made of protein” has been replaced by a more detailed
picture of the three structural components of hair: the cuticle, the cortex and the
medulla. This three-component model has evolved even further to include a variety
of substructures. This article will begin with a review of the basic components of
hair and then describe the current understanding of its more complex physical and
chemical substructure.
By gaining a greater understanding of the complex structure of hair, cosmetic
chemists should be able to identify new targets for improving current products and
maybe even create whole new product categories.
Physical Structure—The Simple Version

In a simplistic view, each hair can be thought of as being made up of two struc-
tures: the follicle and the hair shaft. Since cosmetics are designed only to affect
73
74
Inside the Hair: An Advanced Hair Biology Model Beginning Cosmetic Chemistry
the surface appearance of hair, the rest of this article will focus on the structure
of the hair shaft.
The hair shaft is composed primarily of the same hard material that animal
hooves and horns are made of—keratin protein. Depending on the hair type, this
protein can make up 65–95% of the hair’s mass.
Hair keratin is arranged into three primary elements: the cuticle, the cortex and
the medulla. The outermost element is the cuticle, a protective layer that resembles
the shingles on a roof. An average human hair has seven to 10 layers of cuticles
covering it. As hair grows it is exposed to months, or even years, of grooming that
wears down the edges of the cuticle. Once these “shingles” are chipped and bro-
ken away, the inside of the hair is exposed. This portion of the hair shaft, known as
the cortex, is composed of bundles of protein. While the cuticle provides outside
protection for the hair, the cortex gives it its inner strength. The third component
in this simple hair schematic is the medulla, a spongy vacuole that runs through
the center of the cortex. The medulla is considered to be a minor component that
is present in only a portion of hair fibers and probably is a vestigial component that
once provided an insulating effect when hair was the primary protective covering
for humans.
The cuticle, cortex and medulla constitute a simplified picture of the hair’s true
structure. The whole story is much more complex (see sidebar on the stereochem-
istry of hair). This model can help to gain a better understanding of what really is
inside the hair. There will be a focus on the structures of the cuticle and the cortex,
and an attempt to summarize the work of Swift et al.1 for a beginning audience.
A more complete examination of these structures can inspire new approaches to
designing hair care formulas.
Physical Structure—The Cuticle

Despite their simple shingle-like appearance, cuticle cells have a complex mul-
tilamellar structure (Figure 7.1). Multiple layers are attached to one another in
sheets that form overlapping scales. Each cuticle cell is a square sheet about 50 µm
on each side and about 0.5 µm thick. They are composed of the following discrete
layers: the outer b-layer, the epicuticle, the exocuticle, the endocuticle, the inner
layer and the cell membrane complex. Each of these layers has its own substructure
that is described below.
Outer b-layer: As its name implies, the outer b-layer (OBL) (sometimes called
the upper b-layer) is the outermost surface of the hair, although the OBL also
may appear in inner layers because of the way the hair is formed in the follicle
(see Figure 7.1). The OBL primarily is composed of a hydrophobic fatty acid that
protects the surface of the hair. (The composition of this and other hair lipids will
be described later in this article.) The outer b-layer also is present as part of the
cell membrane complex.
75
Figure 7.1.
Epicuticle: This hydrophobic coating on the outside of the cuticle is respon-
sible for many of the surface properties of hair. It is approximately 10 nm thick and
consists of three subsections:
• F-layer. This layer of covalently bonded fatty acids lays on top of the epicuticle.
It is composed of the same material as the outer b-layer. In fact, the F-layers of
the epicuticles closest to the surface create the outer b-layer.
• Protein matrix. This is a layer of highly water-insoluble proteins sandwiched
in the middle of the epicuticle.
• A-layer. This cystine-rich layer approximately 110 nm thick is cross-linked with
an isopeptide. This combination makes the A-layer very tough and resistant to
mechanical damage. Because the proteins in this segment are so cross-linked,
the A-layer does not swell in water. It tends to be brittle, which allows small
segments of the cuticle to break away when damaged.
Exocuticle: This structure lies just beneath the A-layer and is slightly lower in
cystine content. It is the single largest component of the cuticle and takes up about
50% of the cell by cross-sectional area.
Endocuticle: This layer is formed when residual cytoplasm dehydrates and
hardens. It is a region free of cystine and so it tends to behave more like a gel in
that it swells considerably in water. When the endocuticle is damaged, water-soluble
materials can slip inside the hair. This is the current theory of how materials pen-
etrate the hair shaft; they diffuse along the planes of the endocuticle as opposed
to penetrating straight through the cuticle.
76
Inner layer: This layer is similar in composition to the exocuticle, but is

much thinner. The inner layer is bonded to the next cell by the cell membrane
complex.
Cell membrane complex: The cell membrane complex (CMC) is like a “cuticle
glue” and actually is composed of three internal layers: two b-layers separated by
a d-layer.
• Inner b-layer. This layer is sometimes called the lower b-layer. It is composed
of the same material as the outer b-layer.
• d-layer. The composition of this layer is not fully understood, but it is believed
to be a mixture of lipids and glycoproteins.
• Outer b-layer (OBL). This layer (like the OBL mentioned earlier) is com-
posed of a covalently bonded fatty acid.
Together, these sandwiched layers form the sheet-like structure of the cuticle
that covers the outside of the hair shaft. Below the layers of the cuticle lies the next
major structure: the cortex.
Physical Structure—The Cortex

A close look at the core of the hair reveals that it is far more than a simple
bundle of protein fibers. Much of what is known about the cortex was published
in the 1930s by Astbury and colleagues2 who showed that the proteins in these
bundles have a “folded” structure. It wasn’t until the 1950s that Pauling, Corey
and Branson3 discovered that the proteins forming this folded structure have a
helical configuration.
Today, we have a much clearer understanding of this structure. The cortex is built
from protofibrils, microfibrils (also known as intermediate filaments), macrofibrils
and the intermacrofibrillar matrix. The macrofibrils and intermacrofibrillar matrix
are arranged to form the cells of the cortex. Depending on the arrangement, these
cells are classified as either paracortical or orthocortical. These components are
organized into cortical cells that form the body of the cortex. Below are the major
features of each of these elements.
Protofibrils: These elements consist of five individual protein molecules about
1 nm across that wind around each other in a helix arrangement to form a protofibril
rod that is approximately 2.5 nm in diameter. Protofibrils are the building blocks
of the cortex.
Microfibrils: Five protofibril rods are twisted together to form a larger struc-
ture known as a microfibril (also known as an intermediate filament, or IF). These
microfibrils are entangled such that the protein molecules become tied together,
thus giving the hair a high degree of tensile strength.
Macrofibrils: The microfibrils then bundle together to form a still larger cable
known as a macrofibril. Macrofibrils can form two different kinds of cortical cells
depending on how they are packed together.
Intermacrofibrillar matrix: This is a nonkeratin material that is high in cystine
and is found packed inside cortical cells.
Paracortical and orthocortical cells: Paracortical cells contain macrofi-
brils that are packed so closely together that they fill the entire cell. There is no
77
intermacrofibrillar matrix filling the intercellular spaces in this type of cortical cell.
This configuration makes the paracortical cells more dense and unable to absorb
much moisture.
Orthocortical cells consist of macrofibrils loosely packed together and surrounded
by intermacrofibrillar matrix. This packing configuration makes the orthocuticle
cells less dense, so they are able to easily take in or lose moisture. Therefore this
type of cortical cell is very reactive to humidity.
The cortex is a combination of these para and ortho cells hooked together. Each
microscopic cortical cell is shaped like a tiny spindle, about 100 µm long and 5–10
µm wide. These spindles end with finger-like extensions that can hook onto nearby
cells. The para cells tend to be oriented along the inner edge of the cortex while
the ortho cells are grouped on the outer side.
By itself, the paracortex region is very hard and moisture-resistant and would
cause the hair to grow straight. When combined with the softer orthocortex, which
tends to buckle when exposed to moisture, the hair shaft is made to bend, creat-
ing curl. More orthocortex results in more and tighter curls. According to Swift,
the ratio and distribution of these two cells controls the degree of curliness of the
hair. Asian hair has almost all paracortex, Afro-ethnic hair is mostly orthocortex,
and Caucasian hair has a more balanced proportion of each.
Lipids in the Hair Shaft

While most people are aware of the fact that follicles produce lipid materials
(sebum) that coat the surface of the hair, they may be surprised to know there are
numerous lipids found within the hair and even bonded to it. These internal lipids
affect the hair’s structure and properties.
Lipid composition of the hair: Various analytical studies of hair have shown
that lipids comprise approximately 5% of the total mass of hair. They also have
identified numerous types of internal hair lipids including 18-methyl eicosanoic
acid, hydrocarbons, squalene, wax esters, triglycerides, fatty acids, cholesterol and
ceramides. A recent study by Masukawa et al.4 showed that all of these hair lipids
can be arranged into different groups based on their biological source and func-
tion. One group, called exogenous lipids, contains compounds originating from
sebum. In this group are materials such as squalene, wax esters, triglycerides and
fatty acids. While some of these compounds are found throughout the hair, they
are not believed to be directly involved in hair structure.
Another group, called endogenous lipids, is biosynthesized in the hair matrix
cells of the follicle. Compounds in these groups are involved in the structure of
the hair, and will be discussed next.
Structural fatty acids: At the top surface of the hair is the OBL. This layer really is
just the outer surface of the first epicuticle (F-layer) and is composed of a wide range of
endogenous fatty acids. The primary component (more than 40%) is a fatty acid known
as 18-methyl eicosanoic acid (18-MEA). It is a branched, 21-carbon compound that
most likely is biosynthesized in the hair follicle from the amino acid isoleucine. The
fatty acids in these layers are covalently bonded to the epicuticle via thioester linkages.
78
According to Ward et al.,5 the layer formed is approximately 0.9 nm thick. This layer is
believed to add extra protection and waterproofing to the cuticle.
Another lipid-containing structure previously described is the CMC. Both of the
b-layers of this structure are composed primarily of 18-MEA. Less is known about
the exact composition of the d-layer, but it is believed1 to be a mixture of endogenous
lipids and glycoproteins. This structure helps hold the cuticles together and may
assist in hair moisture retention.1 However, low cohesive forces between the b-layers
and d-layers may explain the ease with which cuticle shingles are broken off.1 It is
possible that if this layer were stronger, there would be less hair damage.
Affect on hair properties: The various lipids found throughout the hair are
thought to be major contributors to the hair’s physical properties. Evidence has shown
that they influence a host of characteristics such as strength, feel and condition.
Work by Duvel et al.6 showed that loss of hair lipids (both exogenous and en-
dogenous) due to environmental exposures resulted in increased cortex degradation
and decreased tensile properties of hair.
A study by Wills et al.7 showed that hair lipid content significantly impacts the
perceived shine, smoothness and softness of hair. In this case, a higher level of
lipids in hair resulted in improvements in each of these properties.
Studies such as these suggest possible development routes for products designed
to restore hair to its natural state.
Conclusion
Scientists spend much of their time investigating their world and creating models
to reflect observations. In the initial stages of these investigations the models are
understandably crude. They become more sophisticated over time as more and
more observations are collected. The changing model for the structure of hair is a
perfect example of how this process can work.
For cosmetic chemists, models for the structure of both hair and skin are
helpful for generating ideas for future products. Only by knowing how hair and
skin is put together will significant improvements be made in the type of products
offered tomorrow.
Published November 2005 Cosmetics and Toiletries magazine.
References
1. JA Swift and JR Smith, Microscopical investigation on the epicuticle of mammalian
keratin fibres, J Microscopy 204(3) 203–211 (2001)
2. DAD Parry, Protein chains in hair and epidermal keratin IF: Structural features and
spatial arrangements, In: Formation and Structure of Human Hair, P Jolles, H Zahn
and H Hocker, eds, Basel: Birkhauser Verlag (1997)
3. L Pauling, RB Corey and HR Branson, The structure of proteins: Two hydrogen-
bonded helical configurations of the peptide chain, Proc Natl Acad Sci 37 205–211
(1951)
4. Y Masukawa, H Narita and G Imokawa, Characterization of the lipid composition at
the proximal root regions of human hair, J Cosmet Sci 56(1) 1–16 (2005)
79
5. RJ Ward, HA Willis, GA George, GB Guise, RJ Denning, DJ Evans and RD Short,

Surface analysis of wool by x-ray photoelectron spectroscopy and static secondary
ion mass spectrometry, Text Res J 63 362–368 (1993)
6. L Duvel, H Chun, D Deppa and PW Wertz, Analysis of hair lipids and tensile properties
as a function of distance from scalp, Int J Cosmet Sci 27(4) 193–198 (2005)
7. J Wills, S Dolphin, L Albiston, P Parmar, GE Westgate and GJ Harrap, Free internal
lipids in hair from pre- and post-menopausal women, IFSCC Magazine 7(4) 293–297
(2004)
Additional Reading
K Tanaka et al., Continuous three dimensional examination of the interior hair
structure, IFSCC Magazine 8(1) 3 (2005)
BC Beard, A Johnson, FM Cambria and PN Trinh, Electron spectroscopy and
microscopy applied to chemical and structural analysis of hair, J Cosmet Sci
56 65–77 (2005)
Chapter 8
New Directions for

Sensitive Skin Research
This brief review provides an insight into the current standing of
sensitive skin research, including recent findings on the possible
role of nerve growth factor as an underlying mechanism and
predictive tool for sensitive skin.
key words: sensitive skin, barrier function, nerve growth factor,

neurosensory symptoms, lactic acid sting test
I n recent years reports of sensitive skin among men and women of various ages
and ethnicities have increased. Approximately 52% of women and 38% of men
have self-diagnosed sensitive skin. Further, 10% of women and 6% of men describe
themselves as having very sensitive skin.1 Individuals who have skin with a lower
tolerance threshold for cosmetic and personal care products than those with sensi-
tive skin are described as having very sensitive skin. Thus, their adverse responses
to these products occur more frequently. As a result, the demand for cosmetic and
personal care products formulated for individuals with sensitive skin has increased
throughout the past 10 years. According to the New York Times, sensitive skin
product sales have jumped 13% since 2000, and sales in the United States average
more than $900 million annually.2
Though currently a plethora of sensitive skin products are on the market, no
industry standard exists for characterizing the condition or for substantiating sensitive
skin product claims.2 This deficiency may be attributed to the lack of understanding
the underlying mechanisms leading to sensitive skin.3–6 The obscurity of the etiol-
ogy may well be attributed to the lack of noticeable signs of irritation, intra- and
inter-subject variability, and an unclear understanding of the effects that age, race
and lifestyle play in the prevalence of sensitive skin.6–12
Clarification of the exact mechanisms of action in sensitive skin and the estab-
lishment of a universal, objective, reproducible and quantifiable testing method
are essential for the further advancement of research in this area. Establishing
these parameters will provide companies an avenue to substantiate their claims
by ensuring that sensitive skin products are being tested on individuals with the
condition, in turn enhancing the safety and efficacy of sensitive skin products
before releasing them.
81
82
New Directions for Sensitive Skin Research Beginning Cosmetic Chemistry
Sensitive Skin Overview

Sensitive skin, also referred to as sensory skin irritation, chemosensory irritabil-
ity, cosmetic intolerance syndrome or status cosmeticus, is a condition with varying
definitions.2,13,14 In general, the disorder is defined as a heightened intolerance
to topically applied substances, mainly cosmetic or personal care products.3,14
Neurosensory symptoms such as itching, burning, stinging, tingling and tightness
are characteristics of the condition and frequently are experienced on the face.
Typically, these symptoms are apparent immediately after product use; however,
they can be delayed minutes to days after product use, and exacerbated by wind,
sun exposure, excessive heat, humidity or cold temperatures.1,4–6,8,12,13,15,16,20
Individuals who suffer from sensitive skin are believed to be in good health
and free of pre-existing skin disorders,8,14 but those suffering from atopic derma-
titis, eczema, allergic contact dermatitis, irritant contact dermatitis, seborrheic
dermatitis, rosacea, acne and psoriasis may have a predisposition to the condition.
It has not been clarified how these skin disorders are linked to sensitive skin but
there is speculation that sensitive skin may be an indicator of more serious skin
conditions such as rosacea and eczema.1,6,13,16 Conversely, the link between sensitive
skin and other skin conditions often categorized with it, such as irritant and allergic
contact dermatitis, has been challenged.17 Robinson et al. showed that people with
self-reported sensitive skin were not more responsive to patch tests with standard
irritants such as sodium dodecyl sulfate.11 Thus, evidence that sensitive skin is not
just a symptom that accompanies other skin disorders, but that it is a true condition
and should therefore be investigated as such.18–20
Testing Methods
In 1977, Frosch and Kligman developed a method for diagnosing sensitive
skin. This method is known as the lactic acid sting test (LAST) and is the most
widely used method for predicting sensitive skin, although many industry ex-
perts argue that it is not a true predictor of the condition.3,5,6,15,20 The original
procedure involved the induction of sweating for 15 min in a 120°F environ-
mental chamber followed by the application of 5% lactic acid to the nasolabial
fold and cheek.21
The LAST method came under criticism in the years following its inception.8
Christensen and Kligman developed an improved procedure for conducting the
LAST method on facial skin. The new method used 10% lactic acid instead of 5%
lactic acid. The purpose of the increase of lactic acid was to allow omission of the
sweat-inducing step used in the previous method. Hilltop chambers, or occlusive
patch test systems used widely to assess the direct and indirect effect products
have on the skin, were used on the cheek for 10 min instead of exposing the area
to lactic acid with a cotton swab as done previously. The time required for stinging
to occur and the peak intensity of stinging, on a scale of 0–3, was recorded.
Many modified types of the LAST method are being used today. Re-
searchers vary the use of Hilltop chambers versus cotton swabs, the exposure
time of lactic acid on the skin, and the scale that is used to measure stinging
83
intensity.3,9,15,18,22 The LAST method has proven to be useful and reproduc-

ible, but it does not allow easy quantification of the magnitude of stinging.8,9
Furthermore, the role ethnicity plays in the stinging phenomenon is unclear,
but it could have a profound effect on susceptibility to stinging. Aramaki et al.
showed that sensitivity to stinging was higher in Japanese women as compared
to German women;22 and the effects of age, sex and product use on the stinging
phenomenon is unclear.8
Presently, a number of other testing methods are being used to evaluate sensitive
skin such as visual scoring, blood flow measurements, ultrasound, confocal light
microscopy and questionnaires.10 Though these methods may prove promising for
the future, there is still a need for extensive research in this arena.
Mechanisms of Sensitive Skin

Today, the majority of the literature on sensitive skin focuses on the premise that
sensitive skin is caused by an increased permeability of compounds through the skin
due to a compromised stratum corneum (SC) barrier. This ideology originated in 1977
when Frosch and Kligman developed the LAST method for diagnosing sensitive skin.
Compromised barrier function has become the most accepted mechanism of sensitive
skin.3–5,21 This hypothesis was supported further when Issachar et al. found higher skin
pH in those who tested positive to the LAST method due a higher lactic acid penetra-
tion of the skin and less remaining on the surface.7 Thus, it is understandable why many
would believe that a compromised SC barrier is the main culprit of sensitive skin.
On the contrary, Yokota et al. reported that a compromised SC barrier was pres-
ent in some individuals with sensitive skin but not in all of them. This phenomenon
was shown by separating individuals with sensitive skin into subgroups according to
mechanism of action. Type I had compromised SC barrier function, Type II had in-
flammation with normal barrier function and Type III was defined as pseudo-healthy
in terms of normal barrier function and absence of inflammation.
Elevated levels of nerve growth factor (NGF) were the only commonality that
researchers found among the groups. NGF levels in the SC were evaluated by tape
stripping the SC and analyzing the tape strips for NGF content. Each sensitive
skin group had significantly higher levels of NGF in the SC as compared to those
without the condition. They also showed that individuals categorized as Type II
and III had higher sensitivity to electrical stimulation than people with normal
skin, which could suggest that innervation plays a role in sensitive skin.23
Recently, hyperinnervation in the epidermis has been implicated as an underly-
ing mechanism of sensitive skin.5,13,20 It has been suggested that this phenomenon
causes heightened neurosensory input that leads to the adverse sensory responses
that individuals with sensitive skin often experience.13 However, this factor has not
been studied extensively. The paucity of research in this area is surprising since
it has been established that cutaneous sensory responses are directly related to
sensory nerve fibers found in the dermis and epidermis.24 Scientists from Shiseido
and investigators of the Massachusetts General Hospital/Harvard Cutaneous Biol-
ogy Research Center showed the direct connection between the skin and brain
84
by confirming the contact point between Langerhan cells in the skin and nerve
cells.25 Hence, it is essential that the connection between hyperinnvervation of
the epidermis and sensitive skin be studied since sensory responses are the key
component of the condition.
Further research on NGF levels in the SC could prove to be useful in fully
understanding sensitive skin. This area should be researched in more depth be-
cause it is has been proven that NGF plays a crucial role in a number of cutaneous
processes such as the determination of the innervation density of skin, survival
and differentiation of neurons during early development and sensitization of nerve
fibers.24,26 Additionally, changes in cutaneous NGF content leads to alterations in
cutaneous innervation densities and abnormalities in sensory neurons in adult
rats.27 Heightened levels of NGF in the epidermis of transgenic mice resulted in
increased and abnormal innervation patterns in the skin.26,28 It is unclear whether
NGF levels in the SC can be directly related to innervation or sensitive skin.
Therefore, understanding what role, if any, NGF and epidermal innervation play
in sensitive skin will shed light on this theory.
Conclusion
Great strides have been made in the study of sensitive skin. However, more
research is needed to fully explain the condition. Clarifying the mechanisms of
sensitive skin would benefit industrial and clinical arenas. Clinically, it will be
much easier to develop an objective and quantitative diagnosis tool if the biologi-
cal basis of the condition was completely understood. In turn, this would lead to
a clear-cut diagnosis of the condition, and it would be helpful in understanding
the link between sensitive skin and other skin conditions.
It is well established that consumers discriminate between products based on
how they feel on the skin during use; however, it is extremely difficult to measure
these types of responses during clinical trials because there is no objective method
for categorizing people with sensitive skin. Thus, companies are limited in their
ability to predict adverse sensory responses because the products are not always
being tested on those who truly have sensitive skin.5,6,9,10,29
If a distinct group of individuals with sensitive skin could be identified and used
for product testing and claim substantiation, adverse effects could be minimized and
efficacy maximized before products reach the consumer. Perhaps if it were further
established that increased levels of NGF in the SC are a commonality among those
with sensitive skin, then tape-strip sampling of the neurotrophin would prove to be
a very reliable and objective method for predicting sensitive skin that also could be
quantified. Until the underlying mechanisms of sensitive skin are explained, it will
be a challenge to develop the robust testing method that is needed.
Published December 2006 Cosmetics & Toiletries magazine

85
References
1. CM Willis, S Shaw, O De Lacharriere, M Baverel, L Reiche, R Jourdain, P Bastien
and JD Wilkinson, Sensitive skin: an epidemiological study, Br J Derm 145(2) 258–63
(2001)
2. N Singer, “Face it princess, your skin is probably quite common,” The New York Times
(Oct. 3, 2005) 3
3. A Sparavigna, A Di Pietro and M Setaro, ‘Healthy skin’: significance and results of
an Italian study on healthy population with particular regard to ‘sensitive’ skin, Int J
Cosmet Sci 27(6) 327–31 (2005)
4. A Pons-Guiraud, Sensitive skin: a complex and multifactorial syndrome, J Cosm Derm
3(3) 145–8 (2004)
5. G Primavera and E Berardesca, Sensitive skin: mechanisms and diagnosis, Intl J
Cosm Sci 27(1) 1–10 (2005)
6. M Marriott, J Holmes, L Peters, K Cooper, M Rowson and DA Basketter, The complex
problem of sensitive skin, Contact Derm 53(2) 93–9 (2005)
7. N Issachar, Y Gall, MT Borell and MC Poelman, pH measurements during lactic acid
stinging test in normal and sensitive skin, Contact Derm 36(3) 152–5 (1997)
8. M Christensen and AM Kligman, An improved procedure for conducting lactic acid
stinging tests on facial skin, J Soc Cosm Sci 47(1) 1–11 (1996)
9. M Robinson and M Perkins, Evaluation of a quantitative clinical method for
assessment of sensory skin irritation, Contact Derm 45(4) 205–13 (2001)
10. MA Farage, A Katsarou, HI Maibach, Sensory, clinical and physiological factors in
sensitive skin: a review, Contact Derm 55(1) 1–14 (2006)
11. M Robinson, Population differences in acute skin irritation responses, Contact Derm
46(2) 86–93 (2002)
12. G Yosipovitch, Evaluating Subjective Irritation and Sensitive Skin, Cosm Toil 114(1)
41–2 (1999)
13. ZD Draelos, Cosmetic selection in the sensitive-skin patient, Dermatologic Ther 14(3)
194–9 (2001)
14. AA Fisher, Part I: “Status Cosmeticus”: A Cosmetic Intolerance Syndrome, Cutis 46(2)
109–10 (1990)
15. S Seidenari, M Francomano and L Mantovani, Baseline biophysical parameters in
subjects with sensitive skin, Contact Derm 38(6) 311–5 (1998)
16. R Jourdain, O De Lacharriere, P Bastien and HI Maibach, Ethnic variations in self-
perceived sensitive skin: epidemiological survey, Contact Derm 43(3) 162–9 (2002)
17. R Wolf, D Wolf, B Tuzun and Y Tuzun, Cosmetics and contact dermatitis,
Dermatologic Ther 14(3) 181–7 (2001)
18. J Coverly, L Peters, E Whittle and DA Basketter, Susceptibility to skin stinging,
non-immunologic contact urticaria and acute skin irritation; is there a relationship?
Contact Derm 38(2) 90–5 (1998)
19. AM Kligman, The Invisible Dermatosis, Archives of Derm 127(9) 1375–82 (1991)
20. ZD Draelos, Sensitive Skin: Perceptions, Evaluation, and Treatment, Am J Contact
Derm 8(2) 67–78 (1997)
21. PJ Frosch and AM Kligman, A method for appraising the stinging capacity of topically
applied substances, J Soc Cosm Chem 28(5) 197–209 (1977)
22. J Aramaki, S Kawana, I Effendy, R Happle and H Loffler, Differences of skin irritation
between Japanese and European women, Br J Derm 146(6) 1052–6 (2002)
23. T Yokota, M Matsumoto, T Sakamaki, R Hikima, S Hayashi, M Yanagisawa, H
Kuwahara, S Yamazaki, T Ogawa, M Hayase, Classification of Sensitive Skin and
Development of a Treatment System Appropriate for Each Group, Int Fed Soc Cosm
Chem 6(4) 303–7 (2003)
24. I Kinkelin, S Motzing, M Koltzenburg and EB Brocker, Increase in NGF content and
nerve fiber sprouting in human allergic contact eczema, Cell & Tissue Res 302(1) 31–7
(2000)
86
25. J Wiechers, Mind over matter: cosmetic claim substantiation issues facing the future,
Cosm Toil 120(9) 3–8 (2005)
26. K Albers, DE Wright and BM Davis, Overexpression of Nerve Growth Factor in
Epidermis of Transgenic Mice Causes Hypertrophy of the Peripheral Nervous System,
J Neurosci 14(3) 1422–32 (1994)
27. DL Bennett, M Koltzenburg, JV Priestley, DL Shelton and SB McMahon, Endogenous
nerve growth factor regulates the sensitivity of nociceptors in the adult rat, Eur J
Neurosci 10(4) 1282–91 (1998)
28. BM Davis, BT Fundin, KM Albers, TP Goodness, KM Cronk and FL Rice,
Overexpression of Nerve Growth Factor in Skin Causes Preferential Increases Among
Innervation to Specific Sensory Targets, J Comp Neur 387(4) 489–506 (1997)
29. M Farage, Are we reaching the limits of our ability to detect skin effects with our
current testing and measuring methods for consumer products? Contact Derm 52(6)
297–303 (2005)
Chapter 9
Axillary Odor: Its

Physiology, Microbiology
and Chemistry
This chapter surveys recent reports on the physiology,
microbiology and chemistry of axillary malodor, as well as the
thresholds for perceiving various axillary odors.
key words: sweat glands, sweat composition, sweat biochemistry,

axillary odor, axillary bacteria
B ody odors originate from many sources. Axillary odor is the most characteristic
and stigmatized of these odors. Early attempts to counter axillary odor masked
it with fragrant oils, an approach that continues to the present.
Breakthroughs in controlling axillary malodor came in the latter part of the 1900s
when scientists explained the structure and function of human sweat glands and the
role of bacterial microflora on the skin. Characterization of underarm secretions and
skin bacteria led to various odor control strategies, such as reducing perspiration by
blocking sweat glands and reducing microorganisms on the body surface.
More recent developments have deepened our understanding of axillary chemis-
try and identified the steroids and acids that create body odor. These developments
coupled with our current knowledge of odor perception and new technologies such
as controlled release, have opened up new avenues to control axillary odor.
Sweating and Sweat Glands

Sweating is the elaboration of a fluid secretion on the bodyís surface by sweat
glands. It controls body temperature through evaporative cooling. Only about 1%
of human body weight need be evaporated as sweat to prevent a 10°C rise in body
temperature.1 Perspiration also eliminates lactic acid2 generated through muscular
activity and prevents skin dryness and loss of elasticity.
Human sweat glands were discovered by Purkinje in 18333 and named apocrine
and eccrine glands by Schiefferdecker in 1917.4 Eccrine glands are structurally
and physiologically intact at birth, and sweating is seen within the first three days
of life.5 Apocrine glands are also functional at birth; they develop in association
with hair follicles and open into them. In 1987, Sato et al. 6 found a third type of
87
88
Axillary Odor: Its Physiology, Microbiology and Chemistry Beginning Cosmetic Chemistry
apocrine-like sweat gland—the apoeccrine gland—that seems to develop from

eccrine or eccrine-like precursor glands during puberty.
The body has 2-4 million sweat glands distributed over almost its entire surface.
Their density is usually 100–200 glands/cm2, but can be as high as 600–700 glands/
cm2 on palmar and plantar surfaces. The back, chest, forehead and lower extremities
also have high sweat gland densities.5 The number of sweat glands in an individual
is fixed and does not increase with age.
The eccrine gland is tubular, approximately 4–8 mm in length and has an out-
side diameter of 30–60 mm. Its secretions form in the coil and flow through a duct
leading to the skin surface. The gland’s length and diameter vary among individuals
and among glands on the same individual.7
The apocrine gland has a large, coiled secretory portion and a relatively straight
duct that opens into the hair follicle canal near the skin surface. The base of the
secretory portion is much larger than the one in its eccrine counterpart.8 Apocrine
glands are found in the more densely haired areas of the body. Gland density varies
with anatomical region. Parisseíreports apocrine glands outnumber eccrine glands
in the axillary region by about 10:1,2 although Gower says apocrine and eccrine
glands have an approximate 1:1 ratio.9
The apoeccrine gland has a long, thin duct (resembling the eccrine sweat duct)
that opens quickly onto the skin. According to Sato, apoeccrine glands only occur in
the hairy area of the axilla and are not found in retroaxillary areas, upper arm near
the axilla or the inguinal area.10 Sebaceous glands are connected to hair follicles
and also play a role in axillary odor.
The Nature of Sweating

Sweating is usually triggered by heat and exercise, although even mental activity
can induce it. The hypothalamus houses the main center for thermo regulation.
Lesions of its preoptic and anterior regions generally cause anhidrosis (diminished
or complete absence of secretion of sweat), while lobotomy is often associated with
hyperhidrosis. There is good evidence that a- and b- adrenergic and cholinergic
agonists can stimulate sweat secretion.1
Each agonist can be blocked by specific antagonists, which implies the existence
of at least three different receptors in the cell membranes of the secreting coil. The
biochemical linkage between receptor binding and activation and sweat secretion
is complex and beyond the scope of this paper. See Quinton1 for a discussion of
the structure and function of eccrine sweat glands.
Apocrine gland secretions are somewhat viscous and rich in proteins and lipids.
They are clear to milky white and vary with skin color, sex and diet.11 Table 9.1
shows the lipid and cholesterol profiles from apocrine secretions.
The apocrine secretory coil is considerably larger than that in the eccrine gland
and makes its product continuously. Even so, the daily amount of apocrine secretion
is miniscule: less than 1 ml in the whole axillary organ.12 The secretion is odorless
and sterile as it emerges from the follicular opening.
Nearly all the fluid in perspiration is secreted by the eccrine and apoeccrine
glands. Eccrine glands are primarily responsible for thermal regulation of the body
89
and release large amounts of fluid, chiefly water, in a relatively short time. Eccrine
secretions also contain amino acids, electrolytes and minerals. This fluid originates
in extracellular fluid and contains many of the same solutes as plasma but in much
smaller concentrations.13
In sweat, glucose concentrations are less than 1% of that seen in plasma. Lactate
concentrations exceed plasma values by up to or more than an order of magnitude,
while urea concentrations slightly exceed those of plasma. About 3% of the total
amino acids in sweat occur as proteins; the rest appear as free amino acids. Nearly
all naturally-occurring amines are present in sweat, but proline is reported only in
sweat from women.
Table 9.1. Percentage composition of glandular secretion20
Glandular secretion Skin surface extract

Apocrinea Sebaceousb Axillae Facial
Cholesterol 76.2 3.4 8.9 1.5
Cholesterol esters 0.9c 21.8 8.8 3.0
Wax esters 3.6c
– 21.2 26.0
Squalene 0.2c 19.0 13.4 12.0
Glycerides and fatty acids 19.2c 55.9 47.4 57.5
Total lipid 20 mg/ml – 60 mg/cm2 100 mg/cm2
a
Stimulated and collected at skin surface
b
Collected from microdissection of gland31
c
Probably of sebaceous origin
While lactate and HCO3– concentrations are higher in sweat than in plasma,
their levels fall significantly as the sweat rate decreases. HCO3– disappears and sweat
becomes acidic (pH<5) when secretion falls below about 20% of maximum. Most
other solutes in sweat are inorganic electrolytes. The concentrations of Na+ and
Cl– depend on the sweat rate and normally range from approximately 10–15 meq/l
at low rates to 40–50 meq/l at high rates.14 Exercise and heat tolerance training
tend to lower Na+ concentrations. Potassium concentration is slightly higher than in
plasma, but, unlike Na+ and Cl– levels, it tends to increase as sweat decreases.15
Since there are no biological water pumps,16 water in biological systems moves
when it is coupled to solutes or subsequent to the transport of solutes and the con-
sequent build-up of an osmotic gradient. Human sweat varies in composition, but
is almost always hypotonic (a solution of lower osmotic pressure). Initially sweat is
isotonic (it has the same osmotic pressure as plasma) and has a sodium concentra-
tion of about 145 mmol/l. The eccrine duct reabsorbs salt (mainly as NaCl) and
is relatively impermeable to water. The typical composition of eccrine sweat is as
shown in Table 9.2.
90
Table 9.2. Composition of eccrine sweat32,33
Water 99.020%
Sodium chloride 0.700
Lactic acid 0.100
Ascorbic acid 0.040
Acetic acid 0.040
Propionic acid 0.006
Caprylic and caprionic acids 0.005
Urea and uric acids Trace amounts
Apoeccrine glands that develop from eccrine glands at puberty are as numerous
as the eccrine glands. Apoeccrine glands can sustain greater fluid secretion than
eccrine glands and may contribute substantial moisture to the axillary environ-
ment.17 Apoeccrine glands secrete nearly seven times as much serous-type fluid
as do eccrine glands.
Sebum from sebaceous glands also plays a role in underarm odor. Sebum is
rich in lipids, especially triglycerides, wax esters and squalene.1
Malodor Precursors
The nature of the precursors in sweat and sebum—especially lipids, cholesterol
and C19 androgen steroids—affects the odor-causing physical and chemical changes
in the axilla. The major lipids present come from sebum contamination, so the
lipid profile (Table 9.1) resembles that of sebaceous lipids. The cholesterol seen
exceeds that expected from sebaceous or epidermal sources and is believed to be
from apocrine secretion. This is converted to cholesterol esters through the action
of Staphylococcus epidermis, which efficiently hydrolyzes glycerides (at pH 6–8.5)
and esterifies cholesterol with the resultant fatty acids.
In 1970, Brooksbank found steroids (dehydroepian-drosterone sulfate and an
androsterone sulfate) in axillary materials collected on cotton wool pads.18 In a
similar study, Gower also found 5a-androst-16-en-3-one.19 Table 9.3 shows the
steroids identified in axilla.20
The steroid 5a-Androstenol is found in human urine. Amoore et al. designated
its oxidation product 5a-androstenone as the primary urinous odor.21,22 Both steroids
are found in human axillae. One study found that androstenone levels were 3–310
ng in males and 3.5–11 ng in females. Other steroids (androstenone, androstenol,
androstadienol, androstadienone) ranged from 10–150 ng and androstenol pre-
dominated in eight of 10 subjects. Studies at Monel found a significant change in
androstenol levels across the menstrual cycle.23
Zeng et al. isolated and identified compounds in male axillary secretion extracts
that contained the characteristic odors present in the axillae.24 They found that several
C6 to C11 straight-chain, branched and unsaturated acids were important contribu-
tors to axillary odor. The major one was (E)-3-methyl-2-hexenoic acid (E3M2H).
91
Other important odor contributors were terminally unsaturated acids, 2-methyl

C6-C10 acids and 4-ethyl C5-C11 acids. Figure 9.1 lists the fatty acid compounds
that were identified in this study as contributing to axillary odor.
Table 9.3. Steroids identified in axilla20

Steroids Analytic method
Apocrine secretion
Cholesterol GC-MS
Androsterone (sulfate)a GC-MS
Dehydroepiandrosterone (sulfate)a GC-MS
Axillary sweat
Androst-4-ene-3-17-dione TLC, RT
DHA (sulfate) TLC, RT
Pregn-5-ene-3-b-ol-20-one TLC, RT
Androst-16-en-3a-ol GC-MS
Androst-16-en-3-one RIA, GC-MS
Androst-5,16-dien-3a-ol GC-MS
Androsta-4,16-dien-3-one GC-MS
GC-MS = gas chromatography – mass spectroscopy
TLC = thin layer chromatography
RT = radioactive tracer studies
RIA = radioimmunoassay
a
Also found in axillary sweat by TLC and/or GC-MS.
Figure 9.1. Fatty acid contributors to axillary odor
In a separate study, Zeng et al. found the same mixtures of odorous components
in female axillary secretions with minor differences.25 The similarity of proteins
present in the aqueous phase and the acidic constituents in characteristic female
and male axillary odors suggest a similar origin for axillary odors in both sexes. Based
on their findings, Zeng et al. made the following observations: 24
92
• Branched and unsaturated compounds seem to have a high odor impact.

• (E)-3-methyl-2-hexenoic acid (E3M2H), which is both unsaturated and
branched, is a major contributor to axillary odor.
• The Z isomer, which is present at one-tenth the concentration of the E iso-
mer, has a high odor impact, but its odor quality is more like that of aliphatic
acid.
• Precursors for these compounds are probably not amino acid-like in com-
position, given the chain length and branching of the acids involved.
• Odor occurs quickly, which suggests it forms by simple bond cleavage and
not complex bacterial catabolism from higher molecular components.
Microbiology of the Human Axilla

The human axilla is an ideal environment for bacteria. It is semi-occluded, so
it minimizes evaporation of the water bacteria needed for growth and it provides
essential nutrients. Eccrine and apoeccrine glands supply water, amino acids,
electrolytes and minerals. Apocrine glands secrete a substance rich in protein and
lipid; sebaceous glands produce triglycerides, wax esters and squalene.
In 1953 Shelley, Hurley and Nicholas showed that fresh apocrine secretions were
odorless, but generated a characteristic axillary odor when incubated for six hours
at room temperature.26 Odor did not develop at 0°C or if sweat was treated with
the antibacterial hexachlorophene. They concluded that axillary odor occurred in
vivo by bacterial action on substrate(s) present in apocrine secretions. Since then,
many studies and reviews of axillary micro-flora have been completed.10,27-29 The
sidebar summarizes some of what has been learned about axillary microflora.
Leyden et al. conducted a quantitative bacteriological survey of 205 individu-
als.27 Those results, from 1981, are shown in Table 9.4.
Table 9.4. Prevalence and density of axillary-resident bacterial flora27
Males (N = 128) Females (N = 77)

Prevalence Densitya SEMb Prevalence Density SEM
Aerobic flora 100% 6.9 x 105 0.06 100% 8.9 x 105 0.09
Micrococcaceae 100 1.2 x 105 0.07 100 3.6 x 105 0.11
Lipophilic diphtheroids 85 2.5 x 10 5
0.09 66 2.3 X 10 5
0.14
Large colony
diphtheroids 26 2.7 x 104 0.21 25 3.7 x 104 0.24
Gram-negative rods 20 2.3 x 10 3
0.25 19 2.1 x 10 3
0.31
Propionibacteria (total) 70 5.1 x 103 0.21 47 1.7 x 104 0.30
P. acnes 47 7.2 x 103 0.29 30 1.8 x 104 0.38
P. avidum 34 4.2 x 103 0.22 21 1.5 x 104 0.43
P. granualosum 8 4.1 x 103 0.32 5 4.5 x 103 0.28
a
Gometric mean per cm2
b
Standard error of the mean, expressed in logarithms
93
Table 9.5, from the same survey, displays the bacteriological differences in
two odor groups (those with acrid and with acid sweat) and demonstrates the role
played by microflora in body odor secretion. Those with typical acrid axillary odor
had significantly more organisms.27
Table 9.5. Bacteriological difference in two odor groups27
Acrid Acid
axillary odor Prevalence axillary odor Prevalence
Number of organisms/cm2 1,300,000 – 480,000 –
Lipophillic diphtheroids/cm2 810,000 100% 53,000 55%
Large colony diphtheroids/cm2 250,000 52 1,600 9
Propionibacteria/cm2 36,000 70 36,000 49
Gram-negative rods/cm2 ª30,000 20 ª30,000 19
Biochemistry of Odor Formation

Axillary odor combines many notes.29 The dominant notes are: “sweat” imparted
by isovaleric acid; “musky odor” imparted by androstenol (which is not considered
unpleasant); hircine or goat-like imparted by 4-ethyl heptonoic acid; and extremely
disagreeable urinous odor imparted by 5a-androstenone. The biochemical reactions
that lead to the formation of these compounds are shown in Figure 9.2.
Figure 9.2. Reactions forming the dominant ‘notes’ in axillary odor
Other substances in the axilla contribute to the total axilla odor profile. These
substances originate from sebaceous and eccrine glands, cell debris, lipid oxidation
and other sources. Squalene, which makes up about 10% of sebum, is a fixative in
fragrances and may help prolong axillary odor.
Rennie et al. examined the relationship between human axillary skin microflora
and underarm odor, in particular the ability of cutaneous bacteria to transform
steroids.29 A study of bacterial population density and axillary odor intensity in 36
males showed an association between the population density of aerobic cornyeform
94
bacteria and odor intensity. No association was found between the population
density of Staphylococci, Micrococci or Propionibacteria and underarm body odor
intensity. Only aerobic coryneforms produced axillary odor in vitro. Micrococci also
transformed testosterone to androstenedione, but Staphylococci and Propionibac-
teria could not metabolize it.
Rennie et al. also demonstrated that extracts from low-odor subjects could
generate intense body odor when incubated with an appropriate underarm odor-
positive bacterium.29 This adds further support to the concept that underarm odor
intensity is dictated primarily by the density and type of skin microflora. They also
showed that bacteria that can generate body odor possess a range of enzymes able
to transform steroids.
Odor Perception
The olfactory system is highly complex30 and people have a wide variation in odor
perception and detection thresholds. To be perceived as an odorant, a molecule
volatized from its source is inhaled into the nasal cavity. It then dissolves in the
mucus layer lining the epithelium, which contains olfactory cells. It is believed that
the molecule is bound by a protein receptor on hair-like protrusions from the cell,
which causes the cell to send nerve impulses to the olfactory lobe of the brain. The
brain interprets the incoming signals by associating them with a previous experience
and assigns them odor descriptors. Much research is underway on how an odorant
and a receptor interact and how olfactory coding occurs within the brain.
Most odors are complex stimuli and combine many chemicals that affect many
olfactory receptors, so synergistic and antagonistic effects must be considered.
Odorants also stimulate trigeminal nerves in the nasal cavity. These nerves respond
to odorant irritancy. Examples of trigeminal-mediated perceptions are the coolness
of menthol and the sting of ammonia.
The nose is often more sensitive than instruments designed to detect odor,
but many adults have flaws in this exquisite system. They may be born without an
olfactory lobe, have severed olfactory nerves or a deviated septum. Some specific
anosmics have a genetic component.
A defined set of population can be statistically surveyed to determine what per-
centage of the subjects is anosmic to specific odors emanating from a human body.
Based on the frequency, the occurrence of olfactory deficits can be recorded. The
deficit may be due to a number of factors, such as a deviated septum or severed
olfactory nerves.
Amoore’s research group looked at the occurrence of olfactory deficits to some
body odorants.21 A high percentage of subjects were anosmic to 5a-androstenone, a
major contributor to acrid human axillae odor. In dealing with odor perception, the
absolute threshold (the lowest concentration perceived) determines an individualís
relative sensitivity. Table 9.6 shows the individualís sensitivity and threshold value
of some of the body odorants. The extremely low threshold values indicate why
underarm body odors are readily detected.
95
Table 9.6. Frequency of occurrence of olfactory defects

to some odorants30,33
Percent of
Characteristic Odor humans not Threshold
Odorant smell source detecting the odor (ppb)
5a-androst-16-en-3-one urinous axillae 45–50 (36)* 0.18
4-ethylheptanoic hircine axillae (goaty) 16 1.8
androstenol musky axillae 12 (6)* 6.2
isovaleric acid sweaty axillae/foot 3 1
* The percentage outside the parentheses is for males; the percentage within the parentheses is for
females.
Summary
This chapter reported on the physiology, microbiology and chemistry of axillary
malodor. Sweat derives from apocrine and eccrine glands, which are present at
birth, and apoeccrine glands that develop during puberty. These glands, together
with sebaceous glands, produce water, amino acids, electrolytes, minerals and other
nutrients that support bacteria resident in the axillae. Bacteria, especially aerobic
coryneforms and Gram-negative Micrococci, create axillary odor by breaking down
precursors in sweat, especially lipids, cholesterol and C19 androgen steroids. While
the thresholds for perceiving various axillary odors, such as the urinous odor of
5a-androstenone, are quite low, a significant portion of the population is anosmic
to them.
Published May 2002 in Cosmetics & Toiletries magazine.
References
1. PM Quinton, HY Elder, DM Jenkinson and DL Borell, “Structure and functions of
human sweat glands.” In K Laden (Ed), Antiperspirants and Deodorants, 2nd edn,
Marcel Dekker Inc, New York: (1999)
2. AJ Parisse, “Antiperspirant.”In WC Wagganer (Ed), Clinical Safety and Efficacy Testing
of Cosmetics, Marcel Dekker Inc, New York (1990)
3. Y Kuno, Human Perspiration, Charles C Thomas Springfield, IL: 43, 223-250(1956)
4. P Schiefferdecker, Zentralbl, Biol Aerosol Forsch 37 534-562 (1917)
5. J Verbou and J Baxter, Brit J Dermatol 90 269–276 (1974)
6. K Sato, R Leidel and F Sato, Morphology and development of apoeccrine sweat
glands in human axillae, Am J Physiol 252 (Regulatory Integrative Comp Physiol 21)
R166–R180 (1987)
7. K Sato and F Sato, Am J Physiol 245 R203-R208 (1983)
8. DR Shaw et al, Biochemistry Physiology and Molecular Biology of the Skin, 2nd edn,
Oxford University Press, London 763, 775 (1991)
9. DB Gower, A Nixon and AI Mallet, “The significance of odorous steroids in axillary
odour.” In Perfumery: The Psychology and Biology of Fragrance Chap 3, pp 47–5
(1974)
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10. K Sato and F Sato, Morphology and development of an apoeccrine sweat gland in
human axillae, Am J Physiol , 252 R166–R180 (1987)
11. HJ Hurley and W Shelley, The Human Apocrine Sweat Gland in Health and Disease,
Charles C Thomas, Springfield, IL (1960)
12. JN Labows et al, “Axillary odor: Current status.” In Frost, Horwitz and Mosby (Eds),
Principles of Cosmetics for Dermatologists, (1982)
13. IJ Shulz, Micropuncture studies of the sweat formation in cystic fibrosis patients, J
Clin Invest 48 1470 (1969)
14. J Bijman and PM Quinten, Influence of abnormal CT impermeability on sweating in
cystic fibrosis, Am J Physiol 247 C3–C9 (1984)
15. HM Emrich and KJ Ulrich, Pflugers Arch 290 298–310 (1966)
16. PM Quinton, Comparative Animal Nutrition, M Rechiyl Jr (Ed), Basel: Krager 100–231
(1979)
17. K Sato et al, Sweat secretion by human axillary apoeccrine gland in vitro, Am J
Physiol 252 R181–R187 (1987)
18. BWL Brooksbank, Experentia 26 1012 (1970)
19. DB Gower, 16-Unsaturated C19 steroids: A review of their chemistry, biochemistry and
possible physiological role, J Steroid Biochem 3 45 (1972)
20. JN Labows Jr, “Odor detection, generation and etiology in the axilla” In K Laden and
C Felger, (Eds), Antiperspirants and Deodorants, Marcel Dekker New York (1988)
21. JE Amoore, Specific anosmias to 5a-androst-16-en-3-one and a-pentadecalactone:
The urinous and musky primary odors, Chemical Senses and Flavour, Dordrecht-
Holland: D Reidel Pub Co vol 2, 217, 401–425 (1977)
22. JE Amoore, Chemical Senses and Flavour, Dordrecht-Holland: D Reidel Pub Co (1977)
vol 2, 267–279
23. G Preti, WB Culter, CM Christensen, HS Lewley, GR Huggins and CR Garcia, Human
axillary extracts: Analysis of compounds from samples which influence menstrual
timing, J Chem Ecol 13 717–731 (1987)
24. X-N Zeng et al, Analysis of characteristic odor from human male axillae, J Chem Ecol
17(7) 1469–1492 (1991)
25. X-N Zeng, JJ Leyden, AJ Spielman and G Preti, Analysis of characteristic human
female axillary odors: Qualitative comparison to males, J Chem Ecol 22(2) (1996)
26. W Shelly, H Hurley and A Nicholas, Axillary odor: Experimental study of the role of
bacteria, apocrine, sweat and deodorants, Arch Dermatol Suppl 68 443–446 (1953)
27. JJ Leyden, KJ McGinley, E Hölzle, JN Labows and AM Kligman, The microbiology of
the human axilla odor, J Invest Dermatol 77 413–416 (1981)
28. JN Labows, KJ McGinley and AM Kligman, Perspectives on axillary odor, J Soc
Cosmet Chem 34 193–202 (1982)
29. PJ Rennie, DB Gower, KT Holland, AI Mollet and WJ Watkins, The skin microflora and
the formulation of human axillary odour, Int J Cosmet Sci 12 197–207 (1990)
30. JN Labows and CJ Wysocki, Individual differences in odor perception, Perfum Flav
9(1) 21–26 (1984)
31. S Puhvel, R Reisner and M Sakomoto, Analysis of lipid composition of isolated human
sebaceous gland homogenates after incubation with cutaneous bacteria: Thin layer
chromatography, J Invest Dermatol 64 406–410 (1975)
32. SN Peck, H Rosenfield, W Leifer and N Bierman, Role of sweat as fungicide, Arch
Dermatol Symposium 39 126 (1939)
33. JN Labows et al, “Axillary odor.”,In K Laden et al, (Eds) Antiperspirants and
Deodorants, 2nd edn, , Marcel Dekker Inc New York (1999)
Chapter 10
Conditioning Agents for

Hair and Skin
A discussion of electrostatic, solubility, hygroscopy and
occlusivity properties in commonly used conditioners.
key words: cationic surfactants, polymers, proteins, emollients,

silicone, humectants, petrolatum, dimethicone
T hink of your skin and hair as your body’s protective armor; it is subject to dam-
age from a variety of external sources, including environmental factors such
as sun, wind and low humidity, as well as physical factors like bathing and hair
styling. The results can be rough, unmanageable and dull-looking hair and dry,
scaly and itchy skin.
Conditioners: Fortunately, health and beauty aids can alleviate the damage
done to your “armor.” Conditioning agents in these products help hair and skin
look and feel better by improving the condition of these surfaces. Hair condition-
ers are primarily intended to make wet hair easier to detangle and comb and to
make dry hair smoother, shinier and more manageable. Skin conditioners primar-
ily moisturize while providing protection from the drying effects of the sun, wind
and harsh detergents. This chapter focuses on the functional raw materials that
provide conditioning.
Substantivity: An ingredient’s ability to improve hair or skin condition de-
pends on it being deposited onto surfaces and preferably remaining intact, even
after rinsing. This resistance to rinse-off is known as “substantivity” and can be
achieved through the use of certain raw materials that, because of water insolubility
or electrostatic attraction, stay on the hair and skin. Examples of the latter include
cationic surfactants, cationic polymers and proteins.
Cationic Surfactants
Quats: Cationic surfactants, in the form of quaternary ammonium salts, or
“quats,” are widely used to condition, particularly in hair care. Quats can be thought
of as ammonium salts with the hydrogen molecules replaced by alkyl groups. At
least one group is a hydrophobic molecule with a long hydrocarbon chain (typically
12–22 carbons). Methyl groups can occupy the remaining sites. The anion is usually
chloride, but it can also be bromide or methyl sulfate.
Quat function: A quat’s ability to condition comes from the hydrophobic nature
of the long hydrocarbon tail and the cationic charge of the polar head group. In
97
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Conditioning Agents for Hair and Skin Beginning Cosmetic Chemistry
aqueous cosmetic formulations, quats dissociate into their ionic components. The
cation attached to the hydrocarbon chain is attracted to anionic charges present in
the skin and hair’s protein structures. This electrostatic interaction, coupled with
the fatty nature of a molecule’s hydrocarbon portion, inhibits rinse-off.
With the fatty portion of the quat deposited on the surface, many benefits be-
come apparent. The hair cuticle is smoothed, resulting in a more lubricious, softer
feel with easier combing ability. Also, quat conductivity reduces static electrical
build up. This reduces fly-away and improves manageability.
Potentials for irritation and formulation compatibility problems are some
drawbacks of quats. For example, combining cleansing and conditioning systems
in products such as 2-in-1 shampoos can lead to stability problems because quats
and anionic surfactants may be incompatible. Another drawback is the relatively
high potential for skin and eye irritation.
Quat diversity: A wide variety of quats exist, including ethoxylated and mono-,
di- and tri-substituted forms. If the degree of substitution increases, more fatty
material is deposited, and quats normally will exhibit better conditioning. However,
this increase also reduces the material’s water solubility, making formulation more
difficult. In a process known as “ethoxylation,” you can overcome this insolubility
by increasing the number of molecular hydrophilic groups. The drawback in this
case is that a higher water solubility reduces quat substantivity.
Cationic Polymers
Cationic polymers are another type of substantive raw material commonly used
in hair-conditioning formulations. They are made by attaching quaternized fatty
alkyl groups to modified natural or synthetic polymers. While structurally similar
to quats, they have many more cationic sites per molecule and much higher mo-
lecular weights.
Solubility: Cationic polymers must be substantive to effectively condition. As
with quats, a polymer’s cationic nature allows substantivity via coulombic attraction
to anionic surfaces. However, cationic polymers are also used in anionic surfactant-
containing formulas, such as shampoos, where they are solubilized and expected
to wash away during use. However, this does not happen because of a unique solu-
bility mechanism. Anionic surfactant systems containing cationic polymers can be
designed so that polymers are soluble in the product but become insoluble during
rinsing and deposit on the hair.
This occurs because of an association between the cationic polymer and the
anionic surfactant in cosmetic formulations like shampoos. With excess surfactant,
the polymer is solubilized, creating a clear solution. However, during rinsing, the
surfactant concentration falls below the critical level required for solubilization,
and the polymer/surfactant complex deposits on the hair.
Benefits: Once deposited, cationic polymers provide hair with slip, manage-
ability and good combability. They increase body in damaged hair, spread well and
evenly, and can improve split ends. Their relatively high activity, which allows low
use levels, and compatibility with anionic surfactants when properly formulated,
99
make them ideal conditioning agents. A potential drawback of using cationic poly-
mers is their tendency to build up with repeated usage. This can weigh the hair
down and give it an unappealing look and feel.
Production: Cationic polymers can be made from a variety of synthetic as
well as natural polymers, such as guar gum and cellulosics. A polymer’s physical
characteristics vary according to the monomer and monomeric ratios used in its
manufacture. Molecular weight is another factor affecting the polymer’s physical
characteristics and performance properties.
Proteins: Proteins, polypeptides derived from various plant and animal sources,
are common conditioning agents. Because of their similarity to the proteinaceous
structure of hair and skin, they are naturally absorbed. Once deposited, proteins are
said to improve surfaces by attaching to the damaged sites. Also, their substantivity
can be enhanced through reaction with quaternized materials.
Emollients
In contrast to the above materials, which primarily depend on electrostatic
association to remain on hair and skin, other conditioning agents also use water
insolubility to stay in place. Such conditioners provide a variety of benefits related
to improved smoothness and lubricity. Known as “emolliency,” this property en-
compasses oils, esters and waxes.
Oil: Oils are water-insoluble hydrocarbon mixtures isolated from organic sources
such as petroleum. Mineral oil, for example, is composed of high-boiling distillates
isolated from crude oil. These distillates include long-chain hydrocarbons and
some saturated ring compounds. Other sources for natural oils include sunflow-
ers, olives, coconuts and peanuts. They are mixtures of triglycerides of myristic,
palmitic, stearic and other long-chain fatty acids. The conditioning effect of these
oils comes from their hydrocarbon nature. They spread easily onto surfaces and
can leave transparent, water-repellent films. These films improve slip, shine and
softness of hair and skin.
These oils are ideal cosmetic ingredients because, in general, they are inert
and compatible with skin. Unfortunately, oils that contain double-bonded fatty
compounds can become rancid. If oils are contaminated during the refinement
process, they can become comedogenic, meaning they can lead to acne.
Silicone oil: Silicone oils are another emollient common to skin- and hair-care
products. As with other oils, they have a long hydrophobic chain. Unlike other oils,
their chain comprises silicone-oxygen units with methyl groups attached. Silicone
oil has very low surface tension, allowing for better spreading and more efficient
film formation. They increase lubricity and ease wet hair combing. They are also
particularly good for improving surface shine and luster.
One drawback of silicone oil is its insolubility in water, alcohol or mineral oil.
This makes it difficult to properly disperse in finished formulations and retain its
functional properties. Furthermore, it has a tendency to build up, and can also
contribute to static charge.
100
Esters: Other common emollients are esters and waxes. Esters are created from
a fatty acid reacting with a fatty alcohol. They provide good slip and a nongreasy,
aesthetically pleasing feel to hair and skin. They are also effective in enhancing
shine and reducing the greasy feel of oils.
Waxes: Waxes are solid mixtures of hydrocarbon materials with relatively high
melting points, such as fatty alcohols, acids and esters. Paraffin wax, obtained from
petroleum, is an example of this type. Another is lanolin, a wax derived from sheep’s
wool. Waxes form a water-repellent film on skin and hair surfaces. They also improve
the emolliency of other oils by raising the melting point of the resulting surface
film. Some drawbacks of using waxes are their tacky feel, variable composition, and
potential difficulty in formulating.
Humectants
Humectants are a class of conditioning agents that work by an entirely different
mechanism. They are “hygroscopic,” meaning they absorb water from the environ-
ment and promote water retention. This is important to skin care since skin, a living
organ, must maintain a specific moisture level to remain healthy. Hygroscopy is less
important with hair since it is essentially dead protein and therefore doesn’t require
moisture to “live.” Still, this mechanism is helpful in controlling certain physical
properties, such as brittleness. A variety of humectants are common throughout
the industry in both hair- and skin-care products.
Polyols: Most humectants are “polyols,” in that they contain multiple hydroxyl
groups that attract and bind water. Glycerin and sorbitol are two common examples
often used in skin-care products to help retain moisture in the skin’s upper layers,
specifically the stratum corneum. Polyol concentrations range from 1–25%. In fact,
in the early days of the cosmetic industry, glycerin diluted with rosewater was a
common skin moisturizer. Today, skin-care emulsions contain humectants at lower
levels, typically 1–5%, in combination with other conditioning agents.
Uses: Due to their inherent water solubility, polyols will not remain on hair after
rinsing. Therefore, although humectants can be useful in hair-care products, their
effectiveness as conditioning agents is limited. Nonetheless, glycerin and related
materials are particularly useful in leave-on products, particularly those formulated
for the ethnic market. Through hydrogen bonding, their hydroxyl groups can interact
with the hair’s amino acid structure to provide moisturizing and softening.
Product quality: Interestingly enough, humectants are often added to emulsion-
type conditioning products for a different reasonóto reduce moisture loss from the
product itself. The same properties that make glycerin a good skin moisturizer also
help it reduce water loss from oil and water emulsions. Polyols prevent “skinning,”
or drying, which leads to film formation on the product. In this manner, they help
improve the consistency and aesthetic desirability of creams and lotions.
There are some negatives associated with humectants. For example, an excess
can cause hair or skin to feel sticky. In cases of low ambient humidity, care must
be taken so the humectant does not draw moisture from the deeper layers of the
skin and release it into the atmosphere. Also, as discussed above, humectants are
101
not substantive to hair and skin and may easily wash away. Therefore, they are not
effective as conditioning agents in hair conditioners or skin lotions that rinse off.
Others: Common humectants in the glycol family include propylene glycol,
dipropylene glycol and various polyethylene glycols. These materials are less com-
monly used as humectants since their water-absorption properties are significantly
lower and they may be somewhat more irritating to skin than glycerin.
Another important moisturizing agent in this category is sodium pyrollidone
carboxylic acid (sodium PCA). This acid is a component of the skin’s natural
moisturizing factor (NMF), a complex blend of lipids and humectants that help
maintain the skin’s moisture level. Although sodium PCA is occasionally employed
in hair-care products, its primary use is in skin lotions, where it helps bind moisture
in the skin’s upper layers.
Occlusive Conditioners
Finally, there are occlusive agents. Like humectants, these materials provide
conditioning via moisturization. They moisturize, not by adding water, but by form-
ing a barrier against moisture loss. In the case of skin care, occlusive agents form
a film on the skin’s top layers to reduce transepidermal water loss, or water vapor
that transpires through the skin.
Petrolatum: Commonly known as petroleum jelly, petrolatum is the most ef-
fective of these materials and is widely used in skin-care products at levels typically
ranging from 1 to 3%. Petrolatum is a refined fraction of petroleum and can form
a particularly effective film barrier against moisture loss. It has some use as a hair-
conditioning agent, usually in ethnic products, where it helps smooth and control
wiry hair. Petrolatum also provides significant sheen.
Greasiness is the primary drawback of petrolatum, typically considered too
greasy for use in leave-on hair conditioners for Caucasian hair. When used at high
levels in skin-care products, it can impart an undesirable greasy, sticky feel. Also,
its hydrophobic nature makes it difficult to remove, which may be an advantage or
disadvantage, depending upon the application.
Dimethicone: Silicone, specifically dimethicone, is another highly effective
occlusive agent and is often found in skin lotions, in combination with petrolatum.
A siloxane backbone makes dimethicone very hydrophobic and capable of form-
ing hydrophobic films that help protect skin from environmental damage, such as
the drying effects of harsh detergents. For this reason, dimethicone is approved
as an active ingredient in the FDA’s Over-The-Counter (OTC) Drug Monograph
of skin-protectant agents. Its use level is typically about 1%.
Dimethicone is also commonly used in hair-conditioning products, but not
for its occlusive properties. Rather, it functions as an emollient and is helpful in
smoothing and enhancing shine.
It is important to note that many emollients, including waxes, esters and oils,
have hydrophobic natures and the ability to form films. Thus, they also have oc-
clusive properties.
102
Summary
We have shown that hair and skin surface conditions can improve with treat-
ment. Such conditioning effects can be achieved with the application of a variety
of chemicals. When formulating, you should be thoroughly aware of each material’s
strengths and weaknesses. Skilled formulators artfully combine these raw materials
to create a well-balanced conditioning product.
Recommended Reading
HW Hibbot, Handbook of Cosmetic Science, MacMillan Co, New York 59–77
(1963)
“Glycerine, A Key Cosmetic Ingredient” In: E Jungerman and N Sonntag (Eds),
Cosmetic Science and Technology Series, vol III, Marcel Dekker Inc, New
York (1991)
RY Lochhead, The History of Polymers in Hair Care 1940-present, Cosmetics
& Toiletries 103 36–49 (1988)
WH Schmidt and DF Williams, Chemistry and Technology of the Cosmetics
and Toiletries Industry, Blackie Academic and Professional, London 17–21
(1992)
Chapter 11
Surfactant Science
Surfactants are the “work horses” of the cosmetic industry, and
all cosmetic chemists would benefit from learning the basic
principles of surfactant chemistry.
key words: wetting agents, foaming agents, emulsification agents,

conditioning agents, and detergents
A s a chemist recently recruited to our cosmetic industry, or as a recent chem-

istry graduate, you may be surprised to discover that the technical foundation
of the personal-care industry is built upon an area of science that is only briefly
discussed in most chemistry curricula. This foundation is the physical chemistry
of surfactants at surfaces.
Surface tension of a liquid is a result of internal attractive forces. These forces
cause the liquid’s surface to act as if it were a stretched elastic membrane, thus
causing it to form spherical droplets1. However, as you may not know, chemicals
which can alter this property are known as surface active agents or surfactants.
The Physical Chemistry of Surfaces

In simple terms, surfactants are compounds that are both hydrophilic (“water-
loving”) and lipophilic (“oil-loving”). The water-soluble portion may be a salt group,
which ionizes in solution to yield a charged, anionic or cationic group. It can also
be a polar moiety, such as a hydroxyl group (OH), which can easily hydrogen-
bond to enhance water solubility of the entire molecule. The oil-soluble portion
is generally a hydrocarbon, usually a relatively long, branched or straight, carbon
chain. Based on the simple chemical principle of “like dissolves like,” the long,
non-polar chain associates itself with oily materials, while the polar head group is
attracted to water.
Molecules that possess at least two groups, which in pure form would be in-
soluble in each other, are referred to as amphilic materials. These molecules are
of major importance because of the way in which they organize in solution. Water,
the most commonly encountered solvent used in the personal care industry is an
amazing material. The unique physical properties of water make it a material that
is necessary for life, as we know it. Table 11.1 outlines the unique properties of
water.2
103
104
Surfactant Science Beginning Cosmetic Chemistry
Table 11.1. Salient Properties of Water
1. Water is a tasteless, odorless liquid at ambient temperature and pressure.

2. Water is a polar molecule. Since oxygen has a higher electronegativity than
hydrogen, the charge difference is called a dipole. The interactions between
the different dipoles of each molecule cause a net attraction force.
3. Another very important force that causes the water molecules to stick to one
another, and have a high surface tension, is the presence of hydrogen bonding.
4. Water has a high surface tension caused by the strong cohesion between
water molecules because it is polar. The apparent elasticity caused by surface
tension drives the capillary waves.
5. Water also has high adhesion properties because of its polar nature.
6. Capillary action refers to the tendency of water to move up a narrow tube
against the force of gravity.
7. Water is a very strong solvent, referred to as the universal solvent, dissolving
many types of substances.
8. All the major components in cells (proteins, DNA and polysaccharides) are also
dissolved in water.
9. Water has the second highest specific heat capacity of any known chemical
compound, after ammonia, as well as a high heat of vaporization (40.65 kJ
mol−1), both of which are a result of the extensive hydrogen bonding between
its molecules.
10. Water is miscible with many liquids, for example ethanol, in all proportions,
forming a single homogeneous liquid. On the other hand water and most oils
are immiscible usually forming layers according to increasing density from the
top. As a gas, water vapor is completely miscible with air.
Perhaps the most important factor to consider in working with surfactants is

how they impact on the hydrogen bond is found between water molecules. In a
discrete water molecule, water has two hydrogen atoms and one oxygen atom.
Two molecules of water can form a hydrogen bond between them; the simplest
case, when only two molecules are present, is called the water dimer and is often
used as a model system. When more molecules are present, as is the case in liquid
water, more bonds are possible because the oxygen of one water molecule has two
lone pairs of electrons, each of which can form a hydrogen bond with hydrogen
atoms on two other water molecules. This process can repeat so that every water
molecule is H-bonded with up to four other molecules (two through its two lone
pairs, and two through its two hydrogen atoms.)
Liquid water’s high boiling point is due to the high number of hydrogen bonds
each molecule can have relative to its low molecular mass, not to mention the great
strength of these hydrogen bonds. Realistically the water molecule has a very high
boiling point, melting point and viscosity compared to other similar substances not
conjoined by hydrogen bonds.
Surfactants, having an oil soluble portion and a water soluble portion, even if
soluble in water, do not partition themselves uniformly in solution. The reason is
105
that oil mixed with water disrupts the hydrogen bonding network that exists be-
tween water molecules. The expression oil and water do not mix is a well-known
adage. Surfactant molecules like oil molecules likewise disrupt hydrogen bonding,
a situation that is energetically unfavorable.
Definitions
As technical people we want to our formulations to be governed by clear tech-
nical rules and to use simple concepts to organize our world. If we organize our
world according to simple definitions, we would observe:
1. A solution is a homogeneous mixture composed of one or more substances,
known as solutes, dissolved in another substance, known as a solvent.
2. A suspension is a colloidal dispersion in which a finely-divided species is com-
bined with another species, with the former being so finely divided and mixed
that it doesn’t rapidly settle out. In everyday life, the most common suspensions
are those of solids in liquid water.
3. An emulsion is a mixture of two immiscible substances. One substance (the
discontinuous phase) is dispersed in the other (the continuous phase).
Solutions
However the simplicity we desire is often simplistic and elusive. Consider
the term solution. Now consider a fully dissolved 1% solution of sodium chloride
in water. This simple system has sodium ion (Na+), chloride ion (Cl–) and water,
roughly equally distributed over the entire mass of the system. The solution is clear
and homogeneous.
Now consider a 1% solution of a surfactant. Surfactant, or surface active agent
has a water soluble head and a water insoluble tail. A very well known surfactant
is sodium lauryl sulfate (CAS 151-21-3). Like NaCl, Sodium lauryl sulfate has two
ions with opposite charge, but sodium lauryl sulfate in water is very different. The
presence of a large fatty portion makes the product surface active. The structure
of sodium lauryl sulfate is shown in Figure 11.1. Please note the oil soluble fatty
group and the water soluble sulfate group. Not only is sodium lauryl sulfate a very
important anionic surfactant, it demonstrates effects when added to water that are
typical for surfactants.
Water Soluble | Oil Soluble
Figure 11.1. Sodium Lauryl Sulfate

106
A 1% solution of sodium lauryl sulfate, like that of sodium chloride, is clear but
not homogeneous. As one adds sodium lauryl sulfate to water, achieving the lowest
overall free energy drives the orientation of the material in the water. In this case
minimize disrupting hydrogen bonding in water. The sodium lauryl sulfate orga-
nizes itself at the air water interface and then begins to self assembly into micelles.
Figure 11.2 shows this phenonmenon2. The first box shows pure water, having a
surface tension is around 72 dynes/ cm2. As surfactant is added, demonstrated by the
second box, surface tension is falling as dilute surfactant organizing at the surface.
As the surface reaches saturation a very significant situation develops. The surface
tension no longer drops even with additional surfactant. It is at this concentration
called critical micelle concentration that micelles become the dominant form of
surfactant. (The third box in Figure 11.2 shows this situation.)
Figure 11.2. Surfactant Orientation
In aqueous solutions, surfactants cause a reduction in surface tension, usu-

ally expressed in mN/cm (or dynes/cm). By reducing surface tension, surfactants
are able to disperse oil in water. The surface tension is generally reduced from
72 dynes/cm2 to 32 dynes/cm2 for fatty surfactants and 22 dynes/cm2 for silicone
surfactants. Surface tension created by a formulation is of great importance to
cosmetic products.
Surfactants are used as wetting agents, foaming agents, emulsification agents,
conditioning agents, and detergents. While each of these applications require a
specific class of compounds to maximize efficiency, all surfactants regardless of
function in a formulation must lower surface tension in order to provide the other
properties listed above.
107
Surfactant Types
Surfactants can be grouped into four main chemical/structure categories based
upon the ionic nature they contain. This system includes:
1. Anionic (negative charge),
2. Cationic (positive charge),
3. Nonionic (no charge) and
4. Amphoteric (capable of both positive or negative charge, or no charge).
Structures for a very limited number of typical products in each class are shown
in Figures 11.3–11.6.
1a. Alkyl Sulfates

CH3-(CH2)11-OSO3– Na Sodium lauryl sulfate
1b. Alkyl Ether sulfates

CH3-(CH2)11-O(CH2CH2O)3SO3– Na Sodium laureth-3-sulfate
2. Alkyl phosphates
CH3-(CH2)15-OPO3– Na Cetyl Phosphate
3a. Alkyl sulfosuccinate

CH3-(CH2)11-O-C-CH2CH-CO– Na+ Sodium lauryl sulfosuccinate
|| ||
O O
3b. Amido sulfosuccinate

O
||
CH3-(CH2)10-C-NCH2CH2-O-C-CH2CH-CO– Na+ Sodium
| || || laurylamido MEA
H O O sulfosuccinate
4. Soap
O
||
CH3-(CH2)16-C-O– Na+ Sodium stearate
Figure 11.3. Anionic Surfactants

108
1. Alkyl Quats
CH3 Stearyl trimethyl ammonium chloride
|
CH3-(CH2)17-N+-CH3 Cl-
|
CH3
2. Alkyl Amido Quats

O CH3 Laurylamidopropyltrimethyl
|| | ammonium chloride
CH3-(CH2)11C-N(CH2)3-N+-CH3 Cl–
| |
H CH3
Figure 11.4. Cationic Surfactants
1. Ethoxylated Fatty Alcohol

CH3-(CH2)11-O-(CH2CH2O)12H Laureth 12
2. Alkanolamide
O
||
CH3-(CH2)10-C-N-CH2CH2OH Lauramide MEA
|
H
Figure 11.5. Nonionic Surfactants
109
1. Propionate
CH2CH2C(O)O– Sodium lauriminodipropionate
/
CH3-(CH2)11-N Na+
\
CH2CH2C(O)O–
2a. Alkyl Betaine

CH3 Lauryl betaine
|
CH3-(CH2)11-N+-CH2-C(O)O– Na+
|
CH3
2b. Alkyl Amido betaine

O CH3 Lauramidopropyl betaine
|| |
CH3-(CH2)10-C-N-(CH2)3N+-CH2-C(O)O– Na+
| |
H CH3
Figure 11.6. Amphoteric Surfactants
Each type of product finds application in different areas, depending upon the
desired application. Table 11.2 shows the structure function relationship in sur-
factants. It is this critical concept that structure has a direct impact on function in
formulation that is key to maximizing formulation performance.
Anionic surfactants are typically employed in cleansing formulations because
they are excellent detergents, providing both foam and detergency. The most
commonly used product type is the alkyl sulfate. An alkyl sulfate is made up of a
long-chain hydrocarbon with a sulfonate group on one end. A common example is
sodium lauryl sulfate (SLS). Ether sulfates are milder and are enjoying increased
usage.
Altering the nature of the polar head group and the carbon chain can create
a multitude of anionic surfactants. For example, alkyl ether sulfates, alkyl phos-
phates, dialkyl sulfosuccinates and alkanolamide sulfates are all variations on the
same theme.
110
Table 11.2. Surfactant Structure/Function Chart
PRODUCT CLASSES FUNCTIONS
CORROSION INHIBITORS
LEVELLING AGENTS
COUPLING AGENTS
FOAM STABILIZERS
FOAMING AGENTS
WETTING AGENTS
RELEASE AGENTS
DISINFECTANTS
SOLUBILIZERS
DISPERSANTS
DETERGENTS
EMULSIFIERS
LUBRICANTS
DETERGENT
SOFTENERS
Alcohol Aloxylates • • • •
Agricultural surfactants • • • •
Alkanolamides (1:1) • • • • •
Alkanolamides (2:1) • • • •
Alkanolamide Ethoxylates • • • • • •
Alkylaryl Sulphonates • • • • • •
Alkylphenol Ethoxylates • • • • • •
Amine
Ethoxlates • • •

Amine Oxides • • • •
Amphoterics • • • •
Benzyl
Quats • • •
Block
Co-Polymers • • • • • •
Fatty Acid Ethoxylates • • •
Glycerol
Esters • • •
Higher
Alcohol Ethoxylates • •
Imidazolines • • • • •
Imidazoline
Quats • •
Lower
Alcohol Ethoxylates • • • • • •
Phosphate Esters • • • • •
Polyethylene
Glycols • • •
Polypropylene
Glycols • • •
Sulfosuccinates • • • •
Sulfosuccinate
(SS-0-75) • •

Sulfosuccinamates •
111
Amphoteric surfactants: Amphoteric surfactants, such as acyl b-aminopro-

pionates (i.e., sodium laurimino-dipropionate), also function as detergents, but
they have somewhat different chemical structures and properties. By definition
amphoterics are zwitterionic; that is to say that they become protonated, acquir-
ing positive charge in an acidic environment. In alkaline environments they lose a
proton and have a net negative charge.
These materials are generally less irritating than other classes of surfactants.
Thus, they are typically used as primary detergents in “mild” formulations, such as
baby shampoos. Amidobetaines are used commonly providing foam and viscosity
build to shampoo systems.
Cationic surfactants, Cationic surfactants are effective conditioners, with some
foaming; however, they can be irritating to skin and eyes at very low levels compared
to other surfactants. Cationic surfactants provide germicidal properties.
Nonionic surfactants, can be very mild, but are generally considered low
foaming. Applications for nonionics include solubilization, emulsification and
detergency.
In 1949 WC Griffin3 introduced the HLB concept, and the basic method of
applying it to nonionic surfactants for making emulsions. The system determines
the balance of the hydrophilic (water-loving or polar) and the lipophilic (oil-loving
or non-polar) groups of the emulsifier. This contribution remains perhaps the most
important single contribution to the science of emulsions. The elegance is in the
simplicity.
HLB Value= % EO in the molecule/5
From this number one can get an idea of the function of fatty alcohol
ethoxylates.
HLB Application
4–6 W/O Emulsifier
7–9 Wetting Agent
8–18 O/W Emulsifier
13–15 Detergents
15–18 Solubilizer
Surfactant Properties
Detergency
One of the most common functional characteristics of surfactants is cleansing.
Cleansing surfactants, or detergents, are key components of such personal-care
products as soaps, facial washes and shampoos. The cleansing power or detergency
of these products can be described as their ability to remove grease and dirt from a
surface. In cosmetic products, the surfaces typically dealt with are hair and skin.
112
To understand the mechanism of detergency, consider how a shampoo works.

When shampoo is applied to wet hair, surfactant molecules are in solution and are
free to orient themselves around oily particles on the hair.
In this first stage of detergency, the surfactant molecules position themselves
along the oil-and-water interface, with their hydrophilic ends pointed toward the
aqueous solution and their hydrophobic ends associated with the oil droplet. As
described in The Principles and Practice of Modern Cosmetics,4 the detergent
molecule wets the hair shaft by “dragging” water along the surface of the hair,
underneath the oil, thus separating the oil from the hair shaft.
The next stage of detergency involves the suspension and removal of the oily
“dirt.” Using the shampoo example, the surfactant separates the oil from the hair,
while simultaneously surrounding and penetrating the rest of the droplet. When
enough surfactant is available, the oil droplet will be completely surrounded and
suspended in the water. This combination of oil and surfactant forms a spherical
particle known as a micelle. This micelle stays suspended until more water can
rinse it away.
The ability of the formulation to remove soil can be evaluated using hair soiled
with sebum at 0.5% concentration, water hardness 50 ppm and 350ppm at room
temperature.
Foaming Properties
It is important to note that detergency is only one of the physical properties by
which a cleansing surfactant is chosen for personal-care product usage. Foaming
properties, for example, are also very important. Although the amount of foam
produced by a surfactant has little to do with its inherent cleaning ability, most
consumers are convinced it has everything to do with this benefit. In fact, it has
been suggested that the single most important factor of a shampoo to a consumer is
its foaming ability5. In addition to foam characteristics, other important surfactant
properties include: wetting ability, risibility and safety (i.e., irritation potential/
toxicology). A surfactant chosen for use in a personal-care product formulation
must excel at both cleansing and foaming.
Ken Klein offers a rather detailed review of evaluating foam in an article appearing
in Cosmetics and Toiletries6. Ken, a very well respected authority in personal care
formulations recommends a blender foam density/stability/ lubricity test developed
by Unilever. Ken’s article is presented as Appendix 11.1.
Appendix 11.1
Ken Klein article Cosmetics and Toiletries Vol. 119 No. 10 p.32–35
113
Solubilization
The same mechanism, which enables a surfactant to remove grease and dirt
from a surface, allows it to solubilize oil in a water-based formulation. This point
is important. While water is the major component in many cosmetic formulations,
other important ingredients are not water soluble, such as emollients or fragrances.
A surfactant can be used to disperse these oil-soluble components. In this process,
known as solubilization, the surfactant once again forms a micelle with the oil. But,
instead of assisting in the removal or rinse-away process, as in the case of detergency,
the function of the micelles is to keep the oil dispersed in the water phase. Through
this, relatively small amounts of hydrophobic materials (e.g., fragrances) can be
carried by water systems without loss of clarity. Typically, nonionic surfactants are
used for this purpose, due to their ability to couple oil and water without negatively
affecting other characteristics of personal-care formulations.
Two types of nonionic surfactants commonly used for solubilization are ethoxy-
lates and propoxylates. These compounds are ethers formed by reacting ethylene
oxide or propylene oxide with a fatty compound. The degree of ethoxylation or
propoxylation will affect the solubility of these compounds in water, alcohol and
oil. Generally, the more ethylene or propylene oxide present, the more hydrophilic
the surfactant will be. Commonly used ethoxylates are polysorbate 80 or sorbitan
oleate. An example of a propoxylate is PPG-10 cetyl ether.
Emulsification
As we know, surfactant molecules can disperse oil in water by virtue of their
ability to reduce surface tension. This ability allows certain types of surface-active
agents to form relatively stable mixtures of oil and water. These mixtures, known
as emulsions, provide the basis for a variety of products ranging from cosmetic
milks, lotions and creams to pharmaceutical ointments. As defined by Paul Becher,
emulsions are two-phase systems “consisting of a fairly coarse dispersion of one
liquid in another, in which it (the first liquid) is not miscible.”6 Becher admits
that this, although accurate, is a rather incomplete definition. He goes on to state
that specific properties must be considered in order to define a given emulsion
completely. Such defining properties include the character of the two phases, the
physical properties of the dispersion (e.g., the size of the dispersed particles) and
how stable the emulsion is over time. A “stable” emulsion can be defined as one
that has no separation during the useful lifetime (shelf life) of the final (finished)
product. A good theoretical discussion of factors that influence emulsion stability
can be found in the Encyclopedia of Emulsion Technology.8
Cosmetic emulsions typically consist of mixtures of hydrocarbon oils and water.
The importance of combining these two immiscible materials is obvious. Water is a
good carrier for many materials; it is innocuous and inexpensive. It also evaporates
without leaving a residue. On the other hand, oily materials, such as those typi-
cally employed in hair conditioners and skin lotions, can be good moisturizing and
conditioning agents. However, they may be esthetically unacceptable if used in
114
concentrated form. By employing emulsifying surfactants, formulators can combine

the benefits of both oils and water in one product.
We can demonstrate how the structure and properties of an emulsifying surfac-
tant (i.e., an emulsifier) differ from those of a detergent, using sodium lauryl sulfate
(SLS) as in the previous example. As we described, SLS is very water-soluble, by
virtue of the salt-like nature of its polar, sulfate group and its relatively short car-
bon chain. But imagine that, instead of it having a 12-carbon, lauryl backbone, the
chain was lengthened to 18 carbons. And, instead of the molecule being capped
with a sulfate anion, it is closed with a carboxylic acid group (COOH). We now
have stearic acid.
This material has a substantially higher melting rate, and is significantly less
water-soluble than SLS. But, it is still surface active, since it contains both a lipophile
(long-carbon chain) and a hydrophile (COOH group). Furthermore, its properties
are significantly different than SLS. Instead of imparting high-foaming detergency
when added to water, stearic acid can help form emulsions. The exact configuration
of the emulsion depends on the composition of the materials in the internal and
external phases, and the specific emulsifiers employed.
As with detergents, emulsifiers can be anionic, cationic, nonionic, or amphoteric
by nature. McCutcheon’s Detergents and Emulsifiers9 lists numerous examples of
these materials.
Nonionic surfactants are commonly used in cream and lotion products. Unlike
anionic surfactants and cationic surfactants, nonionic surfactants have no electric
charge; therefore, they are compatible with a variety of materials. Furthermore, they
are generally unaffected by pH and salt concentration. This allows formulators more
latitude. Those nonionics containing ethylene oxide linkages have “adjustable” water
solubility. The exact balance of water and oil solubility can be varied by changing
the nature of the carbon chain and the number of moles of ethylene oxide.10
A system of indexing the ratio of hydrophile to lipophile is commonly used
to categorize nonionic emulsifying materials. This system, known as hydrophile-
lipophile balance (HLB), is used to characterize the surfactant requirements of a
given water-and-oil mixture.
Conditioning
Surfactants have other properties not directly related to their ability to disperse
oil; “conditioning” is one such property. Conditioning can be defined as “putting a
material into a workable state.”11 In the case of hair, this usually means leaving the
hair smooth, soft and not prone to static flyaway. For skin, it may mean leaving the
surface of the skin feeling smooth and “moisturized.”
Cationic surfactants are used to condition because of their dual ability to be
substantive to hair and skin, and to impart lubricity and emolliency. In the case of
cationic surfactants, this substantivity—or ability to resist being rinsed away—is
due to the interaction of the positive charge on the polar portion of the surfactant
molecule with the negative charges, which occur as a result of damage to the protein
structure of hair or skin.
115
Wetting
Wetting is one of the most important, and overlooked attribute of a personal
care product. When we wash hair, condition hair, apply pigments to skin or almost
any other process used in personal care, we are spreading a formulation on hair or
skin. This requires proper reduction in surface tension of the formulation so the
product spreads easily and in a cosmetically acceptable manner. Generally nonionic
surfactants and dialkyl sulfosuccinates function to provide wetting.
Draves Wetting is a commonly used method to determine the wetting properties
of a surfactant or a formulation. (ASTM test method D 2281). The Draves Wetting
test involves determining the time required for a cotton skein, a truss of hair or
sample of skin to sink in a solution of surfactant or formulated product.
Special Effects
We have demonstrated that surfactants (as detergents, conditioning agents and
emulsifiers) play a critical role in the primary form and function of many personal-
care products. Surfactants may also have secondary effects. For example, auxiliary
surfactants can be used to alter the performance or properties of detergent systems.
Specifically, amides may be used to enhance the foam of a shampoo while sulfosuc-
cinates or amphoterics can be used to improve mildness. Many anionic surfactants
are also excellent viscosity builders in detergent systems.
In emulsion systems, surfactants, such as cetyl alcohol, help provide thickness
and body to creams and lotions. Other surfactants aid in the rinsing of emulsion
products. Still other surface-active agents provide the slip and emolliency desired
in certain skin- and hair-care formulations. Surfactants like glycol stearate provide
pearlizing or opacity to cosmetic products. In hair conditioners, cationic surfactants
also help control static electrical charge. Some cationic surfactants may possess
antimicrobial properties that are useful in cosmetic products.11
Conclusion
This brief review of surfactant science demonstrates that surfactants are
the “workhorses” of the cosmetic industry. Furthermore, the basic principles of
surfactant chemistry discussed in this article are used by many other industries,
including household products, paints and coatings, pharmaceuticals, textiles and
even automotive products. It is unfortunate that such a critically important area
of industrial technology is so frequently overlooked by academia. All industrial
chemists could potentially benefit from more education offered in the field of
surfactant science.
Published Beginning Cosmetic Chemistry, Second Edition.
References
1. Encyclopedia Britannica, V IX, 15th ed, Encyclopedia Britannica Inc, 689
2. Wikipedia http://en.wikipedia.org/wiki/Water
3. Griffin WC: “Classification of Surface-Active Agents by ‘HLB,’” Journal of the Society
of Cosmetic Chemists 1 (1949): 311
116
4. RG Harry, The Principles and Practice of Modern Cosmetics, Chemical Publishing Co.
Inc, New York 371–372 (1962)
5. M Rieger, Surfactants in Shampoos Cosm & Toil 103(3) 62 (1988)
6. K Klein, Cosm & Toil 119 (10) 32–35
7. P Becher, Principles of Emulsion Technology, Reinhold Publishing Corp New York
(1955)
8. P Becher, Encyclopedia of Emulsion Technology, v2, Marcel Dekker Inc, New York:
(1985)
9. McCutcheon’s Detergents & Emulsifiers North American Edition, McCutcheon
Division, MC Publishing Co, Glen Rock NJ (1994)
10. H Edelstein, Hair conditioners and conditioning, Cosm & Toil 100(4) 31 (1985)
11. Kirk-Othmer Encyclopedia of Chemical Technology, V22, 3rd ed, Wiley-Interscience
332–432 (1983)
Chapter 12
Oils of Nature
Natural oils, fats and waxes, and the processes that turn these
primary ingredients for cosmetic formulations and surfactants.
key words: triglycerides, surfactants, oils, waxes, methyl esters,

fats, butters
T he possible number of materials useful in the formulation of personal-care

products is truly staggering, with new products being introduced all the time.
Understanding the source of many of the raw materials and the technology needed
to make them functional in formulations is very important. One needs to start by
considering the most basic raw materials, what I call the primary ingredients.1
These basic raw materials find their origins in natural oils, fat and waxes, and in
petroleum feedstocks such as propylene and ethylene. This chapter will concentrate
on natural oils, waxes and butters.
Nature has provided a plethora of materials that are potentially useful in personal-
care applications. Man, by selection and bioengineering, has further expanded the
possibilities. The type and source of natural raw materials are major variables to be
considered by the formulator in making new cosmetic products. The formulator
needs to know some basic information on the sources and chemistries of these raw
materials to make informed decisions on product formulation. Performance, cost
and label copy are all determined by the selection of oils and waxes, both as such
and in surfactant molecules.
When one undertakes the task of choosing a triglyceride used in a product, one
must first determine the reason that the particular oil is being added. Triglycerides
derived from plants are natural, non-animal, renewable, biodegradable and organic
and can be ecocert certified. These factors while important are not helpful if the
formulation does not provide consumer perceivable advantageous. Reasons to
choose a specific oil are outlined in Table 12.1.
Table 12.1. Why select a specific oil?
1. Cosmetic Elegance
2. Label Name (Marketing)
3. Unique Chemistry
4. Unique Components
Acids
Antioxidants
117
118
Oils of Nature Beginning Cosmetic Chemistry
One could well assume that since natural oils have been around for a long period
of time, that there is nothing additional to discover about their use. This assumption
is incorrect. US Patent Application 20050069516, filed March 31, 2005 discloses a
product for application to the hair, comprising: (i) a first hair conditioning agent,
wherein said first hair conditioning agent penetrates into the core of the hair; (ii)
a second hair conditioning agent, wherein said second hair conditioning agent
penetrates into the cortex region of the hair but does not substantially penetrate
into the core of the hair; and (iii) a third hair conditioning agent, wherein said
third hair conditioning agent remain on the hair surface and does not substantially
penetrate into the cortex of the hair; wherein said product comprises advertising
stating that said first hair conditioning agent, said second hair conditioning agent,
and said third hair conditioning agent condition different regions of the hair. The
patent application goes on to teach that examples of first hair conditioning agents
include, but are not limited to, avocado oil, apricot kernel oil, olive oil, sesame oil,
and coconut oil, Examples of second hair conditioning agents include, but are not
limited to, meadowfoam seed. Examples of third hair conditioning agents include,
but are not limited to sunflower oil, and almond oil.
Many patent applications relate to synergistic effects between formulation ad-
ditives and many natural oils. With the growing interest in green products, one can
reasonably expect that the use of natural oils in formulations will increase.
Oils, Fats, Waxes and Butters

The terms oils, fats, butters and waxes have been misused over the years. Part
of the confusion relates to the fact that oils, fats and waxes are terms that relate to
physical properties, namely titer point, and wax is term defined by chemical na-
ture. Wax is an ester of a fatty acid and a fatty alcohol. Triglycerides are a triester
of glycerin.
Triglycerides: Triglycerides are the tri-ester of glycerin with three equivalents of
fatty acid. Fatty acids are defined as those acids having alkyl or alkylene groups that
are C-5 and higher. Figure 12.1 shows the reaction that produces a triglyceride.
CH2-OH O CH2-OC(O)-R
| || |
CH-OH + 3 RC-OH ———> CH-OC(O)-R + 3 H2O
| |
CH2OH CH2-O-C(O)-R
Glycerin Fatty Acid Triglyceride Water
Figure 12.1. Production of Triglyceride
Triglycerides are a very important class of raw materials for making fatty deriva-
tives, including surfactants. Saponification is a general term to define the chemical
119
reaction that breaks the ester linkage. When the triglyceride is saponified to make
a surfactant, such as soap, glycerin is liberated. When a wax is saponified, a fatty
alcohol is liberated. Thus, the types of products that can be made using the two
types of materials are quite different functionally. Glycerin, produced as a by-
product of saponification, is water-soluble and fatty-insoluble. The fatty alcohol
produced as a by-product of the saponification of a wax is water-insoluble and
generally fatty-soluble.
Differentiating among triglycerides: Normally, a physical property such
as melting point is used to differentiate among the members of a chemical fam-
ily. Because oils, fats, butters and waxes are complex mixtures of homologues of
similar chemical structures, it is difficult to obtain a true melting point. As the
lower molecular weight fractions melt, they act as solvents to dissolve the higher
molecular weight products. This results in a very wide melting “range” for these
compounds. For this reason, titer point is generally determined on fats, oils, waxes
and butters.
The titer is defined as the re-solidification point of the melted oil, fat, butter or
wax. The procedure is to heat the product to be tested until it is completely liquid,
then to slowly cool with stirring. This process is done until the temperature stays
constant for 30 seconds, or begins to rise. The titer point is the highest temperature
indicated by this rise.1
Fats have a titer point of greater than 40.5°C. Oils have a titer point of less than
40.5°C. Butters have a titer between 20–40.5°C.
Oils are liquid at room temperature. We now use this word to describe any
compound that is a liquid and is insoluble in water. As a result, jojoba is referred
to as an oil, despite the fact it is really a liquid wax. It is therefore very important
to realize that the terms wax and triglyceride define the chemical nature of a com-
pound; the terms oil, butter and fat define a physical property.
Classification: The Cosmetic, Toiletry & Fragrance Association (CTFA) now
requires the genus and species of the plants or insects that produce a given wax,
oil, butter or fat and all products that are derived from the various oils, fats, butters
and waxes. This is due, in part, to the European Union’s use of the Latin names for
ingredient listings. This information helps the formulator understand the source
of the fatty portion of the surfactant.
Triglycerides can be classified according to their carbon chain lengths. For
instance, in Table 12.1 the triglycerides are grouped by carbon chain lengths less
than C-18, equal to C-18, and greater than C-18.
Oil Preparation
The process that allows for the transformation of a plant seed into a clear, low-
odor oil suitable for cosmetic use is a process that we generally take for granted. The
properties of the oil are determined by the plant source and the processing used.
The oils discussed in this article are referred to as “vegetable oils.” This distinc-
tion differentiates them from the “essential oils” that are steamed out of a variety
of plant parts, including flowers, leaves, peels and some seeds. These essential
120
oils, which often have an attractive aroma, are not triglycerides. Instead, they are
usually “isoprenoids,” which indicates that they come from a different chemical
pathway in plants. Plants store vegetable oils (triglycerides) as energy sources for
seeds when they germinate.
Pressing: Steam works well to extract essential oils like coriander oil, but it does
not work well for triglyceride oils. Triglyceride and wax ester oils can be squeezed
out of seeds using a turning screw that presses the mashed-up seed against a metal
barrel with slits in the side. The oil and some fine particles squeeze out through the
narrow slits. This operation would be called an oil expeller or seed oil press.
The oil from the seed oil press can be filtered and called “virgin” oil, especially
if it isn’t heated up to get more oil out. The oil from the seed oil press can also be
called “crude” oil. Alternatively, oil can be dissolved in solvent, which can then be
evaporated, leaving the extracted oil.
Often, seeds are flaked to increase surface area. The seeds are processed into
thin flakes before pressing or solvent extraction. The flaking improves oil yield by
breaking open the small oil pockets in the seeds. Sometimes the seeds are heated
before flaking so that the proteins in the seed won’t break down the oil or other
things in the seed. The preheating is also called preconditioning. The oil comes out
more easily if it is hot, but excessive heat damages the oil quality.
Sometimes the seeds are crushed and formed into pieces called “collets” that
have lots of holes or openings. This step also is done before solvent extraction so
the oil can flow out more easily. Solvent extracted oil with some solvent still in it
is called the “miscella.”
Crude oil can usually be good enough for chemical uses. In a process called
“winterization,” a well-filtered “virgin” oil can be kept cold to remove any solid
waxes that might crystallize out.
Many cosmetics applications require cold-pressed, virgin oil. On the other hand,
some seeds are too low in oil to economically remove the oil by pressing. In any
case, once you have the crude oil, you can move onto refining.
Refining: Refining is done by filtering the oil through clay or silica (like fine
sand) that can remove color. In an operation called “degumming,” alkali in water
is added to the oil and some ingredients, especially fatty acids and “phospholipids,”
go into the water or settle out or are filtered out. Finally, in an operation called
deodorization, steam can be passed through the oil to remove odor. This step also
breaks down oxygen attached to the oil, which might lower oil quality.
After all of this refining, the oil should be light in color, odorless, and have no
oxygen breakdown products or solid wax. The customer’s requirements for the oil
in terms of color, odor and the like will determine the number of steps needed to
get an acceptable product. Consequently, the amount of useable oil you have left
after refining is often related not only to the amount of crude oil present in the
seed, but is also related to the requirements of color, titer point and properties you
impose for the final oil.
Functionality: The oils that are commonly used in cosmetic products are com-
plex mixtures of different triglycerides, but also contain various other components
that are useful. For example, olive oil can be processed to contain highly desirable
121
tocopherols, or alternatively processed to remove those tocopherols. For example,

solvent extraction or steam distillation would remove much of the tocopherols. If
the oil is in the formulation for the benefit derived from the tocopherols, how the
oil is processed is key to the functionality and usefulness of the resulting oil.
The winterizing of oils (that is, cooling and filtration of solids from the liquid)
results in a loss of the higher molecular weight fractions. Many times it is exactly
these fractions that provide the unique skin feel or conditioning to the product. It
should be clear that the different processes used in the preparation of an oil may
be critical to functionality.
Natural Oils by Class

Natural oils can be classified as shown in Table 12.2 by their carbon chain
length and the source (animal or plant).
Table 12.2. Classification of triglycerides
Class 1 Animal-derived products rich in carbon chain lengths below C-18

Class 2 Animal-derived products rich in C-18 unsaturated carbon chain lengths
Class 3 Animal-derived products rich in carbon chain lengths greater than C-18
Class 4 Plant-derived products rich in carbon chain lengths below C-18
Class 5 Plant-derived products rich in C-18 unsaturated chain lengths
Class 6 Plant-derived products rich in carbon chain lengths greater than C-18
Class 7 Products having unusual carbon chain lengths or composition
Table 12.3 indicates a large number of products classified by that scheme.
Table 12.3. Natural Oils by Class
CLASS 1 Animal-derived products rich in carbon chain lengths below C-18
Number Name Source CAS Number Predominant species

1. Milk Fat cows milk 8029-34-3 C16 triglyceride
CLASS 2 Animal-derived products rich in C-18 unsaturated carbon chain lengths

2. Tallow animal fat 61789-13-7 C18:1 triglyceride
3. Japan Wax Rhus succedanes 8001-13-6 C16 wax
CLASS 3 Animal-derived products rich in carbon chain lengths greater than C-18
4. Beeswax Cera alba 8006-40-4 C26 wax
5. Shellac Wax Shellac cera 97766-50-2 C30 wax
122
CLASS 4 Plant-derived products rich in carbon chain lengths below C-18

6. Coconut Oil Cocous nucifera 8001-31-8 C12 triglyceride
7. Babassu Oil Orbignya olefera 91078-92-1 C12 triglyceride
8. Palm Kernel Elaeis guineenis 8023-79-8 C12 triglyceride
Oil
CLASS 5 Plant-derived products rich in C-18 unsaturated chain lengths

9. Soybean Oil Glycerin soja 8001-22-7 C18:2 triglyceride
10. Peanut Oil Arachis hypogaea 8002-03-07 C18:1 triglyceride
11. Corn Oil Zea mays 8001-30-7 C18:1 triglyceride
12. Sunflower Helanthus annus 8001-21-6 C18:2 triglyceride
Seed Oil
13. Grape Seed Vitis vinifera 8024-22-4 C18:3 triglyceride
Oil
14. Safflower Oil Carthamus 8001-23-9 C18:2 triglyceride
tinctorius
15. Poppy Seed Populus nigra 8002-11-7 C18:2 triglyceride
Oil
16. Sweet Prunnus
Almond Oil amygdalus dulcis 8007-69-0 C18:1 triglyceride
17. Hazelnut Oil Corylus americana C18:1 triglyceride
18. Walnut Oil Juglans regia 8024-00-2 C18:2 triglyceride
19. Olive Oil Olea europasa 8001-25-0 C18:1 triglyceride
20. Avocado Oil Persea gratissima 8024-32-6 C18:1 triglyceride
21. Sesame Oil Sesamum indicum 8008-74-0 C18:1 triglyceride
22. Tall Oil Tallol 8002-26-4 C18:1 fatty acid
23. Cottonseed Gopssypium 8001-29-4 C18:2 triglyceride
Oil
24. Palm Oil Elaesis guineensis 8002-75-3 C18:1 triglyceride
25. Rice Bran Oil Oryza sativa 68553-81-1 C18:1 triglyceride
26. Canola Oil Canola 8002-13-9 C18:1 triglyceride
27. Apricot Prunus armeniaca 72869-69-3 C16 triglyceride
Kernel Oil
28. Cocoa Butter Theobroma cao 8002-31-1 C18 C18:1 triglyceride
29. Shea Butter Butyrospermum 977026-99-5 C18 triglyceride
parkii
30. Wheat Germ Triticum vulgare 8006-95-9 C18:2 trglyceride
Oil
31. Illipe Butter Bassia latifola 68424-60-2 C18 triglyceride
CLASS 6 Products rich in carbon chain lengths greater than C-18

32. Meadowfoam Limnanthes alba 153065-40-8 C20:1 triglyceride
Seed Oil
33. Rapeseed Oil Brassica capmestris 8002-13-9 C22:1 triglyceride
123
CLASS 7 Products having unusual carbon chain lengths or composition

35. Borage Borago officinalis 801201608 C18:3 (n=6)
Seed Oil triglyceride
36. Linseed Oil Linum 8001-26-1 C18:3 (cong)
usitatissimum triglyceride
37. Castor Oil Ricinus communis 8001-79-4 C18:1 OH triglyceride
38. Veronia Oil Veronia 169360-96-7 C18 epoxy triglyceride
galamensis
39. Tung Oil Aleurites fordii 8001-20-5 C13:3 (cong)
triglyceride
40. Jojoba Oil Buxus chinensis 61789-91-1 C20 ester
41. Candelilla Euphorbia cera 8006-44-8 C31 hydrocarbon
Wax
42. Ongokea Oil Ongokea gore C18:3 acetylenic
triglyceride
A very important use for natural oils is food. When this market segment is
removed from considerations, a handful of oils make up the majority of product
consumed for industrial application.
Cosmetic Applications of Oils

The usage of oils, fats, butters and waxes in personal-care products per se is
relatively low compared to the usage in food applications. Figure 12.2 shows the
percentages of various oils used for non-food purposes.
% NON-FOOD OIL USE
ALL OTHER 6
CASTOR 1
LINSEED 4
TUNG 5
RAPESEED 5
SOYBEAN 9
COCONUT OIL 20
TALL OIL 50
0 10 20 30 40 50 60
Figure 12.2. Relative percentages of selected oils used for non-food purposess
124
The selection of oils in personal-care products is strictly governed by the func-

tional attributes the oil confers and any desire for market claims related to the
perception of the oil’s benefits. This criterion is not the case when choosing oils
for making derivatives. Derivatives by far are the principal use of oils in personal-
care products. In the case of derivatives, the choice of an oil is based upon cost,
availability and carbon chain distribution.
Dry oils: The skin and hair are major areas which oil may be applied for a
beneficial effect. The exact benefit depends principally on the particular oil chosen.
Oils that have a very dry feel, which we classify as ultra light oils, find applications in
sunscreens and massage oil, where a non-greasy feel is critical to product aesthetics.
This class of oils also finds application in aromatherapy.
Light oils: Light oils have a transient conditioning effect when applied to the
hair and improve comb properties, without contributing much to the bulk of the
hair. Many of these oils also contribute gloss to the hair.
Intermediate oils: Intermediate oils find application in skin care as moistur-
izing oils and conditioners on the hair. This type of oil is used in bath oils and is
recommended where a slick feel is desired.
Drying oils: Drying oils form film when exposed to air. The formation of film
is due in large part to the presence of unsaturation in the oil. The use of drying
oils is found primarily in industrial applications, like paints and varnishes, but the
judicious use of these oils in personal-care applications can result in an interesting
class of resin products. Drying oils include linseed oil and tung oil. These oils pos-
sess multiple double bonds, some of which are conjugated.
Functionalized oils: Functionalized oils are those oils that have organic groups
other than alkyl or alkylene pendant groups. While these oils are less well known,
they have unique functionality in personal-care products. For example, castor oil
has a hydroxyl group present in the center of the fatty molecule. The presence of
this group in the molecule gives castor oil its usefulness in making lipsticks.
Derivatives
Natural oils are important raw materials for making a variety of downstream
products. These include fatty alcohols, fatty acids, and methyl esters. These inter-
mediates can be fractionated into specific carbon number products (for example
C12 or lauryl alcohol), or not fractionated and remain coco alcohol.
Fatty alcohols, fatty acids, and methyl esters are in turn are reacted with other
materials to become surfactants, See Chapter 11 “Surfactant Science” for more
details on these materials.
Wax esters: Wax esters are defined as esters of long-chained acids that have
been reacted with long-chained alcohols. Other chemicals are called waxes if they
possess tactile properties similar to a true wax. An example is beeswax. Polishes
are a major application area for this class of materials. Wax esters have two fatty
groups. One is contained in the alcohol portion of the molecule, the other is in
the acid group. Esters are synthesized by the reaction of an organic acid with an
organic alcohol (Figure 12.3). Esterification is the reverse of saponification, in
that ester linkages are formed.
125
O O
|| ||
R-C-OH + R’OH ————> RC-OR’ + H2O
Acid Alcohol Ester Water
Figure 12.3. Synthesis of wax esters
Methyl esters: Triglycerides may be easily turned into methyl esters by reaction
with methanol and catalyst. Base catalysts are preferred. As the reaction proceeds,
the reaction mixture turns hazy as glycerin is liberated. Once complete, the excess
methanol is distilled off, glycerin is removed from the bottom after it settles, and
the methyl ester is distilled into its fractions.
The methyl ester formed by the reaction, if not distilled, is still referred to by the
oil name (for example methyl cocoate). However once fractionated, the material is
named by carbon distribution. Methyl cocoate is fractionated into methyl laurate,
methyl myristate, and so on. The triglyceride source is lost in the name of the methyl
ester. The names for the common alkyl groups are given in Table 12.4.
Table 12.4. Commonly used fatty acid nomenclature
Designation Name Formula

C6 Caproic acid C6H12O2
C8 Caprylic acid C8H16O2
C10 Capric acid C10H20O2
C12 Lauric acid C12H24O2
C12:1 Lauroleic acid C12H22O2
C14 Myristic acid C14H28O2
C14:1 Myristoleic acid C14H26O2
C16 Palmitic acid C16H32O2
C16:1 Palmitoleic acid C16H30O2
C18 Stearic acid C18H36O2
C18:1 Oleic acid C18H34O2
C18:2 Linoleic acid C18H32O2
C18:3 Linolenic acid C18H30O2
C20 Arachidic acid C20H40O2
C20:1 Gadoleic acid C20H38O2
C22 Behenic acid C22H44O2
C22:1 Erucic acid C22H42O2
C22:2 Clupanodinic acid C22H40O2
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Designation Name Formula

C24 Lignoceric acid C24H48O2
C26 Cerotic acid C26H52O2
C28 Montanic acid C28H56O2
C30 Myricic acid C30H60O2
C32 Lacceroic acid C32H64O2
C34 Geddic acid C34H68O2
Transformation into Surfactants

The selection of a hydrophobe to prepare a surfactant is one of many factors
that have a profound effect upon the final properties of the molecule. The process
used to make the surfactant, the by-products, impurities and co-products are also
important to functionality.
The commercial processes that allow for the transformation of products into
useful surfactants via the processes outlined in Charts 12.1–3 can produce prod-
ucts that have different functional properties when placed in formulations. Care
must be exercised to insure that the raw material chosen is sufficiently defined to
assure formulation performance.
Natural Petroleum-Based
Triglycerides Ethylene Alpha-olefin
Alkanolamide Acid See Chart 4 Alcohol See Chart 3
Methyl Ester
See Chart 5
Chart 12.1. Basic Surfactant Raw Materials

127
Ether Ether
Sulfosuccinate Sulfate Phosphate Sulfate Phosphate
Alkyl Ether
Glycosides Fatty Alcohols Ethoxylates Sulfosuccinate
Ether
Esters Carboxylates Ether Carboxylate
Ester
Esters
Guerbet Alcohols Ethoxylates Phosphates
Sulfates
Ester Phosphates
Sulfates
Chart 12.3. Alcohol Reactions
Amphoterics Phosphobetaine
Sulfobetaine
Complex Esters
Quats Imidazoline
Betaines
Amphoteric
Fatty Amine (See Chart)

Fatty Alcohol
Amine Oxide Ethoxylated Ethoxylated Amines

Amines
Fatty Acid Alkanolamide Aminosulfosuccanate
Ester
Betaine
Amido Amine
Amine Oxide Sorbitan Esters Ethoxylated Sorbitan
Esters
Quats
Sulfobetaine Phosphobetaine
Chart 12.4. Acid Reactions

128
Sulfato Ester Ethoxy Ester
Methyl
Alkanomide
Ester
Alcohol
Chart 12.5. Methyl Ester Reactions
Conclusion
The preparation of useful surfactants in the personal-care market is dependent
upon several factors. These include the process used by the converter of the natural
materials into intermediates, the converter of the intermediates into surfactants, and
the skill of the formulator to make products that deliver a benefit to consumers. The
importance of the selection of the raw material feedstock is also an important factor
in the preparation of products that all is too often is overlooked. The formulator of
products should consider all of these factors in preparing products.
Published Beginning Cosmetic Chemistry, Second Edition
References
1. AJ O’Lenick, D Steinberg, K Klein and LaVay, Oils of Nature, Allured Publishing Corp,
Carol Stream, IL (2007)
2. AJ O’Lenick, Surfactants Chemistry and Properties, Allured Publishing Corp, Carol
Stream, IL 13–15 (1999)
Chapter 13
Understanding Emulsions
A definition of emulsions and their effect on formulations.
key words: emulsions, hydrophilic, lipophilic, hydrophobic,

microemulsion, macroemulsion, flocculation, HLB
A t some point in your career as a formulator, you will need to combine incom-
patible materials into one product. Many methods have been developed for
accomplishing this task, but none has been employed more than emulsions.
Definitions
Various definitions for emulsions have been suggested, some simple, others
quite complex. In this chapter, we will consider an emulsion to be any heteroge-
neous system that has at least one immiscible or barely miscible liquid dispersed in
another liquid in the form of tiny droplets, like an insoluble oil dispersed in water.
For the interested reader, a more rigorous definition can be found in Becher’s
Encyclopedia of Emulsion Technology.1
Emulsions are the most common type of delivery system used for cosmetic
products. They enable a wide variety of ingredients to be quickly and conveniently
delivered to hair and skin. The types of emulsions used for cosmetic products are
typically semisolid materials consisting of an aqueous (hydrophilic) portion and an
oily (hydrophobic) portion. These two portions make up the internal and external
phases of the emulsion. The internal phase is composed of the materials that make
up the tiny dispersed (or emulsified) droplets, while the external phase is made up
of the rest of the materials. Usually, the external phase (also called the continuous
phase) is the more abundant of the two.
O/W and w/o: The most typical emulsion is one in which an oil is dispersed
in water. Understandably, this type is called an oil/water emulsion (o/w). Another
type of simple emulsion is a water/oil emulsion (w/o), in which water is emulsified.
Whether an emulsion is the o/w or w/o type depends on many factors, including
the concentration of each material in the system, the type of emulsifier and the
processing steps used to create the emulsion.
Size: The particles that make up the emulsion’s internal phase are polydisperse
(meaning they have variable sizes), and their average size is often used for emul-
sion classification. For example, if their average diameter is less than 100 Å, it is
referred to as a micellar emulsion. A particle diameter of 100–2000 Å is known as
a microemulsion. Larger particles make up macroemulsions, which are the most
common type used in cosmetic product formulations.
129
130
Understanding Emulsions Beginning Cosmetic Chemistry
Multiple emulsions: In addition to the simple two-phase emulsions, more

complex systems can be developed. These emulsions may have many internal
phases and are consequently known as “multiple emulsions.” They are emulsions
within emulsions. For instance, water can be dispersed in an oil, which can further
be dispersed in another water phase. This type of emulsion is known as a water/
oil/water (w/o/w). Other multiple emulsions may have three, four or more internal
phases.
Emulsion Components
Because an emulsion is a mixture of incompatible ingredients, one might wonder
how they stay together. In reality, they do not. One of the essential characteristics
of an emulsion is that eventually, given enough time or energy, it will separate into
its original phases. However, cosmetic products are not meant to last forever, and
the true challenge for the cosmetic formulator is designing systems that will remain
stable over the useful life of the product. One way to make this task easier is to have
a good working knowledge about the characteristics of each part of an emulsion
including the oil phase, the aqueous phase and the emulsifier.
Oil phase: This phase is composed of nonpolar compounds that are generally
not compatible with water. These include materials such as fats, oils and waxes
and all of their derivatives, including fatty alcohols and acids, esters, hydrocar-
bons, glycerides and silicones. For cosmetic applications, these materials provide
numerous benefits. On skin, they act as emollients, providing an appealing feel.
They can also soften and improve the skin’s moisture retaining properties because
they leave behind a water repellent film. When used on hair, they provide con-
ditioning to aid in styling and shine to improve the hair’s appearance. While the
components of the oil phase provide many benefits, they are formulated into an
emulsion because, in concentrated form, they can give too much of a good thing
and make hair oily or tacky.
Aqueous phase: This part of an emulsion is made up of water and all the other
hydrophilic materials in the system. These materials can be humectants like glycerin
or propylene glycol, water soluble polymers which thicken or provide conditioning,
preservatives, colorants, electrolytes or feature ingredients such as plant extracts
or hydrolyzed proteins. The aqueous phase has the added benefit of reducing the
greasy feel of the oil phase and reducing the cost of the overall formulation.
Emulsifiers: These compounds make emulsions possible by stabilizing the
dispersion of the internal phase in the continuous phase. They are the surfactants
that reduce the interfacial tension between the two phases. Typical emulsifiers
are molecules that have a hydrophilic portion and a lipophilic portion. They are
classified as either anionic, cationic, nonionic or amphoteric, depending on the
nature of their water soluble head group. Stearic acid is an example of an anionic
emulsifier. It has a long, lipophilic carbon chain (tail) attached to a hydrophilic
carboxylic acid group (head).
When placed in water, emulsifiers have a tendency to align themselves in a
manner that reduces the interaction between their hydrophilic and lipophilic ends.
If enough emulsifier is present, spherical structures called micelles can be formed.
131
These structures are aggregates in

which the lipophilic tails are orient-
ed toward the center of the micelle
and the hydrophilic heads form the
outer surface (Figure 13.1).
Emulsion Structures
While micelles are a common
structure found in emulsions, they
are only one of many possibilities.
The exact structure adopted by
any composition depends upon
the component concentrations,
their solubility characteristics and
the method by which they are pro- Figure 13.1. Emulsion micelle
duced. At higher concentrations, the
internal phase can pack itself into
long, hexagonal columns. At even higher concentrations, lamellar structures, which
are planar sheets of surfactant, are formed. These liquid crystalline structures are
similar to the lipid bilayers common in biological membranes. They are typically
employed in skin products and are said to give more effective results.
Emulsion Stability
As most chemists know, oil and water do not mix. If they are put together in a
container and shaken, the oil may break into smaller particles and disperse for a
few moments. However, when the shaking stops, the dispersed oil particles quickly
combine and separate from the water. When an emulsifier is added to this system,
the oil particles stabilize because they are incorporated into the lipophilic interior
part of the micelles. In this way, the oil particles are shielded from each other and
their coagulation is inhibited, resulting in a stable emulsion.
Although emulsifiers help stabilize the interaction between the oil and water
phases, emulsions are still inherently unstable according to the second law of
thermodynamics; they eventually will separate. The speed at which this occurs or
how complete the separation is depends on the composition of the emulsion. For
instance, a system of mineral oil and water will form a macroemulsion when agitated
that immediately separates upon standing. If a small amount of an emulsifier such
as polysorbate 80 is added, the system may remain stable for a few days. Other
emulsions with different oil phases and emulsifiers can remain stable for years but,
in theory, every emulsion will separate.
Emulsion Destabilization
Investigation into the process of emulsion destabilization has revealed four
primary mechanisms. They are creaming, flocculation, coalescence and inversion.
Although explained separately here, they occur simultaneously in real life emul-
sions (Figure 13.2).
132
Figure 13.2. Emulsion destabilization processes
Creaming: The droplets in an emulsion have varying densities and are, there-
fore, prone to a destabilizing process known as creaming. In this process, the less
dense particles tend to rise to the top. The resulting emulsion has two sections,
one having more of the internal phase and the other having more of the external
phase. A classic example is unhomogenized milk in which the fatty cream rises to
the top. Creaming represents a less serious stability problem then, because none
of the particles actually combine. It can be reversed by agitation.
Flocculation: During this process, the internal phase droplets form a weak,
reversible association. This process is typically caused by inadequate surface
charge on the micelles, which reduces the repulsive force between them. The two
particles remain distinct, and they do not change in size. This development can be
demonstrated by taking two billiard balls and touching them to each other. While
they are touching, an association is formed. However, it can easily be disrupted
by removing one of the balls. In the same way, flocculation in an emulsion can be
reversed by providing agitation to the system. For this reason, flocculation is also
a less serious threat to emulsion stability.
Coalescence: When two internal phase droplets get close enough, they can
combine to form one larger particle. This process represents a more serious sta-
bility problem because it is irreversible. If enough particles coalesce, the result is
a complete separation of the two phases. A similar phenomenon called “Ostwald
ripening” also happens in emulsions. This process, first described by Wilhelm
Ostwald in 1896, involves the tendency of smaller particles to combine with larger
particles producing even larger particles and less stability. From a thermodynamic
standpoint, molecules at the surface of a particle are energetically less stable than
those packed in the middle. For smaller particles the ratio of surface to internal
molecules is much higher than those of larger particles. Smaller particles will thus
combine with larger ones to reduce the overall energy of the system. This process
can eventually lead to phase separation.
133
Inversion: While separation is one consequence of the emulsion destabilization

process, phase inversion is another. When a phase inversion occurs, the external phase
becomes the internal phase and vice versa. A change like this is usually undesirable
because the physical characteristics of the resulting emulsion will be different.
Other factors: It has been found that elevated storage temperatures accelerate
the emulsion destabilization while reduced temperatures slow it down. Evapora-
tion of the aqueous phase can reduce emulsion stability. Factors such as microbial
contamination and undesired chemical reactions can also accelerate instability.
To some degree, any emulsion is susceptible to each of the destabilizing pro-
cesses. The impact these processes have on the different types of emulsions can
be varied. For instance, transparent microemulsions can become translucent due
to flocculation. This outcome is typically not desirable for clear products, and steps
must be taken to prevent it. When flocculation occurs in a macroemulsion, however,
it is not as noticeable because these emulsions are opaque from the start. Coales-
cence is more of a problem for macroemulsions because it can cause a variation
in rheology. Only when an emulsion is properly formulated can the effects of the
destabilizing forces be minimized.
As emulsions become unstable, their physical and chemical compositions may
vary. Different methods can be used to determine the degree of destabilization.
The simplest of them includes direct observation and pH and viscosity checks.
Other more involved methods include light scattering techniques, conductivity
measurements, microscopic evaluation and even NMR.
The Stepwise Approach

Formulating an emulsion can be tricky with the thousands of different ingre-
dients that can be used to make one and all the destabilizing processes that can
ruin it. However, the science of emulsion formulation has come a long way since
the days when our ancestors put together crude systems of beeswax, olive oil and
rose water. Using a stepwise approach, formulating an emulsion can be a much
more manageable task.
The process begins by determining the type of product desired. This choice,
in turn, determines the type of emulsion used, the composition and concentration
of the oil and water phases, and the type of emulsifier employed.
Type of product: If one wants to create a hand cream, antiperspirant, moistur-
izing cream or shaving cream, he or she should consider the common o/w macro-
emulsion. This versatile system has controllable characteristics. It can be made to
feel dry or greasy depending on the amount and type of oil phase utilized. It can
be made into thick pastes or thin lotions. This type of emulsion is typically chosen
for applications requiring a relatively small amount of fatty material. For example,
hand creams are typically o/w emulsions with approximately 10–25% oil phase.
When a large amount of oil is desired, a w/o emulsion is typically a better
option. This system has a greasier feel and will leave a longer lasting residue. It
has the advantage of not easily drying out, so in some respects it is more stable.
Products that are good candidates for a w/o emulsion include emollient creams,
134
hairdressings, sunscreens and certain types of cleansing creams. Microemulsions

are good for clear products.
Developed in the early 1940s, they are formed by first making a w/o emulsion,
then mixing that emulsion with a water phase. These types are particularly useful
for encapsulating materials that give prolonged release when applied to a surface
such as skin.
Microemulsions demonstrate better stability than macroemulsions and appear
to be less irritating. An interesting phenomena related to microemulsions are mi-
croemulsion gels. When the right amount of material is combined, a viscoelastic
gel is formed, termed a “ringing gel.” Its name comes from the ringing sensation
the system makes when shaken. Products such as hair relaxers, permanent waves
and depilatories have all been successfully produced using microemulsions.
Multiple emulsions are an interesting and yet not fully explored type of emulsion.
They have great potential for use in prolonged ingredient release, odor masking
and the stable delivery of materials such as vitamins and enzymes. Unfortunately,
they are much less stable than conventional emulsions.
Composition/concentration: The product type will also determine the kinds of
materials included in both the oil and water phases and the concentration of each.
A full listing of the types of materials and their function is beyond the scope of this
chapter, however for more information is available please consult references 2–3.
Once the type of emulsion and composition of the oil and water phases are de-
termined, the emulsifier must be chosen. Fortunately, systems have been established
to help choose an appropriate emulsifier for any desired oil and water system.
Emulsifier: The most widely used method for choosing an emulsifier is known
as the hydrophilic/lipophilic balance (HLB) system, first proposed by Griffin.5 This
system uses a relative scale of 1–18 to rate emulsifiers, based on their affinity for
oil and water. Compounds with a low HLB are more lipophilic, while higher HLB
materials are hydrophilic. The type of emulsion that will be formed depends on a
material’s HLB value. In general, materials with an HLB rating of 3–8 will result
in a w/o emulsion, while those with a value of 10–18 will give an o/w emulsion.
This system was originally developed for nonionic emulsifiers; however, it has now
been applied to other surfactant types.
Using the HLB system, it is also possible to calculate the required HLB value
for a given oil system and the type of emulsion desired. For example, mineral oil
requires a material with approximately a 4.5 HLB to create a w/o emulsion. To
make an o/w emulsion with mineral oil requires an emulsifier with an HLB value of
about 11. Determining a material’s HLB value can be done experimentally, however,
published charts are available. It should be noted that while the HLB system can
provide information about the type of emulsion a material can produce, it does
not give information about the concentrations required. These determinations can
only be made through experimentation.
Because the HLB system did not always work when silicone was introduced
into a system, a new method known as the 3-D HLB was developed. This method
uses phase diagrams to refine the HLB values of materials that will be used in
systems with silicones.
135
The HLB and 3-D HLB systems are not the only ones that are available for
formulators. Because it is known that a material’s ability to emulsify changes with
temperature, the Phase Inversion Temperature (PIT) system was developed. It is
very similar to the HLB except that it rates materials based on the temperature at
which the emulsifier causes o/w emulsions to invert to w/o emulsions. Another, more
sophisticated system is known as the Cohesive Energy Ratio (CER) system. This
system rates materials on the basis of thermodynamic principles. It is particularly
useful for many anionic surfactants.
Conclusion
The usefulness of emulsions for cosmetic products has been demonstrated by
their continued use since the dawn of time. They will undoubtedly be an important
product form for many years to come. While emulsions are an indispensable tool
for formulators, it is unfortunate that more attention is not given to them in the
typical college chemistry curriculum. Perhaps this review will inspire the reader
to learn more about these interesting systems.
Published 1995 Cosmetics & Toiletries magazine.
References
1. P Becher, Encyclopedia of Emulsion Technology, Vol 3, Marcel Dekker, NY (1996)
2. Cosmetic Bench Reference, Allured Publishing, Carol Stream, IL (1998)
3. Harry’s Cosmeticology 8th edition, CHS Press, New York (2000)
4. P Becher, Emulsions: Theory and Practice, Reinhold Publishing Corp, NY 2 (1965)
5. W Griffin, J Soc Cos Chem 1 311 (1949)
Additional References
1. HW Hibbot, Handbook of Cosmetic Science, Macmillan Company, NY 175 (1963)
2. L Prince, Microemulsions Theory and Practice, Academic Press Inc, NY 1–2 (1977)
3. C Fox, An introduction to multiple emulsions, Cosm Toil 11(101) 101–112 (1986)
4. G Whalley, Surfactant structures and micelles, Happi 8 62–6 (1997)
5. P Becher, Encyclopedia of Emulsion Technology, Marcel Dekker, NY 133 (1983)
6. GM Eccleston, Application of emulsion stability theories to mobile and semisolid o/w
emulsions, Cosm Toil 11(101) 73–6 (1986)
7. MM Rieger, Stability testing of macroemulsions, Cosm & Toil 5(106) 59 (1991)
8. GM Eccleston, Application of emulsion stability theories to mobile and semisolid o/w
emulsions, Cosm Toil 11(101) 135 (1986)
9. C Fox, An introduction to multiple emulsions, Cosm & Toil 11(101) 109-11 (1986)
10. K Gallagher, Microemulsion gels: a formulatorís guide, Happi 2 58–64 (1993)
11. G Dahms, Stabilization and delivery of vitamins and enzymes using multiple
emulsions, J Soc Cosm Chem 47 (4) 278 (1996)
12. A O’Lenick and J Parkinson, Applying the three dimensional HLB system, Cosm Toil
112(11) 59–64 (1997)
13. L Prince, Microemulsions Theory and Practice, Academic Press Inc, NY (1977)
Chapter 14
Silicone Chemistry
Silicones are increasingly important in cosmetic formulations,
and silicone science is an area where many new developments
are being made.
key words: silicone, compounds, quartz, polymer, compounds
O ne of the first questions encountered in dealing with silicone based products

relates to the origin of silicone compounds. Because of its electronegativity,
free Si (silicon) does not exist. Rather it combines with oxygen to produce SiO2.
Called sand, quartz, opal and by many other names, this material makes up over
25% of the earth’s crust. It is very common and well known1.
Silicon is the element. It has an atomic number of 14 and an atomic weight
of 28.0855. It is prepared by the reaction of SiO2 with C at elevated temperature.
Table 14.1 shows the reaction.
Table 14.1. Preparation of Silicon Metal
SiO2 + C → Si + CO2
The metamorphosis of quartz into Si metal is the first step in a series of steps
that ultimately provide compounds useful in the personal care market. Figure
14.1 shows the quartz and silicon.
Figure 14.1. Quartz to Silicon. The top left shows SiO,2 which is converted into Si.
© 2005 Thomas O’Lenick Used with permission
137
138
Silicone Chemistry Beginning Cosmetic Chemistry
The term “silicone” is reserved for materials that contain a Si-O-Si linkage.
These materials are well known and are used extensively in the personal care area.
The difficulty is that the term silicone is applied to a wide range of materials rang-
ing in solubility from insoluble in both water and oils, to soluble in water or oil.
To complicate things further, the molecular weight of the polymer will determine
if the resulting product is a wetting agent, a conditioner a gum or a film former.
Silicones are likely the most rewarding class of raw materials to add to a formula-
tion because of the unique attributes these polymers confer and at the same time
one of the most frustrating classes of compounds with which to work because of
the variability of properties available within the class.
Silicone compounds have been known since 1860, but were of little commercial
interest until the 1940s. Over the years, silicone compounds have received growing
acceptance in many personal care applications. In fact it has been said that four of
10 new personal care products introduced in the 1990s have silicone in them.
When the term “silicone is applied to a compound, one thinks of silicone fluids.
While historically silicone fluids are the oldest derivative used in personal care ap-
plications, they are used only sparingly in our industry. The early work with silicone
fluids in our industry has resulted in Silicone Misconceptions, shown in Table 14.2.
While specific product classes that have some of the attributes shown in the table
exist, so do a plethora of materials that are likewise silicone compounds that have
different properties. Understanding the structure/function relationship in selecting
silicones is key to efficient formulations.
Table 14.2. Silicone Misconceptions
• All silicones defoam.

• Silicones are difficult to use in formulations.
• Silicones are water-insoluble.
• Silicones polymerize.
• Silicones are toxic.
• Silicones are difficult to emulsify.
• Silicones are available only at low HLB.
• All silicones are greasy.
Group Opposites
Since water, mineral oil and silicone oil are mutually insoluble, the terms “hy-
drophilic and “hydrophobic” need to be expanded to include silicone compounds.
The following terms have been recommended1;
Hydrophilic (water loving) Hydrophobic (water hating)

Oleophilic (oil loving) Oleophobic (oil hating)
Siliphilic (silicone loving) Siliphobic (silicone hating)
139
• Hydrophobic (water hating) materials can be either oleophilic or siliphilic.

• Oleophobic (oil hating) materials may be either hydrophilic or siliphilic.
• Siliphobic (silicone hating) materials may be either oleophilic or
hydrophilic.
This means that when a fiber, like hair, is treated with either silicone or with
hydrocarbon, very different hydrophobic coating results. If treated with silicone,
the fiber will also be oleophobic. If treated with oil, the fiber will also be siliphobic.
For application in waterproofing fibers, selection of the proper molecule is critical.
Improper selection will result in unacceptable oil staining. This also results in an
expansion of the traditional well accepted two-dimensional HLB system of Griffin2
into to the 3D HLB system when oil soluble, water-soluble and silicone soluble
portions are all in a molecule.3
A recent trend has arisen toward developing personal care products that contain
silicone-derived materials. In fact, it has become rather rare that each issue of your
favorite trade journal does not have a story, press release, or a new product introduc-
tion that contains, includes or involves silicone. Notwithstanding this, the chemistry
of the silicon atom and the various derivatives remain much less understood, ap-
preciated and utilized than the carbon based analogues. Some desire in does exist
in some areas to keep secret the structure function relationship that exists in the
silicone world from becoming as well known as it is in the world of carbon based
molecules. This secrecy coupled with reluctance on the part of some formulators
to use silicone products results in the following questions:
• Why do silicone compounds fail to act in a predictable way in my
formulation?
• Why is there so much trial and error in using silicone compounds?
• Why are compounds purporting to have the same INCI name act so
differently?
The simple fact is that INCI names are given to provide a uniform method of
labeling products. They are not intended to provide the necessary information to
allow one to know with full detail the structure of the compound. In fact one of the
most difficult jobs encountered by a formulator is to match a competitive product
by label for formulations containing silicone.
The functionality of silicone compounds is directly related to the structure.
Unlike traditional fatty compounds, the “structure” is more complex. It requires
an understanding of three components of structure. These are (1) Construction,
(2) Functionalization and (3) Derivitization. Each is critical to functionality.
• Construction relates to the make up of the silicone backbone.
• Functionalization relates to the groups that are on the silicone backbone.
• Derivitization relates to chemistry conducted on the groups added by
Functionalization.
1. Construction—Polymer Backbone Preparation

Silicone chemists like lawyers, accountants and other scientists have created
a jargon that makes communication within the group easier, but at the same time
makes the technology more obscure for outsiders. The “Construction” of silicone
140
polymers relates to the structure of the polymer backbone. It is prepared by react-

ing various silicone precursors to make the “silicone backbone.” The “M”, “D”, “T”
are part of the construction.
A shorthand jargon has been developed to describe construction. It is based
upon the number of oxygen atoms connected to the Si. It is as follows:
CH3
“M unit” is monosubstituted O1/2 –Si–CH3
CH3
CH3
“D unit” is disubstituted –O1/2 –Si–O1/2 –
CH3
O1/2
“T unit” is trisubstituted –O1/2 –Si–O1/2
CH3
–O1/2
“Q unit” is Quadsubstituted –O1/2 –Si–O1/2 –
–O1/2
If the Si atom has anything other than CH3 on it, it is referred to as a “*” com-
pound. It is the Si-H materials that are reacted with vinyl groups in the function-
alization reaction that allows for organofunctional silicone polymers.
CH3
“M unit” is monosubstituted O1/2 –Si–H
CH3
CH3
“D unit” is disubstituted –O1/2 –Si–O1/2 –
H
141
O1/2
“T unit” is trisubstituted –O1/2 –Si–O1/2
H3
Construction Examples
There are three classes of compounds based upon their construction:
Comb—Internal Si-H compounds
CH3 CH3 CH3 CH3
CH3—Si–O—(—Si—O–)50—(–Si—O–)10—Si—CH3
CH3 CH3 R CH3
This type of construction is referred to as M D50 D*10 M.
Terminal—Terminal Si-H compounds
CH3 CH3 CH3
R—Si–O—(–Si—O–)10—Si—R
CH3 CH3 CH3
This type of construction is referred to as M* D10 M*.
Multifunctional—Internal and terminal Si-H compounds.
CH3 CH3 CH3 CH3
R—Si–O—(—Si—O–)50—(–Si—O–)10—Si—R
CH3 CH3 R CH3
This type of construction is referred to as M* D50 D*10 M*.
It should be clear that each class of compound will have different properties
based upon its construction.
142
2. Functionalization—The hydrosilylation reaction

The “Functionalization” relates to the functional groups that are present. They
are generally a direct consequence of Si-H groups reacted with unsaturated groups
in a process called “Hydrosilylation”.
A table of functionalization reagents was shown in Table 14.3. The common
property is the alpha vinyl group.
Table 14.3. Functionalization Reagents
Vinyl Compound Example Produces

Alkoxylated allyl alcohol CH =CH-CH -O-(EO)aH PEG-dimethicone
2 2
Alpha olefin CH =CH- (CH ) CH Alkyl dimethicone
2 2 n 3
Fluoro alpha olefin CH =CH-CH - (CF )n CF Fluoro dimethicone
2 2 2 3
Combinations Mixtures Multifunctional
The “construction” is the molecular knitting machine that makes the silicone
backbone.
The “Functionalization” is the “Lego Set” of appendages that provide
functionality.
“Construction” without “Functionalization” results in silicone homopolymers
(fluids).
“Functionalization” is not possible without “Construction”.
PEG/PPG Dimethicone
Consider the reaction:
CH3 CH3 CH3 CH3
CH3—Si–O—(–Si—O–)a—(O–Si—)b—Si—CH3 + a CH2=CH–CH2O(CH2CH2O)8H m
CH3 H CH3 CH3
CH3 CH3 CH3 CH3
CH3—Si–O—(–Si—O–)a—(O–Si—)b—Si—CH3
CH3 (CH2) 3 CH3 CH3
O(CH2CH2O)8H
143
Regardless of the value of “a” and “b” the INCI name is PEG-8-dimethicone.
The question then becomes is PEG-8-Dimethicone water-soluble? The answer
is it depends upon how many “a” and “b” units there are in the molecule (Table
14.4).
Table 14.4. PEG-8 Dimethicone Properties
Product Old INCI Name New INCI Name

MD10D*5M Dimethicone Copolyol PEG 8 Dimethicone
MD10D2*M Dimethicone Copolyol PEG 8 Dimethicone
MD40D22*M Dimethicone Copolyol PEG 8 Dimethicone
Solubility (1%/10% Weight)

Water Mineral Propylene Cyclo Silicone IPA
Oil Glycol Methicone Fluid
MD10D*5M I/I I/I S/S I/I D/I S/S
MD10D*5M S/S I/I S/S I/I D/D S/S
MD10D2*M I/I I/I I/I I/I D/I S/S
MD40D22*M I/I I/I D/D D/I D/D S/S
Legend I = Insoluble D = Dispersible S = Soluble
3. Derivitization
In instances where the functionalization results in a molecule that has a reactive
group present, subsequent chemistries can be applied to that group. An illustrative
group is the PEG-8-dimethicone
CH3 CH3 CH3 CH3
CH3—Si–O—(–Si—O)a—(–Si—O)b—Si—CH3
CH3 CH3 (CH2) 3 CH3
O–(CH2CH2O)8H
Since the OH group is a carbanol, it can be reacted in many of the same ways
the hydroxyl group in lauryl alcohol ethoxylates can be reacted. These reactions
are called derivitization. Many reactions have been conducted using products of
construction and functionalization as reactants. These are the derivative silicones.
The attached table is an example of products made using this powerful technique.
In fact an entire world of compounds that are analogous to hydrocarbon based
surfactants are available in the world of silicone surfactants. Many of these materials
were patented; some still remain covered by patents.
144
COMPARISON OF HYDROCARBON COMPOUNDS

WITH SILICONE-MODIFIED COMPOUNDS
Anionic Compounds
Hydrocarbon Products Silicone Products
Phosphate Esters Silicone Phosphate Esters5,6
Sulfates Silicone Sulfates7
Carboxylates Silicone Carboxylates8,9
Sulfosuccinates Silicone Sulfosuccinates10,11
Cationic Compounds
Alkyl Quats Silicone Alkyl Quats12
Amido Quats Silicone Amido Quats13
Imidazoline Quats Silicone Imidazoline Quats14
Amphoteric Compounds
Amino Proprionates Silicone Amphoterics15
Betaines Silicone Betaines16
Phosphobetaines Silicone Phosphobetaines17
Nonionic Compounds
Alcohol Alkoxylates Dimethicone Copolyol
Alkanolamids Silicone Alkanolamids18
Esters Silicone Esters19,20,21,22
Taurine Derivatives Silicone Taurine23
Isethionates Silicone Isethionates24
Alkyl Glycosides Silicone Glycosides25
Example Consider PEG-8 Dimethicone Copolyol Succinate. It has the follow-

ing structure:
CH3 CH3 CH3 CH3
CH3 CH3 (CH2) 3 CH3
O–(CH2CH2O)8—C(O)–CH2CH2 –COH
145
It is the product of (1) construction, (2) functionalization and (3) derivitization.

The molecule is marked to show each. Construction in red, functionalization in
green and derivitization in blue.
CH3 CH3 CH3 CH3
CH3 CH3 (CH2) 3 CH3
O–(CH2CH2O)8—C(O)–CH2CH2 –COH
An example of modifying the properties of a compound via derivitization is a

compound known as CetylsilR S
CH3 CH3 CH3 CH3
CH3 CH3 (CH2) 3 CH3
O–(CH2CH2O)8—C(O)–CH2CH2 –C(O)O–
CH3(CH2)15—N+—(CH3) 3
This complex has unique properties, in that it reduces irritation of the quat by
more than an order of magnitude.
25% Active Testing
Product Eye Irritation*
Cetyltimonium Chloride 106.0
Cetylsil S 8.3
This trend is seen at very low concentrations as well.

0.5% Active Testing
Product Eye Irritation*
Cetyltimonium Chloride 6.0
Cetyltimonium Chloride Complex 1.3
*FHSLA 16 CFR 1500.42
The Cetylsil S product is low irritation, does not build up and has very low
irritation properties.

146
References
1. www.siliconespectator.com
2. AJ O’Lenick., J of Surfactants & Detergents, 3 (2) 229 (2000)
3. WC Griffin,, J Soc Cosm Chem, 1, 311 (1949)
4. AJ O’Lenick et al., Cosm & Toil, 111 (10) 37 (1996)
5. AJ O’Lenick et al., Cosm & Toil, 112 (11) 59 (1997)
6. US Patent 5,149,765 to O’Lenick (September 1992)
7. US Patent 4,724,248 to Dexter et al. (February 1988)
8. US Patent 4,960,845 to O’Lenick (October 1990)
9. US Patent 3,560,544 to Haluska (February 1971)
10. US Patent 5,296,625 to O’Lenick (March 1994)
11. US Patent 4,717,498 to Maxon (January 1988)
12. US Patent 4,777,277 to Colas (November 1998)
13. US Patent 5,098,979 to O’Lenick (March 1992)
14. US Patent 5,153,294 to O’Lenick (October 1992)
15. US Patent 5,196,499 to O’Lenick (February 1993)
16. US Patent 5,073,619 to O’Lenick (December 1991)
17. US Patent 4,654,161 to Kollmeier (March 1987)
18. US Patent 5,237,035 to O’Lenick (August 1993)
21. US Patent 4,724,258 issued to Dexter (February 1988)
23. US Patent 5,280,099 to O’Lenick (January 1994)
24. US Patent 5,300,666 to O’Lenick (April 1994)
25. US Patent 5,120,812 to O’Lenick (June 1992)
Chapter 15
Creating Colorful
Cosmetics
An introduction to colorants in the personal care industry.
key words: colorant, inorganic, organic, color additives, dyes,

norms, development, quality control
A dding color to the cosmetic products has many implications. It can be aimed to
hide the sluggish yellowish hue of some bases, or to fulfill the esthetic require-
ments for increased consumer attraction, or, finally, to temporarily color the skin
surface. Indeed, this task is surprisingly complicated and difficult. It is important for
chemists to not only understand the esthetics of color and its impact on consumer
perception, but also to be watchful for problems with color stability/compatibility
in formulations. They must be knowledgeable of the associated regulatory issues,
on a worldwide basis, too.
New chemists are often surprised that colorants are a separate and complex
step in a formulation process. As an introduction to colorants, this chapter will
describe the basic chemistry of these materials, the key regulatory issues associated
with the use of colorants and fundamental factors to consider when formulating.
Unless otherwise noted, specific regulations are based on the US code of Federal
Regulations. Readers are urged to review the CTFA International Color Handbook
for rules for specific regions. Other important norms to be taken into account when
exporting/importing product containing colors are issued by EU and Japan, just to
mention the most significant ones.
Colorants
History: For centuries—in an attempt to imitate the attractive plumage of
many animals—people have used a variety of natural materials, such as coal, chalk,
copper ore, henna, saffron, and other mineral and plant derivatives, to impart color
to the body. Until the 20th century, few limitations were placed on the types of
colorants that could be used in personal-care products or in foods. Such a lack of
legislation proved to be dangerous; many compounds that provided brilliant color
might contain toxic metal complexes. Near the turn of the century, a number of
illnesses and deaths in the United States were attributed to products formulated
with unsafe colorants used in foods.
This tragedy led to the passage of the Food and Drug Act of 1906, which estab-
lished a list of approved color additives. Restrictions for colors used in cosmetics were
147
148
Creating Colorful Cosmetics Beginning Cosmetic Chemistry
added to this legislation in 1938 with the passage of the Food, Drug and Cosmetic
Act, a more comprehensive version of the law. This legislation required that each
individual batch of so-called “coal-tar” colorant must be confirmed as conforming to
the standards set forth in the law to be considered approved or “certified.”3 Despite
efforts to safeguard the public from unsafe colorants, in the early 1950s, several
children fell ill after eating foods that contained high levels of color additives. This
mishap resulted in the Color Additives Amendments of 1960, which allowed the
FDA to set use limitations on colors to ensure that harmful levels would not be
used. It resulted in requirements that color manufacturers provide thorough test
data (“certification”) indicating the safety of their individual batch of colorants. Such
safety concerns in the past 50 years have caused the number of approved colors to
dwindle. In 1959, 116 certifiable colors existed; in 2007, only 36.1,2
Today the debate continues about the safety of specific colorants. Indeed, color
additives are one of the most carefully scrutinized cosmetic ingredients worldwide.
This scrutiny is, in part, because of the chemical reactivity of these colorants, their
impurities, the extended and continuous human exposure through food, cosmetics
and drugs. Strangely enough, for some colorants, the leading international norms
have different views about their safety characteristics, so that quite striking dif-
ferences in purity parameters and acceptance criteria exist in the different part of
the cosmetic planet.3,4
Chemical Classification of Colorants

Colorants are classified as either organic or inorganic, depending on their chemical
structure5. Many organic colors were originally called “coal tar” or “aniline” colors
because they were derived from coal sources, like aniline. In time, synthetic colors
have been obtained through more modern processes. These colorants are avail-
able in a variety of shades and are either water soluble, oil soluble (called dyes) or
insoluble in both vehicles (called pigments). A common insoluble form is known
as a “lake” colorant, which is obtained by precipitating a water soluble dye with
an inorganic substrate (generally insoluble metallic hydroxides or sulfates) with
which it forms absorption and adsorption (as in the chemical definition of a lake)
bonds. Also some simple mixtures of primary colors with approved substrates are
called lakes. Other organic colors are derived form the vegetal world, while most
inorganic colorants are typically metals, metallic oxides or salts.
Organic synthetic colorants: Organic synthetic colorants are complex mol-
ecules with long chemical names such as: ethyl[4-p-[ethyl(m-sulfobenzyl)amino]-
α-(o-sulfo-phenyl)benzylidene]-2,5-cyclohexadien-1-ylidene](m-sulfobenzyl)
ammonium hydroxide, disodium salt.1
For ease of reference, countries have adopted special nomenclature systems for
naming color compounds assigned to modify the shade of cosmetics (C), food (F) and
drugs (D). The United States designates approved colors as FD&C, D&C or Ext.
D&C (Table 15.1), while the European Union (EU) employs Colour Index (CI)
numbers for identification. For example, the color additive named above is known
as “FD&C Blue No.1” in the United States, “Blue No. 1” in Japan4, and “CI 42090”
in the EU3. In the United States, manufacturers must document that each batch
149
of organic colorant meets or exceeds the FDA standards before it can be sold for
cosmetic, drug or food use. In EU and Japan, specific purity criteria exist, that must
be respected when using the color additives, but no batch certification is required by
specific labs. The CTFA International Color Handbook2 contains a comprehensive
list of the nomenclature of approved colorants in different countries.
Table 15.1. Certifiable color definitions for United States
Colorant Type Definition

Food, Drug, and Cosmetic Certifiable colors that are for use in coloring
(FD&C) food, drugs and cosmetics.
Drug & Cosmetic (D&C) Certifiable colors that are for use in coloring drugs
and cosmetics including those in contact with
mucous membranes and those that are ingested.
External Drug and Cosmetic Certifiable colors that are for use in coloring
(Ext. D&C) drugs and cosmetics that do not come in con-
tact with mucous membranes or those that are
ingested.
In general, synthetic organic colorants used in cosmetics can be classified as

belonging to one of six different chemical groups, according to the characteristic
moiety of their chromophore.
• The Indigoid Group to which D&C Red No. 30 belongs; the Xanthene
Group, which may be either acid type (like D&C Yellow No. 7) or base
type (like D&C yellow No. 8.) ; the Azo Group, which includes a relatively
large number of certifiable colors. It includes both dyes (i.e. soluble) and
pigments (i.e. insoluble), and they may be either sulfonated or unsulfonated.
Examples include D&C Red No. 36, D&C Red No. 17, and D&C Orange
No. 4. The Nitro Group is represented only by the certifiable colorant Ext.
D&C Yellow No. 7. The Triphenylmethane Group includes sulfonated acid
dyestuffs like FD&C Blue No. 1 and FD&C Green No. 3. D&C yellow No.
11 and D&C Yellow No. 10 belong to the Quinoline Group, known for their
good light stability. Finally, the Anthraquinone Group includes D&C Green
No. 6, and D&C Violet No. 2.2
Organic vegetal colorants: This group includes beta-carotene, annatto,
carmine, henna, chlorophyllin-copper complex; capsanthin*, capsorubin*
and guaiazulene, all extracted from plants (* these substances are not even
considered colorants in United States but just cosmetic ingredients). Gua-
nine, an organic pearled agent, is an exception as it derives from fish scales,
while caramel is prepared by controlled heating of sugars. They are exempt
from certification.
Inorganic colorants: In addition to the organic colorants, inorganic colo-
rants may be used in cosmetics as well. Inorganic pigments are composed
of insoluble metallic compounds, such as the following:
150
• Iron oxides
Iron oxide ores are difficult to purify so their synthetic forms are more eco-
nomically acceptable. Those iron oxides used in cosmetics include the yellow
hydrated iron oxide, as well as brown, red and black iron oxides. Structural
differences among them reside in the combined water amount and in the
crystal shape and size. In black iron oxide, bivalent and trivalent iron atoms
coexist. Providing all the colors of rust, iron oxides are widely used to give all
skin-shades, when blended with titanium dioxide, a very white pigment.
• Carbon blacks
These pigments are black, as the name implies, and are useful in mascara
and eye-liner formulations. Carbon blacks are produced from carbon de-
posits burned onto an iron surface with a natural gas flame or by controlled
calcination of animal bones. Since they need batch certification, they have
been included in the synthetic organic colorant bundle6.
• Chromium oxide greens
Chromium oxide greens consist of anhydrous and hydrated Cr2O3, purified
by acid washings. Their hues are respectively olive-green and blue-green
• Ultramarines
Ultramarine colors are created by melting together sulfur, soda ash, china
clay and charcoal pitch. They are available in pink and blue.
• Bismuth oxychloride: is a white inorganic pearling agent7
• Metallic powders: Aluminum, copper and bronze are used for providing
metallic luster.
Other inorganic pigments include a light violet manganese complex (manga-
nese ammonium pyrophosphate) and the dark-blue ferric and ferric-ammonium
ferrocyanides.
A list of white or off-white powders, like talc, zinc oxide, kaoiln, mica, pyro-
phyllite and the like are also included in the colorant list, but their main use is as
extenders, fillers, skin adhesion, transparency, shine or flow promoters.
Inorganic pigments are not considered to have the same kinds of health risks
associated with the organic colors and, therefore, do not require certification in the
United States. Nevertheless both in the United States as in the EU and Japan1,2,3,4,
their purity criteria, concerning the toxic or allergenic heavy metal impurities have
to met specific set standards. Inorganic colors are not soluble, so their applications
are limited to the make-up category, as the majority of pigments.
Hues
Furthermore, inorganic pigments are not available in the range of hues that
the organics offer and their color tone is a lot less brilliant than that provided by
organic colorants8
See Table 15.2 for a partial list of inorganic pigments and other colorants that
do not require certification.
151
Table 15.2. Common examples of organic (Certifiable) colorants,

their common names and approved uses 7
FD&C Blue No. 1 Brilliant blue FCF, Food blue2, allowed in lip/Oral, Eyes,
External, Rinse-off products
D&C Blue No. 4 Alphazurine FG, allowed in External, Rinse-off products
D&C Brown No. 1 Resorcin brown, allowed in External, Rinse-off products
FD&C Green No. 3 Fast green FCF, food green 3, allowed in lip/Oral, External,
Rinse-off products
D&C Green No. 5 Alizarin cyanine green, allowed in lip/Oral, Eyes, External,
Rinse-off products
D&C Orange No. 5 Dibromofluoroescein, allowed in lip/Oral, External,
Rinse-off products, 5% max in lipsticks
D&C Red No. 6 Lithol rubin B, allowed in lip/Oral, External, Rinse-off
products
D&C Red No. 21 Tetrabromofluorescein, allowed in lip/Oral, External,
Rinse-off products
D&C Violet No. 2 Alizurol purple SS, allowed in External, Rinse-off products
Ext. D&C Yellow No. 7 Fluorescein, allowed in External, Rinse-off products
D&C Yellow No. 8 Uranine, allowed in External, Rinse-off products*
* as an example, this color is permitted in Europe in all products at 6% maximum
Mode of action
Pigments provide color to the products via reflection at their surface of a part
of the incoming light. The reflected color is the component of the light spectrum
that is not absorbed by the pigment surface; black pigment absorbs all the visible
spectrum. Therefore, their pigmenting force and hue in a product depends on their
aggregation state and amount of exposed surface (therefore, on particles dimension).
They are not transparent and provide temporary superficial colors to the skin by
adhesion mechanism provided by the make-up vehicle. Moreover, any chemical
modification of their surface can modify their shade and coloring strength9.
Soluble colorants impart color to solution by absorbing in a precise interval of
wavelengths, while the non absorbed light pass trough and hits the eye. They do
not affect transparency of solutions
Selecting Colorants
Most, but not all, cosmetic products have some type of colorant added, but it
can be difficult for formulating chemists to decide which one to use. Many factors
determine the appropriate colorant choice, including the regulatory status of the
colorant, the physical and chemical properties of the formula, the chemical stability
of the colorant, and, of course, the exact shade of color desired10.
152
Type of product: This first subdivision concerns the reason for coloring the
finished product. If is intended to impart temporarily color to the skin by adhesion,
product belongs to the make-up field and pigments must be used (soluble colorants
bleed onto the skin). In all other cases, a key factor to consider when selecting a
colorant is the time of permanence of the product onto the skin (rinse-off or leave-
on) and where on the body it will be used (application site). This information will
determine which regulatory class of color may be used.
Regulatory state: In the United States, precise limits exist so that synthetic
organic (certified) products intended to be applied near the eye or onto the lips
and around the oral cavity, must bear clear indications of allowed use in this areas,
that must literally appear (e.g. “approved for the eye area”) in the law1 or use in-
organics. Among the colors allowed in cosmetics (FD&C, D&C, Ext. D&C) the
last category is allowed only on eternal parts of the body, and not to the lips or any
part covered by mucous membrane. Cosmetics (and OTC drugs) that are used in
or around the oral cavity must use FD&C colors or specifically approved D&C
colors, because of the risk of incidental ingestion. Pearls, layered materials that
provide interference phenomena with visible light, may also represent an alterna-
tive way for using colored traces around the eyes. Four inorganic colors not allowed
are silver, henna, lead acetate, chlorophyllin-copper complex and bismuth citrate.
Certified organic colors that are approved in the United States for the eye area
are FD&C Yellow No.5 and its lakes, FD&C Blue No.1 and its lakes, FD&C Red
No.40 and its lakes, D&C Black No.2 and No.3 (for specific eye-area products)
and D&C Green No.5.
The chemist should also be aware that some certifiable colors have specific use
level limits. In general, the inorganic colorants may be used without restriction in
any of these products, but, for instance, ultramarines, chromium oxides and ferric
and ferric-ammonium ferrocyanides cannot be used in the lips area.
Table 15.3. Examples of inorganic colorants and other materials not requiring
certification but only compliance to CFR
Material CI Number CFR Reference

Aluminum powder 77000 73.2645
Annatto 75120 73.2030
Bronze Powder 77400 73.2646
Chromium hydroxide green 77289 73.2326
Ferric ferrocyanide 77510 73.2299
Manganese violet 77742 73.2775
Ultramarines 77007 73.2725
Iron oxides 77491/77292/77499 73.2250*
*As an example, in Europe, specifications for Iron oxides require compliance with food grade
quality norms.
153
Solubility: Remember, the application of colors is also regulated by their solu-

bility or insolubility (as in make-up) in the vehicle and on their coloring aim (i.e., if
they are intended to color only the formulated product or they are aimed to color,
for instance, the water bath). Pigments for make-up are typically insoluble.
Formulation requirements: Once the chemist has determined the class of
colorant to use from the point of view of their national or international regulatory
status, the physical and chemical requirements of the formula should be taken into
consideration. The composition, the physical and use characteristics of the product
determine the type of colorant used. If the product is an aqueous solution, and if
certified colors are used, FD&C and D&C colors are very useful. If the product
is in solid form, e.g. as soap, it is not desirable to use a water-soluble colorant be-
cause it may bleed, smudge or streak during usage. Therefore, formulators prefer
to use insoluble certifiable or inorganic pigments. If the product has limited water
content or is in a nonaqueous solution, such as an alcoholic skin toner or a body
oil, then colorants with appropriate solubility on the hydroalcoholic system or in
the oil blend should be chosen from the right regulatory category.
Stability: Colors are so named for their capability to impart a color to product
even at very low concentration and because of the electron mobility within their
molecular structures (organic) or in their metal atomic orbitals (mineral). This easy
displacement involves necessarily a comparatively high chemical reactivity. When
selecting a colorant, the formulator should also be aware of how the following fac-
tors may affect its stability:8
• Exposure to light and heat. Products in clear packaging may be exposed to
excessive amounts of light which can destabilize or fade the color. FD&C
Blue No.1 is notorious in this regard.
• Extremely high or low pH. Some colorants are more or less stable in alkaline
or acid conditions. Others may exhibit entirely different shades at a different
pH.
• Concentration. Colorants used at very low levels are more likely to show
fading compared to higher levels.
• The presence of incompatible ingredients. Surfactants, cationic or anionic
surfactants, reducing or oxidizing agents, formaldehyde releasing preserva-
tives etc. may impact color lasting quality.
• Contamination with microorganisms. Some colorants may be degraded by
bacteria.
• Packaging materials. Some plastics can absorb preferentially colored
ingredients
• Suspended solids. Energy rich solid surfaces (e.g. fillers, titanium dioxide,
zinc oxide) can adsorb electron-rich soluble color molecules
• Interaction with the base color: colors developing from the base for any
reason (oxidation, hydrolysis, light exposure, pH changes, internal reaction
between perfume ingredients and other raw materials) may interfere with
color yield and hue provided by added colors. This interaction explains why
light blue colored solutions frequently turn green on stability.
154
Shades
One of the most basic considerations in color selection is the desired shade
of the product being formulated. Cosmetic products rely on color to promote a
certain image or convey a consumer concept.
In make-up products, such as eye shadow and lipstick, that image may require
that the product’s color to be continually updated to keep pace with the latest
fashion trends. This ongoing evolution of new and different product colors can be
a challenge for the formulator. When the chemist attempts to match the color of
another commercial product, the ingredient statement on that product may provide
a good starting point. But in make-up the color list is comprehensive of pigments
that are present in all shades (by the wording “may contain”. The specific certified
color name must be included in the ingredient statements for products marketed
in the United States for EU, specific purity criteria requirements and allowed body
area of use must be checked in the permitted colorant list of the European law.
Picking an inorganic pigment may be more difficult because the pigment name
(iron oxide, for example) may apply to several shades.. In the case where an ingre-
dient statement is not available or the chemist is not directly matching the color of
another cosmetic product, the formulator must rely on experience to judge which
colorants are most appropriate. A good eye for color and the patience to learn by trial
and error are valuable skills to have when color matching. Color chart collections
like the Pantone® or instruments like colorimeters or spectrophotometers could
be of help for precise matching and for “color communication” among different
company departments.
In all other products, the selection and dosage of colors is a lot easier, as today
the choice of available shades of soluble permitted colors is quite restrict. A mini-
mum of creativity is required to obtain specific hues by blending colorant. Generally
blends require a maximum of three soluble dyes.
Table 15.4 Comparison of properties between

typical inorganic and organic pigments
Inorganic organic
dull brilliant
polar medium polarity
high concentration diluted on substrate
hard soft
pH stable * pH sensitive
light fast may discolor
high specific gravity low density
hard to micronize easy to micronize
difficult to wet with oils easily wet by oils
*except ultramarines and manganese pyrophosphate

155
Cost: A relatively minor consideration in color selection is cost. Colorants tend

to be very expensive on a weight basis. Fortunately, minute quantities are required
for most products so they contribute very little to the final cost of the formula. Of
course, an exception to this rule is again the field of make-up, where pigments are
the “actives”. Chemists should also know which colorants their company already
purchased as a cost-saving measure.
Batching with Colorants

Fluids: Most colorants are supplied in concentrated powder form. Typically,
very little must be added to the formula to impart color. Chemists should be familiar
with the techniques used to add colorants to formulations. For example, to color a
liquid product, such as a shampoo, may require as little as 0.00001% dye. For a 1 kg
batch of shampoo, the formulator would, therefore, need to weigh out 0.01 grams of
colorant. While this measurement can easily be accomplished with a sensitive scale,
it is tedious to work with such small quantities. More important, the likelihood of
making an error in color matching increases when it only takes a minute amount to
change a color dramatically. It is more convenient and accurate to prepare dilute,
adequately preserved, stock solutions (such as 0.1%) of water-soluble dyes that can
quickly and easily be added to the batch. On a larger production scale, colorant is
usually preweighed into a separate vessel and dissolved in water before it is added
to the main batch. This practice helps to avoid adding the incorrect colorant and
ensures even mixing. When dealing with very pale products, the base color can
influence the outcome of the hue of the finished product. Adequate preliminary
trials on a limited amount of batch should be set when such possibility exists and
the necessary corrective actions planned in advance.
Powders: Products in powder form, such as eye-shadow and blush, require special
processing to add colorants. The pigments must be evenly dispersed throughout the
powder matrix. This dispersion is accomplished by grinding or milling with special
equipment. A variety of equipment, including the hammer mill and the ball mill,
is used in the make-up industry to disperse pigments in powders. These devices
pulverize agglomerated pigments particles, micronize and intermingle them with
talc and other powdered ingredients in the formulation. This process creates a fine
dispersion that allows the true color to develop. Similarly, adding colorants to an
oil- or wax-based product requires that the pigment be dispersed in the waxes and
oils, as happens in lipsticks. This dispersion can be achieved with a roller mill, or
a hammer mill, devices that repeatedly force the product through closely spaced,
rotating steel cylinders or hammer heads to evenly divide color throughout the
batch. The dispersing vehicle, provided of adequate wetting power, will avoid
reagglomeration of the milled pigment.
Emulsions: Pigment powders are generally used in emulsions for preparing
mascara, eye-liners and foundations. Most commonly used pigments are iron oxides,
titanium dioxide, carbon blacks and ultramarines. While mascara have generally dark
colors and are distributed on the limited surface of lashes, the different wettability
and particle dimensions of the different oxides can lead to a sort of chromatography
of pigments over the skin during application of foundations. Milling of pigments
156
may equalize their skin distribution, as the adoption of adequate wetting agents11,
or the use of coated pigments.
Color Quality Control

Matching the color of an existing product or producing a new shade for a cos-
metic is not an exact science. One reason is that the final color of a product can
vary because of small lot to lot variations in pigment color or as a result of weigh-
ing errors and processing variables (e.g. milling time, speed and temperature) 12.
Indeed, milling operations increase dramatically the temperature of the powders
and catalytic reaction could take place on the wetting oils. Another reason for color
variance is that the inherent color of the base formula can shift the shade. When
keeping color reference of finished products, one should take into account that
vehicle diffusion, oxidation phenomena and other instability parameters can exert
a yellowing/darkening influence on the reference hue. Therefore this reference
must be regularly updated/substituted.
Chemists can ensure consistency in the color quality by comparing incoming
batches of colorant to an approved standard before using the color in a batch. As
colors in mass are very intense and difficult to distinguish, the colorant must be
evaluated in a sample of the product base or in a so-called extension, where the
color is diluted with an inert white base (e.g. titanium dioxide at 10%, then milled,
in case of make-up powders) and compared visually or with suitable instrument
with a standard made in the same conditions.
To evaluate the color of a wax or oil based product, a technique known as
“drawing down” is used to spread a thin film of product on paper. Ideally these
evaluations should be conducted under controlled conditions using a color-matching
cabinet with different lighting configurations (fluorescent or simulated sunlight, for
example). If it is determined that the product color does not meet specifications,
certain techniques may be used for reworking the batch to correct the color or the
composition of a whole set of formulae should be accordingly modified. This task
is quite common in make-up production. Application onto the operator skin, the
volar part of forearm being the preferred site (or nails in case of varnish!) is a funny
but fruitful way to compare hues in a similar-to-real use conditions. It should be
remembered that special optical phenomena, like those provided by pearls, can
make color matching and instrumental color control very difficult. This difficulty
is the reason why trained colorists play key roles in the color cosmetic industry in
color development and quality control.
New ingredients: pigments coating, mainly for inorganics, is a group of su-
perficial treatments of growing importance and application in make-up products.
Indeed, coating provides important changes to the superficial characteristics of
pigments, their wetting ability, their dispersion capability and compatibility with
the vehicles, together with enhanced products stability due to decreased catalyst
action of metallic ions. 13 Many types of coating materials exist and several binding
systems for securing the coating agent to the surface of the pigment.
157
The Future of Colorants

Given the complicated and highly regulated nature of colorants, chemists must
be up-to-date on approved colors, including those that vary from country to country.
Modern analytical techniques can detect extremely low levels of contaminants that
may have deleterious health affects. These findings have caused some concern,
inciting the argument that certain colorants should be delisted. Chemists should
have a complete knowledge not only of the permitted colorants, but also of the
specification requirements and have the required analytical documents easily trace-
able. Additional chemical analysis could be necessary in some cases. As make-up
products could be prepared by contract manufacturers, and be cross-contaminated
by unknown residues of other batches or solvents (e.g. methylene chloride), some
random analysis for checking compliance to regulatory norms and internal purity
criteria is advisable. Should a color raw material used in a product be made un-
available, a chemist should be prepared to propose alternatives, even if this task
has been given reduced freedom with the reduction of available certified colors.
Milling colored pearls, even if this process is a quite expensive operation, is being
increasingly adopted for solving such color problem in make-up14. New optical ef-
fects are now achieved by particles reflecting and refracting light so to hide wrinkles
and skin imperfections, acting together with pigments and other fillers. 15,16,17
References
1. Code of Federal Regulations, 21 CFR 74.
2. CTFA International Color Handbook, 4th ed., The Cosmetic, Toiletry, and Fragrance
Association, Inc., Washington (2007)
3. EU Official Gazette L97/1 (April 4th, 2006)
4. The Comprehensive Licensing Standards of Cosmetics by Categories, YAKUJI NIPPO,
LTD. Australia (1999)
5. T Mitsui, New Cosmetic Science, Elsevier, Amsterdam 370–405 (1997)
6. J Hollenberg, “Meet D&C Black no2: A New, Old Cosmetic Color Additive” Cosm Toil
120(4) 87–90 (2005)
7. Q Peng and M Tellefsen, Bismuth Oxychloride—“A Multifunctional Color Additive,”
Cosm Toil 118(9) 53–62 (2003)
8. E Desmarthon and M Seu-Salerno. “A Co-Precipitation Process for Inventing New
Lakes,” Cosm Toil 121(3) 105–14 (2006)
9. B Brewster, Pigments: Achieving the Effect, Cosm Toil 120 26–34 (2005)
10. Color Formulary Review, Cosm Toil 119 (6) 86–12 (2004)
11. L Rigano et al, A new approach to powder dispersion in Liquid Foundations
Proceedings, IFSCC Conference—Acapulco 239–57 (1997)
12. H Epstein H, Color Quality Control, Cosm Toil 111(3) 21–4 (1996)
13. E Desmarthon, Cream in Powder Form: A New Concept in Make-up, Cosm Toil 122(12)
70–6 (2007)
14. M Graziano and B Adhia, Metallic Pigments in Personal Care Applications, Cosm Toil
121(10) 63–72 (2006)
15. B Brewster, Reflecting on Soft Focus, Cosm Toil 118(9) 16–21 (2003)
16. T Tanaka et al., Development of a New Chiaro-scuro Make-up Product Using Mica
Coated with Titanium Lower Oxides, Proceedings of the X IFSCC Congress—Venezia
261–81 (1994)
17. M Medelnick, Color Variable Pigments, Proceedings of the XXI IFSCC Congress—
Berlin (2000))
Chapter 16
Pigments:
Achieving the Effect
A look at pigments and how they are achieving special effects.
key words: pigments, colorant
I n the land of pigments, one can quickly arrive at the region of math and physics.
We will avoid that region but still manage to sample a few numbers and take a look
at pigments and how they are achieving special effects, like interference and pearl-
escence. New materials and new technologies are driving these effects. Regulatory
agencies are overseeing them. Market researchers are counting them. Consumers
are demanding them. And cosmetics are more varied because of them.
Let us first clarify that although the terms pigment and colorant are often used
interchangeably, they actually have different meanings, as explained by Sanjoy
Ganguly, industry manager, Cosmetic Americas, Sun Chemicals.
“Colorant truly carries a broader classification,” Ganguly says. “Colorant en-
compasses anything that imparts color to a substrate, including pigments and dyes.
Pigment, however, has a narrower definition and relates to an insoluble organic and
inorganic molecule that is physically and chemically unaffected by its vehicle.”
The Market
In July 2005, The Freedonia Group issued a report1 showing pigment demand
by type for the US cosmetics and toiletries industry (and other industries) in 2004
with projections through 2014. Freedonia breaks pigments into three types:
• Organic. These are complex molecules whose long chemical names are usually
expressed instead as a color, a shade, and the regulatory approval status—such
as D&C Red No. 6. Organic pigments may be water-soluble, oil-soluble, or
insoluble. The insoluble form (a dye precipitated on an insoluble substrate)
is known as a lake, such as D&C Red No. 6 Barium Lake. The carbon blacks
are also organic pigments.
• Inorganic. Inorganic pigments are composed of insoluble metallic compounds,
such as iron oxides, chromium oxides, titanium dioxide, ultramarines, and
ferric ammonium ferrocyanide.
• Special effect. These pigments are intended to achieve interactive visual ef-
fects supplementary to the basic color. They use materials such as synthetic
fluorphlogopite, guanine, bismuth oxychloride, and mica. Some popular effects
are described as pearlescence, interference, and color travel.
159
160
Pigments: Achieving the Effect Beginning Cosmetic Chemistry
According to Freedonia, “demand for pigments in the cosmetic and toiletry

market is projected to increase 6.1% per year to US$94 million in 2009, with vol-
ume totaling 15 million pounds at that time. Gains will be led by inorganic and
specialty pigments. Product development will help to drive inorganic use, while
specialty pigments continue to achieve favorable gains due to their ability to create
pearlescent, frosted, glitter, metallic, glassy, and glow-in-the-dark effects.”
Table 16.1 shows the demand and the dollars behind Freedonia’s projection.
It shows our industry’s demand for organic pigments to be essentially stagnant over
the 20-year period, while the demand for specialty and inorganic pigments will
grow by multiples of more than three and five, respectively.
Table 16.1 also shows that the cosmetic and toiletry industry’s demand for
pigments remains a very small percentage—less than 3%—of the total pigment
demand, which comes primarily from the need to color paints, coatings, plastics,
and inks.
Table 16.1. US Cosmetics and toiletries: Pigment demand by type

(with dollar amounts based on the US dollar in 2000)
Item 1994 1999 2004 2009 2014

Cosmetics/Toiletries Shipments (bil $) 24.1 27.0 32.2 36.6 41.1
Cosmetics/Toiletries Pigments (mil lbs) 8 10 12 15 18

$/lb 5.00 5.80 5.83 6.27 6.94
Cosmetics/Toiletries Pigment Demand 40 58 70 94 125

Specialty 16 24 32 42 55
Inorganic 10 18 26 38 54
Organic 14 16 12 14 16
% Cosmetics/Toiletries 2.2 2.5 2.7 2.8 2.9
Total Pigment Demand 1814 2317 2640 3400 4300
Source: The Freedonia Group, Inc.
A cosmetic formulator choosing a pigment from among these several categories

would need to be aware of stability, compatibility, and desired effect, according to
Phil Linz, senior cosmetic chemist at the Rona Cosmetic Business Group of EMD
Chemicals, Inc., a New York affiliate of Merck KGaA in Darmstadt, Germany.
“Inorganics tend to be more stable, meaning light-fast, than organics. Organic
colorants generally give colors that are brighter, cleaner, and more intense than
inorganics. In practice, formulators would generally blend both organic and inor-
ganic pigments to achieve their desired effect.
“Pigments can take the shape of irregular particles or platelets. Some effects,
such as pearlescence, color travel, or mirror effects, can only be obtained from the
use of inorganic pigments because the inorganics provide the required flat surface.
An irregular surface produces light-scattering, which destroys the pearlescent effect
from a mica surface or the mirror effect from a metallic surface,” Linz explained.
161
Development of improved pearlescent pigments offering new colors and im-

proved processing characteristics will spur demand, Freedonia says.
In addition, other specialty pigments are finding greater use in the cosmetics
market. “Borosilicate-based pigments, for example, offer higher color purity and
higher transparency than mica-based pigments. Borosilicate pigments are finding
greater use in nail polish, among other cosmetic applications,” according to the
Freedonia report.
The Effects
The effects of pigments have been described in numerous publications, and
are summarized here from several sources.2–4
Conventional organic and inorganic pigments are considered absorption pig-
ments because they absorb certain wavelengths of the incident white light. The
phenomenon of color is produced by scattering of the remaining unabsorbed com-
ponent of the formerly white light. For these particles the effect is independent
of geometry.
Metallic pigments consist of tiny flat pieces of aluminum, copper, gold, zinc,
and other metals that reflect light the way a mirror does. Zinc is approved as a
cosmetic colorant only when alloyed with copper. Gold is approved in Europe and
Japan but not in the United States as a cosmetic colorant. For metallic pigments,
the effect depends on the viewing angle.
Interference pigments (including pearlescent pigments) are typically composed
of thin, translucent platelets coated with metal oxides, such as titanium dioxide
and/or iron oxide. White light striking the surface of these pigments is refracted,
reflected and scattered by the layers that make up the pigment. Through a super-
imposition (or interference) of the reflected rays of light, a changing play of color
is created, with the most intense color seen at the angle of reflection. The colors
produced by interference are dependent on the angle of observation and the angle
of illumination.
Phil Linz notes that absorption effects and interference effects can be combined.
For example, absorption colors can be added to a mica-based pigment coated with
TiO2. “If carmine is added and the interference color is red, a red pigment would
result; but if that same system were changed slightly so that the TiO2 layer were
slightly thicker and now gives a blue interference, the combination of the blue
interference and the red carmine mass tone would give a purple pigment,” Linz
said. “The other important parameter in these pigments is particle (lateral) size of
the mica substrate; larger pigments give more sparkly, more transparent effects;
smaller particles give more opacity and more of a silky/satiny effect.”
The Pigments
Let’s look at some interesting pigments mentioned in the Freedonia report. Here
we’ll focus on effects pigments from Eckart Cosmetic Colours LLC (Painesville,
Ohio USA), Engelhard Corporation (Iselin, NJ USA), and the Rona Business Unit
of EMD Chemicals Incorporated (Hawthorne, NY USA). Also mentioned was Sun
162
Chemical Corporation (Cincinnati, Ohio USA), whose recent launch of several

inorganic pigments is discussed in the sidebar.
SunPURO Launched
Sun Chemical has launched the SunPUROe product line with a series of
synthetic yellow, red, and black iron oxides. The line is said to be universally
compliant. Its colors far exceed existing regulatory specifications in the United
States, Europe, and Japan.
Sun Chemical manufactures these colorants using meticulously controlled
processes to ensure their high purity, low metal content, and small particle
size, according to the company’s Web site.
Other pigment products available from Sun Chemical include SunCRO-
MAe organic and inorganic pigments, SunSHINEe pearlescent pigments
composed of TiO2-coated synthetic fluorphlogopite, and SynMICA functional
filler composed of synthetic mica.
e
SunCROMA and SunPURO are trademarks of Sun Chemical. SunSHINE is a registered
trademark of Sun Chemical.
Eckart Visionaire metallic effect pigments: Visionairea metallic pigments

are flakes of aluminum, bronze, or copper that are microencapsulated in silica to
allow greater flexibility in formulations and better durability of the pigment in pro-
cessing. Eckart claims they are the only metallic pigments on the market designed
specifically for the cosmetics and personal care markets.
“The encapsulation in silica overcomes the problem with traditional unencapsu-
lated metallic pigments that had to be “passivated” before use in an aqueous system.
Unencapsulated aluminum will evolve hydrogen gas in water-containing formula-
tions. Unencapsulated bronze and copper will turn water-based formulations blue
due to oxidation to copper ions,” explained Martha Graziano, manager-applications
development and technical services at Eckart Cosmetic Colours LLC.
“Most passivation technology is not suitable for the personal care markets, or
applications,” Graziano said, “but the encapsulation used in the Visionaire products
imparts the most robust passivation technology for this market and provides more
durability to the metallic flakes during processing by the end user.”
Metallic pigments reflect and scatter incident light. Their flat surface can
help impart brilliance to many other cosmetic colors. “Although the high level of
international regulations leaves a restricted list of allowed colorants for personal
care and cosmetics, the use of metallic pigments can greatly increase the color
palette available to cosmetic formulators when mixed with other colorants, such as
organics and/or pearlescent pigments,” Graziano said. “A combination of metallic
pigments with pearlescent pigments and/or organic colorants can create sensational
polychromatic effects.”
163
Visionaire line of metallic pigments comes in nine shades, which are achieved
by the natural color of the metals: a silver shade from aluminum; a cinnamon
shade from copper; and three shades of bronze based on varying the percentages
of copper and zinc in the bronze alloy. The copper and bronze shades are further
processed to yield an additional four shades.
Engelhard borosilicate Reflecks pigment: In March 2005, Engelhard in-
troduced four new colors. Three are in the Reflecksb Colors family. The fourth
is Twinkles of Turquoise, a unique blue-green iridescent pigment in Englehard’s
Reflecks line of iridescent and pearlescent borosilicate-based pigments that re-
portedly takes effect-enhancing pigments to new levels of chroma, color purity,
brightness, transparency, and reflectivity. These pigments are said to be especially
dramatic in transparent formulas such as gels and clear sticks.
Borosilicate, the substrate in these Reflecks pigments, is chemically stable
glass containing essentially calcium borosilicate and sodium borosilicate (Table
16.2). The designated INCI name for this material is calcium sodium borosilicate.
The unique effects of the Reflecks effect pigments are attributed to their cleaner
substrate and their unique morphology.
Table 16.2. Compositions of borosilicate3
Ingredient % wt/wt
SiO2 65-72
Al2O3 1-7
CaO 4-11
MgO 0-5
B2O3 0-8
ZnO 0-6
R2O (Na2O + K2O) 9-17
Borosilicate is pure, transparent, corrosion-resistant, and the plates have a

smooth flat surface. These are all optical advantages, compared to the properties of
mica, according to Gabriel Uzunian, director, cosmetic applications at Engelhard
Corporation.
The mica surface is not always smooth. “The delamination process leaves the
surface with nanometer-sized steps; thus there is a broad thickness distribution for
mica. This irregular surface gives mica its pearlescent appearance and a degree of
opacity,” Uzunian has written.3 “By comparison, borosilicate-based effect pigments
have a sharper luster and interference color, and they are more transparent.”
Mica and borosilicate also differ in terms of color. Macroscopically they have
roughly the same optical appearance. Microscopically, however, there is a big differ-
ence between coated mica and coated borosilicate. “Under the optical microscope,
164
all of the TiO2-coated borosilicate pigment particles have a uniform color, while the
TiO2-coated mica pigment particles consist of a range of colors,” Uzunian wrote.
In addition, mica and borosilicate differ in terms of their reflectance spectra.
Uzunian studied the reflectance spectra for pearl mica pigments at the 0° specu-
lar angle on micas of four different thicknesses (0–600 nm). He found that each
thickness of mica produced a different interference color. Borosilicate pigment
substrates are typically thicker. In a similar study on borosilicates of five different
thicknesses (3000–5000 nm) he found that there is no interference phenomenon
for the light penetrating through the borosilicate substrate.
In summation, borosilicate pigments provide color, luster, and hiding power
that are different from other effect pigments. They are stable in both alkaline and
acidic environments, and in common solvents and aqueous systems. Borosilicate’s
advantages mean that many other companies are using this material. For instance,
EMD Chemicals launched its Ronastarc calcium-aluminum-borosilicate-base Silver
White pigment in 2003. It is described as a sparking pigment, particle size 20-200
µm, with multicolor effect. Other shades (gold, blue, and copper), prepared on the
Ronastar platform, are now available, with more expected soon.
However, Martha Graziano points out that mica-based pearls are likely to be
around a long time. “Borosilicate-based technology does provide a new look, but
the cost is roughly 10 times the cost of mica-based pearls—which realistically can-
not be economical in many formulations,” Graziano said.
EMD Chemicals Timiron Splendid pigments: Now let’s spend a few minutes
with Phil Linz as he describes the multilayer technology5,6 used by EMD Chemi-
cals to make their Timirond Spendid interference pigments, a line of six pigments
launched in 1999. The same technology is used in the company’s Xironae line of
currently six effect pigments launched in 2002.
“The ordinary classic interference pigment is composed of a layer of mica
coated with a layer of TiO2. The color is developed in the same way that color is
developed in an oil slick on water. There’s a thin film of TiO2; some of the light hit-
ting that surface is transmitted, some is refracted, and some is reflected. Because
of this selective reflection, and by determining the thickness of that layer, you can
generate an interference color of green or gold or red or whatever. That’s roughly
the technology of the 1960s.
“In the last five to seven years we learned that if you put another layer of silica
on top of that TiO2 and then you put another layer of TiO2, there are more surfaces
to reflect and there are more chances for the light to be intensified.
“So the classic interference color is OK, and we will sell products with that, but
clearly the newer multilayer pigments will give you much more brilliance, much
more color intensity than a monolayer pigment.
“That was the initial thrust. But then our researchers said, “What if we change
the thickness of the silica layer?’ If light comes in at a shorter angle, it comes out at
a correspondingly shorter angle. Because the reflected light depends on wavelength
and the path length the light is traveling, you’ll get a color at the short angle. But
if light comes in at a wider angle, you’ll also have a reflection at that wider angle
but it will have a much longer path length and the effect will be that it will reflect
165
a different color. That’s what our color travel pigments are about: one pigment
giving multicolored effects. And again, it comes out of the same basic multilayered
technology.
“So basically we’ve gone in two directions with our multilayer pigments. The first
phase was simply making a stronger interference pigment. The second phase was
color travel, where you can create a pigment that looks purple at 1 viewing angle
and green at another. It’s the same technology, but a variation on the theme.
“What’s next? Basically, in all these systems you’re dealing with a substrate that
is coated in some way, usually with a cosmetically acceptable metal oxide. We’ve
prepared materials with various substrates (mica, silica, alumina, and borosilicate);
other substrates may yet find their way into commercial use. And methods of coating,
or even coating materials, may yet be improved, to give more uniform reflection,
therefore higher brilliance.
“Who’s doing it? Look at any list of pigment companies. We’re all doing it!”
Published October 2005 Cosmetics & Toiletries magazine.
References
1. P Prokop, Pigments: Inorganic, Organic & Specialty, The Freedonia Group, Inc.
Cleveland USA (Jul 29, 2005)
2. C Weingrod, Three-Dimensional color, available at http://www.danielsmith.com/learn/
inksmith/200211/ (accessed Aug 10, 2005)
3. G Uzunian, B Aucar and L Song, Borosilicate-based effect pigments, undated article
in Cosmetics & Toiletries Manufacture Worldwide; also available at www.ctmw.com/
articles2004/ctmw%20Engelhard.pdf
4. L-P Sung, ME Nadal, P Stutzman and ME McKnight, Characterization of coating
microstructure using laser scanning confocal microscopy, available at http://slp.nist.
gov/appearance/acs_aug2000.pdf (accessed Aug 1, 2005)
5. P Linz, Formulation approaches to interference pigments, Cosmet Toil 116(2) 61–66
(2001)
6. P Linz and Q Peng, Color-Travel cosmetic pigments: Interference to the max, Cosmet
Toil 118(12) 63–70 (2003)
Chapter 17
The Science of Reactive

Hair Care Products
A review of changing natural hair appearances to meet
consumer expectations is offered in this chapter.
key words: permanent wave, relaxer, oxidative color, bisulfite,

disulfide, oxidation, alkaline, relaxers, pigmentation
Background
The physiological function of hair on humans is insignificant compared to its
psychological significance. Humans place great social value on the color, texture,
shape and appearance of hair. The properties that are prized vary from time to time
and culture to culture, but what remains constant is that people generally want their
hair to be different in some regard than it exists in its natural state. This very basic
desire to alter the appearance of the hair has resulted in the need for many different
procedures and processes for safely altering the hair. Providing the desired color,
tint, texture, straightness, and other cosmetically appealing properties to the hair
while avoiding damaging the hair and causing irritation of safety issues to the hair
is a key challenge to the cosmetic chemist and the topic of this chapter.
During formal education, chemists are taught how to control chemical reac-
tions. In making the transition from academia to the cosmetic industry, chemists
may be surprised to find that reactions are generally undesirable in personal care
products because they may well have negative effects associated with the reaction.
Unwanted reactions in a cosmetic product may interfere with its stability and, even
more important, the wrong reaction could have dangerous side effects on hair and
skin. Most of the procedures and processes carried out by the cosmetic chemist do
not include reactive processes. Wetting, foaming, conditioning, and emulsification
performed on the hair are physical processes caused by selection of the proper
molecule added to the formulation.
Nonetheless, reaction chemistry does play an important role in at least one major
category of personal care products. These products are intentionally designed to
cause reactions that have beneficial effects on hair: relaxers, permanent-waving
products and oxidative hair colors. This chapter introduces this class of reactive
hair care products and their chemistry.
167
168
The Science of Reactive Hair Care Products Beginning Cosmetic Chemistry
A. Permanent Waving
In the interest of fashion, a wide variety of changes are made to hair in its
natural state to provide properties that are of interest. The first to be addressed is
shape. Almost an unlimited amount of curl can be placed into, or removed from
the hair. It is desirable to style hair into attractive configurations and to have it hold
its shape for an extended period of time. Shaping hair (providing it with wave),
has been practiced for centuries in one form or another.1 In the early 1900s, wav-
ing was accomplished by heating hair with cumbersome and dangerous electrical
devices.2 During the past 50 years, cosmetic science has developed increasingly
effective chemical techniques to impart a lasting wave or curl to hair. This process
is known as permanent waving or perming. The adjective “permanent” is a bit of a
misnomer because the wave only affects existing hair at the time of treatment; as
new hair grows out of the scalp, it will grow in its original, unwaved configuration.
Permanent-wave products are available in different forms known as acid, cold or
neutral waves. The technology employed in these products is based primarily on
two types of chemicals: thioglycolates and bisulfites.
Before beginning the discussion of how permanent waves work, it should be
understood by the reader that the science of reactive hair care products is very
involved and that this chapter is meant only as an introduction for the uninitiated
chemist. A number of technical articles describe these processes in detail.3,4,5 To
understand the basics of permanent waving, it is important to realize that hair is
composed of helical protein structures. Protein structures are made up of amino
acids linked in a peptide bond. The sequence of the amino acids is referred to as
primary structure. This structure cannot be modified without destroying the hair.
However, what can be modified is the interaction of sulfur rich amino acids. These
amino acids can bond with each other and form crosslinked protein polymers by
sulfur-sulfur bonds. This reaction results in a structure to the protein that alters
the shape of the hair. The structure of hair showing the sulfur-sulfur interaction is
shown in Table 17.1.
Table 17.1. Hair Protein Interactions

169
These bonds are responsible for hair’s structure, and they can be disrupted by
certain reducing reactions. (An experienced chemist will note that this explanation
is a simplified version of what is, in reality, a very complex process.)6
As previously noted, the most common reducing agents are thioglycolic acid
derivatives and bisulfite. These chemicals are used more than any others because
they have the best history of efficacy and have been the workhorses of the perma-
nent wave industry since the 1940s. Highly effective permanent-waving solutions
can be formulated by combining these reactive agents with other ingredients to
control pH and viscosity.
The process: The first step in the perming process is to physically rearrange the
original configuration of the hair on curlers or rods. The size of the rod determines
the size of the curl. Before rolling hair onto the plastic rods, thin sheets of tissue
paper, known as “end wraps,” are used to cover the ends of the hair. These end
wraps help the hair hold the proper configuration and protect the fragile ends by
absorbing excess perming solution.
When all the plastic rollers are in place, apply the perming solution and work
into the hair. During this stage of the process, the sulfur–sulfur bonds of the hair
break. The length of time required for this stage depends on a number of factors,
including the strength of the perm solution, the degree to which the hair will be
restructured and the condition of the hair. During this processing step, the hair is
plasticized as the disulfide bonds controlling its original structure are disrupted.
Some types of perming products require the use of heat from a hair dryer to ac-
celerate the reaction.
After a set amount of time, the hair is rinsed with water to stop the reducing
action. Next, a neutralizing solution is added to oxidize the protein residues. This
oxidation step relinks the sulfur-sulfur bonds. However, because the hair has been
stretched and curled on plastic rods, the newly rearranged disulfide bonds hold the
hair in a curled arrangement even after removing the plastic rods.
Achieving a good permanent wave depends on proper control of the reduction
and oxidation reaction kinetics so hair is not under- or over-processed. A detailed
discussion of protein reaction kinetics is beyond the scope of this chapter but
several excellent references are provided for the technically ravenous reader.7 It is
important for the chemist to understand that the perming process causes significant
damage to hair because of the breakage of the bonds and the swelling that ensues.
This swelling action results from exposure to the highly alkaline materials and can
cause significant cross-sectional or lateral damage. Damage can also occur when
treating improperly wrapped hair with a reducing solution.
Permanent wave formulations: In general, perms contain a number of ingredi-
ent classes (Table 17.2).6
These ingredients are formulated into three general types of perms: alkaline,
acid and bisulfite. Alkaline perms, also known as cold waves, use thioglycolic acid
as the active. This name may seem like a misnomer, but the name is derived from
the final pH of the product. Alkaline perms typically have a pH greater than 9.
Borish gives examples of commercial products in each of these categories.8 He also
170
discusses the subcategory of exothermic perms that rely on hydrogen peroxide to

generate heat by oxidizing thio in situ. Such exothermic products are designed for
hair that is hard to perm; they are the original “self-timing” perms.
Table 17.2. Permanent Wave Ingredients
Reducing agents thioglycolic acid, thiolactic acid, glycerol sodium sulfite.

Wetting agents sodium lauryl sulfate, disodium laureth sulfosuccinate,
sodium laureth sulfate, cocoamphodiacetate.
Buffering agents ammonium carbonate.
Conditioning agents Keratin hydrosylate, collagen hydrosylate, guar hydroxy-
propyltrimethyl ammonium chloride.
Oxidizing agents hydrogen peroxide, potassium bromate.
Stabilizers citric acid, sodium stannate, phenacetin.
Ancillary agents various emulsifiers, thickeners, fragrances.
Acid perms are customarily made with glyceryl monothioglycolate, a thioglycolic

acid derivative that is effective at a lower pH of 7–8. Even though the pH is neutral
to alkaline, these products have historically been referred to as “acid perms” in
comparison to their higher pH cousins. The name also has some marketing equity
since acid perms are perceived to be less damaging.
Bisulfite perms were designed for mildness; they are based on hydrogen bisulfite
rather than thio derivatives.8 Bisulfite reacts with hair and ruptures the disulfide
bonds at a lower pH than thioglycolic acid, so there is less swelling and cuticle
damage. The reaction between bisulfite and keratin may form what is known as a
Bundte salt (Equation 17.1).
KS-SK + RSH → K-SSR + KSH

←
EQUATION 17.1
Because of this salt formation, it is difficult to react the sulfo groups to reform
all of the disulfide bonds, and, therefore, bisulfite perms can leave hair physically
weaker and with a softer, less stable perm. Still, these formulations are popular in
the marketplace because they are less aggressive and can be used at a lower pH.
B. Hair Relaxers
Another process commonly used on the hair is “referred to as relaxing hair”.
“Relaxing” is the name given to the reactive process used to straighten excessively
curly hair. This process is typically used on African hair, which is significantly curlier
than Caucasian or Asian hair. This curliness is the result of the unique structure
of African hair, which is more elliptical and varies more in diameter. These factors
171
produce hair shafts that are extremely twisted or kinked.9 For fashion reasons, or
simply for manageability, some desire to make this type of hair less curly or even to
straighten it. Straightening can be done mechanically by pressing the hair with hot
implements or chemically by breaking the bonds in the hair with reactive products.
The latter method is the topic of this discussion.
Relaxers work in a manner similar to permanent waves: They rely on reactive
chemicals to break amino-acid-based sulfur bonds, thereby allowing the structure
of hair to be rearranged. The process of hair straightening is also known as lanthi-
onization, which refers to the conversion of the amino acid, cystine to the amino
acid, lanthionine.
In very general terms, there are two key differences between relaxing and waving
hair. First, because the relaxing process is intended to straighten hair, it does not
require hair to be wrapped on to rods or curlers. Second, relaxing tends to break
more bonds than perming. Accordingly, the chemistry of relaxers is somewhat dif-
ferent than the thioglycolate/bisulfite waving systems described above. Relaxers
are commonly based on metal hydroxides (such as ammonium hydroxide, sodium
hydroxide, lithium hydroxide or guanadine hydroxide.) These agents react more
aggressively with the hair than the perming solutions. Having said this, we also note
that some mild relaxers are, indeed, based on ammonium thioglycolate.
The procedure for a relaxer treatment is as follows: first, the hair is divided into
sections to simplify application. A thin layer of protective processing cream (typi-
cally petroleum jelly) is then applied to the hairline, ears and ends of the hair. This
hydrophobic layer shields skin from a harsh reaction from the aqueous solution.
The ends of the hair should also be protected from absorbing too much solution
and being over-processed.
After taking precautionary measures, the hair is parted equally and the cream
relaxer is brushed on section by section. The hair is then smoothed with the back of
a comb until achieving the desired straightness. Processing time varies from 10–20
minutes depending on hair type, condition and degree of straightening required.
Care must be taken not to leave the relaxer on too long or considerable hair dam-
age, such as breakage and scalp irritation, may occur. The relaxer cream is then
rinsed off with warm to very warm water. Good rinsing is critical to ensure that
the reactive agents have been completely removed; otherwise, additional damage
to hair and scalp could occur.
Some relaxers do not require a separate oxidation step. However, it is common
to shampoo the hair with a neutralizing shampoo immediately after relaxing. This
shampoo/rinse cycle removes relaxer cream and neutralizes excess alkalinity.10 In
addition, the neutralizing shampoo ameliorates the effects of the highly alkaline
treatment. The result is that the bonds of the hair are locked into their newly
straightened configuration. Most relaxers require an additional conditioning step to
help offset the damage caused by the reactive process. As with perms, the relaxing
process only lasts until new hair growth occurs.
Relaxer formulations: Since the 1950s, the market has seen the introduction
of a variety of formulations. These formulas are primarily based on three key com-
ponents: water-soluble/water-dispersible alkaline agent, oil phase and water phase. 11
172
They all contain materials, such as petrolatum or mineral oil to help protect the
scalp, or fatty alcohols to thicken the product and emulsifiers that are alkali-stable.
The various types differ by the type of alkaline agent employed. Lye relaxers con-
tain between 1.85–2.4% sodium hydroxide, depending on the strength required.
“No Lye” relaxers are formulated with guanadine hydroxide and are significantly
less irritating than the sodium type. Because of its inherent instability, guanadine
hydroxide must be formed in situ by mixing calcium hydroxide with guanadine car-
bonate. These components must be separate until the product is ready to be used.
Some brands claim to be “No Lye” and “No Mix;” these capitalize on the common
use of the term “lye” to apply only to sodium or potassium hydroxide (they are, in
fact, based on lithium hydroxide). Relaxers can also be formulated with different
specialty ingredients such as conditioning agents.
3. Hair Bleaching
Another process that uses reactive chemistry to change the hair is bleaching.
When hair is bleached the natural color is destroyed either partially, resulting in
lighter color hair, or entirely, resulting in blonde hair, devoid of color bodies. The
color bodies that exist in hair are melanin particles embedded in the cortex. The
color observed is dictated by the type, size, shape, distribution and concentration
of particles in the hair. Since, natural pigment exist inside the cortex the color
changing effect of bleaching must occur after penetration both cuticle and cortex.
This penetration causes damage, which does not repair. For this reason frequent
bleaching is a problem. Hydrogen peroxide under alkaline conditions is effective
in bleaching hair. The addition of persulfate dramatically improves the efficient of
hydrogen peroxide on hair.
The color of hair is measured by level shown in Table 17.3. Generally bleaching
will lighten the hair about 2 levels. Very aggressive bleaching will lighten by 4–6
levels, but much more damage is done to the hair in the process.
Table 17.3. Hair Color Levels
Level 1 Black
Level 2 Dark brown
Level 3 Medium brown
Level 4 Light brown
Level 5 Lightest brown
Level 6 Dark Blonde
Level 7 Medium blonde
Level 8 Light blonde
Level 9 Very light blonde
Level 10 Lightest blonde
Level 11 Extermely blonde
Level 12 Ultra light blonde
173
Formulation of hair bleaching products requires at least two components (1) a

peroxide solution in water at a concentration of between 6–9%, stabilized at about
pH 3.5 (generally with phosphoric acid and EDTA) and (2) An alkaline solution
generally ammonia at a ph of between 9–10. The two components are generally
mixed together immediately prior to bleaching. Formulations include thickeners,
surfactants to facilitate wetting and a variety of other additives.
4. Oxidative Hair Color

In addition to curling, straightening hair and bleaching, the ability to alter hair
color is also highly prized. In ancient times colored extracts were used to alter
the color of hair. Today, cosmetic chemists have developed several ways to alter
hair color, some of which involve complicated processes that introduce reactive
compounds into hair that has been swelled, react the molecules coupling them
into larger molecular weight species, and then shrinking the hair. This reactive
technique is known as oxidative or permanent, hair coloring. To understand this
process, the chemist should be familiar with the chemistry of hair pigmentation.
Primarily two melanin-based pigments affect natural hair color: eumelanin, which
is responsible for blond, gray, brown and black shades, and pheomelanin, which
produces reds and yellows. Keith Brown points out that these same melanin pig-
ments occur throughout nature and can be found in squid ink, bird feathers and
the colors of various mildew and mold.12
Two shortcomings are associated with the hair color produced by natural pig-
ments. First, hair tends to lose color as we age, and second, hair tends to turn grey
as we age. Neither shortcoming is easily modified. For these reasons, people have
often sought ways to improve the natural color of hair; either to ward off the signs
of aging or to adopt a different, fashionable color. Oxidative coloring addresses
both of these problems by producing lasting changes in hair color. In this process,
color is produced inside the hair shaft from aromatic amines and phenols reacting
with hydrogen peroxide; the resulting hair color is “locked” inside the hair shaft.
As new hair grows, the dyeing process must be repeated, approximately every
30–45 days.
How permanent hair color works: Oxidative dyes are small, colorless mol-
ecules that penetrate the cuticle and pass into the cortex. These reactive species are
then oxidized to form larger molecules that combine with other additives, known
as couplers, to form various colors. The resultant polymers, too large to pass out of
the hair again, are essentially permanent. As in the case of perming and relaxing,
this process is practiced under highly alkaline conditions, which swell the hair, al-
lowing better penetration of the dye precursors.
The high alkalinity also increases the oxidative reactivity of hydrogen peroxide
and promotes rapid lightening and color formation. Lightening the original hair
color is possible because hydrogen peroxide will destroy some (or much) of the ex-
isting natural pigments in the hair. This step is an important consideration because
it allows hair to achieve a color that is lighter than its original state.
Oxidative hair coloring involves several steps. Before application, these colorants
should be tested to ensure they will not adversely react with the skin. The product
174
is applied to a small patch of skin, the inside of the elbow, for example. Patch test-
ing may need to be done 24 hours before the coloring treatment is to take place.
A small curl of hair should be tested, too, before application to the entire hair to
assess tone of color and timing of contact.
After testing has shown no problems, the actual coloring process can begin.
First, the peroxide and the tint are mixed together in the applicator bottle. The hair
is partitioned and the tint is applied from the scalp to the porous ends. The hair is
left alone for 10–20 minutes while the reaction proceeds. During the last five or 10
minutes, the solution is spread toward the ends to even the color. The hair is then
rinsed and shampooed to remove excess color and halt the reaction.
The degree of color imparted to the hair depends on the concentrations of dye
and peroxide, processing conditions, even the condition of the hair at the time of
application. Also note that these coloring and bleaching processes are inherently
damaging to hair because some of the protein bonds are destroyed by the oxida-
tion/reduction reactions. Hair should not be color-processed for several weeks after
perming to avoid compounding this damage. Likewise, hair should not be colored
before perming as the perm process will physically remove some color, and it could
chemically alter the color.
Permanent hair color formulations: Permanent dye formulations consist
of two components that are separate until the product is ready to be applied. The
first component contains the oxidative dye precursors that are typically aromatic
p-diamines or p-aminophenols, such as p-phenylene diamine. These colorless pre-
cursors react to form dye intermediates, which, in turn, react with dye couplers to
produce color. The dye couplers include such materials as resorcinol, 1-napthol, and
hydroquinone. Formulations may contain five or more dye precursors or couplers,
so many reactions may occur at the same time.
Clarence R. Robbins gives an excellent discussion of oxidation reactions. He
notes the active intermediates react “with resorcinol to form polyindophenols and
trinuclear dyes, with m-diamines to form indamines, with m-aminophenols to form
indamines; and with naphthol and hydroquinone to form indophenols.”13
An alkali is used as part of the dye base to swell the hair and enhance penetra-
tion of the dye precursors. In addition, this portion of the formula may include
solvents, surfactants, thickeners and metal chelating agents. The second formula
component contains hydrogen peroxide and stabilizing agents. The two compo-
nents are mixed together just before use to initiate the reactions that will form the
permanent dyes.
When formulating hair coloring products, regulatory and toxicological consid-
erations are extremely important. These issues are not discussed in detail in this
chapter, but the formulator working in this area should be aware of the safety con-
cerns. The concerns include minor short-term effects, such as contact dermatitis.
Sensitization caused by these reactive products can lead to itching and redness. In
addition, concerns about the long-term systemic effects of these materials persist
because several aromatic diamines test positive as mutagens in the Ames test.11
Therefore, any dye products for hair coloring are scrutinized to ensure they pres-
ent no risk. For example, after the US Food and Drug Administration determined
175
that a product containing the dye 2,4-diamino anisole must include a cancer warn-
ing label, the industry removed this ingredient from formulations.11 This example
shows how the cosmetic industry is responsive to safety issues, not only for reactive
products, but for personal care products in general.
Conclusions
This chapter was intended to introduce some very basic concepts to the cos-
metic chemist about a very complicated group of reactive processes applied to hair.
The processes are complicated not only by the raw materials used, but also the
methods of application and the duration of application. It is our recommendation
that before any of the information is used to begin formulation of the products
discussed in this chapter, the chemist consult various text books and literature with
more extensive information.
The processes that are described here are used in a $2 billion annual market
for the United States and a $7 billion annual market worldwide. Consumers are
likely to demand continued improvement in both ease of use and final results
obtained when the products are used. This allows creative cosmetic chemists the
opportunity to improve products.
References
1. AE Lee, JB Bozza, S Huff and R de la Mettrie, Permanent Waves: An Overview Cosm
& Toil 105 37–66 (1988)
2. W Edman, Current cold wave formulations, Soap Cosm Chem Spec (9) 42 (1979)
3. MG De Navarre, The Chemistry and Manufacture of Cosmetics, Van Nostrand, New
York, 471–481 (1941)
4. ML Garcia, EM Nadgorny, LJ Wolfram, Phsiochemical changes in hair during waving J
Soc Cosm Chem 41 149-151 (1990)
5. J Nothen, V Bollert, G Blankenburg and H Hocker The influence of the osmotic
swelling behavior on the quality of the permanent wave. Proceedings of the 16th
IFSCC International Congress, New York (1990)
6. ET Borish, Hair Waving, Hair and Hair Care, Marcell Dekker, New York191–215 (1997)
7. P Busch et al, Testing Permanent Waves, Cosm & Toil 111(4) 41 (1996)
8. US Patent 3,864,476 Bisulfite Permanent Waving, issued Feb. 4, 1975
9. 10 AN Syed, et al, African-American Hair, Cosm & Toil 110 (10) 39 (1995)
10. A Syed, “Ethnic hair care products.” In Hair and Hair Care, Marcel Dekker, New York
235 (1997)
11. P Obukowho, et al, Hair Curl Relaxers, Cosm & Toil 110(10) 65 (1995)
12. KC Brown, Hair coloring Hair and Hair Care, Marcel Dekker, New York, 192 (1997)
13. CR Robbins, Chemical and Physical Behavior of Human Hair 2nd ed, Springer-Verlag,
176 (1988)
Chapter 18
The Essence of Fragrance

This chapter introduces the beginner to fragrance chemistry
by discussing fragrance ingredients, the development process,
formulation issues and fragrance regulations in the EU.
key words: fragrance, notes, fragrance house, fragrance brief,

compatibility, stability, regulations, allergens
W illiam Shakespeare once wrote, “A rose by any other name would smell as
sweet.” But had he been a cosmetic scientist instead of a playwright, Shake-
speare might have asked, How does fragrance make a personal care product smell
as sweet as a rose? To answer this question, the formulator must understand the
basic principles of fragrances and how they are employed in personal care prod-
ucts. This chapter introduces the beginner to fragrance chemistry and how these
compounds are used in formulations.
How Fragrances Are Created

Beginning the creative process: Simply stated, fragrances are compounds
added to personal care products to improve their odor or to create a certain aes-
thetic impression on the user. They are created by specialized companies known as
“fragrance houses” that consist of perfumers, chemists, evaluators, marketers and
other trained professionals. Fragrance suppliers work with product manufacturers
to develop new fragrances in a process that can take many paths. In some cases, the
fragrance house can proactively develop scents based on their internal knowledge
of trends in the marketplace. In other instances, they may develop a fragrance fol-
lowing specific guidelines established by the client company.
The key attributes desired by the client may be summarized in a document
known as a fragrance brief (See Sidebar 18.1 Example Fragrance Brief ). The brief
establishes the project objective, the conceptual direction, and the cost constraints.
It also describes the type of product that the fragrance will be used in and what
kind of testing will be required to validate the acceptability of the fragrance. Many
larger companies use a dedicated liaison, known as a fragrance coordinator, who
deals with the fragrance houses and facilitates this creative process.
Fragrance Descriptions: Table 18.1 shows how we plan to execute the four
variants.
177
178
The Essence of Fragrance Beginning Cosmetic Chemistry
Fragrance Vocabulary
Before understanding fragrance chemistry it is helpful to understand
some of the terminology used to describe fragrances. Some key terms are
defined below.
Accord: A combination of several fragrance notes used as a backbone
around which the rest of the fragrance is built.
Balanced: A fragrance whose components have been so carefully blend-
ed together that no single aromatic body or effect is readily identifiable.
Body: Containing complex overtones and “color;” a fragrance lacking
body is considered to smell “thin.”
Character: The distinct impression the fragrance gives (fruity, floral,
green, etc.)
Diffusion: The degree to which a fragrance radiates from the product or
from the user after application of the product.
Essential oil: A volatile oil obtained from a specific botanical; typically
smells reminiscent of the parent plant or flower.
IFRA: The International Fragrance Association, a non-profit organization
that issues recommendations on the limitations of fragrance ingredients
based on safety data.
Lift: The impact of a fragrance. Highly diffusive fragrances exhibit good
lift.
Strength: The relative intensity of a fragrance impression.
Synthetic: Either derived from natural products or manufactured from
coal tar derivatives and other chemicals. Synthetics may be of a more uniform
quality than their naturally derived counterparts.
Volatility: The degree to which a component freely diffuses into the
atmosphere.
Sidebar 18.1. Example Fragrance Brief

Date: March 21, 2005
Project: Pomegranate-Mint Aromatherapy Foot Scrub
Project #: A-05025
Project Objective: Develop fragrances that meet or exceed the consumer
expectations generated by the Pomegranate-Mint aromatherapy foot scrub
concept.
Concept: New Pomegranate-Mint Aromatherapy Foot Scrub lets you feel like
you have a spa pedicure at home. This unique deep cleaning scrub removes
rough dry skin and gives your feet an invigorating clean feel while releasing
an aromatherapy scent that will stimulate your senses. Foot Scrub comes in
four different types of mint.
179
Submissions due: No later than May 25, 2005

Cost: Fragrances should contribute no more than $0.20/lb to total formula
cost
Fragrance submissions: One submission (8 oz) per variant for a total of four
fragrances.
Base provided: Clear and creamy base will be provided.
Fragrance validation: All fragrances will have to be validated against the
benchmark determined for that fragrance family. We will be conducting
usage tests to validate the in-use experience. However, the House should
submit internal data to support that the fragrance is a good performer (both
in-use and after use).
Table 18.1. Fragrance descriptions and execution from fragrance brief
Skin Benefit Fragrance Profile Formula Profile Color

Energizing Exfoliating/ Pomegranate Clear—maybe Orange
Stimulating with peppermint clear with beads or yellow
Deep
Refreshing Pomegranate Clear—maybe Green
Cleansing with spearmint with a tingly cue
(using menthol)
Calming Moisturizing Pomegranate with Thick, creamy Blue or
wintergreen/mint white
Restoring/ Moisturizing Pomegranate with Thick, creamy Purple or
Nourishing/ (maybe “ultra” “icy cool” type (potential for pink
Pampering moisturizing) mint shimmer or
“moisture” beads)
Building a fragrance: Once the creative direction and the guidelines have
been established the perfumer can begin work. Utilizing years of experience and
training, perfumers literally build the fragrance from a seemingly endless list of
raw materials. The structure of a fragrance is analogous to a pyramid, with the base
being larger than the top.
Like the upper tip of a pyramid, the top notes of the fragrance are the smallest
part. The top notes make up 15–25% of the fragrance, and these notes are those you
smell when you first open the bottle or use the product. They’re usually fresh and
sparkling; they give the fragrance immediate appeal, but they disappear quickly.
The notes that make up the middle section are about 30–40% of the total fra-
grance and they become noticeable after the top notes have faded. The middle
notes are the heart of the fragrance and are typically made up of a complex blend
of flowery notes.
The “base” of a fragrance is made of ingredients known as “bottom notes” that
comprise approximately 40–55% of the fragrance. These bottom notes tend to be
180
long-lasting and less volatile, so they constitute the final stage of the fragrance and
don’t appear until it dries down.
Types of Fragrance Ingredients

To create their fragrance pyramid, perfumers use a variety of essential oils that
can be either natural or synthetic. Natural oils are extracted from plant sources
such as flowers, herbs, spices, mosses, roots and leaves. Extracts from animal
sources such as musk glands have been used historically but they have been largely
replaced by synthetics due to concerns about animal-based products. Synthetic
raw materials are increasingly common as replacements for natural ingredients, in
part because they can also provide new notes that are not found in nature. Some
of the most common notes used in modern fragrances are described here.
• Citrus. These notes are derived from lemon, bergamot, mandarin and orange
and are considered lighter and refreshing. They are very volatile but not very
long-lasting because they diffuse quickly.
• Fruity. Fruity notes are comforting notes based on edible flavors. These
notes are perceived as fresh, natural, clean and crisp, and commonly include
peach, strawberry, apple and coconut. They tend to be strong and diffusive
and are good for covering powerful base odors.
• Herbaceous. Herbaceous notes are crisp, leafy, green, piney or herbal scents.
They are fresh, clean and natural smelling and are usually very diffusive, so
they make good top notes. Sources for herbaceous notes include grass, pine,
basil, rosemary and sage.
• Fougere. Fougere is a note traditionally found in men’s colognes. It is based
on several notes of citrus fruits, green, herbs, geranium and lavender. They
are clean and crisp, often have a soapy quality and can be reminiscent of
fresh air, the outdoors and/or the ocean.
• Floral. Floral notes are the most varied of fragrance ingredients and are the
most popular category for women’s fragrances. They are familiar, clean, gentle
and fresh and include several subtypes. Floral aldehydes are powerful and
fatty-smelling alone, but small amounts can make blends more diffusive and
brilliant. Green floral notes have grassy, fresh cut leaves or grass notes added
and can also be described as “stemmy” or vegetable-like. Fruity florals, as the
name implies, have fruity notes added as accents. They’re bright, diffusive,
volatile and natural smelling.
• Oriental. Oriental notes smell completely different and are loosely described
as being ingredients originally sourced from the Far East. Examples include
amber, frankincense, myrrh, incense notes, sandalwood, vanilla and fir balsam.
These long-lasting scents are used sparingly because they are so heavy and
sweet and because their saturated dark color tends to discolor products. A
related class of ingredients is florientals—floral notes blended with an Asian
accord. They are popular in women’s perfumes but are often too heavy for
personal care products.
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The Development Process

Because the appeal of fragrance is so subjective, it can be a daunting task to
choose the “best” one for the job, no single right answer exists. As described above,
during the planning stage the fragrance house and the client set the direction.
Based on this creative direction, the perfumers and their staff blend fragrance
ingredients with the proper diluents. This development is a science in itself be-
cause fragrance materials are very sensitive to reaction with other ingredients in
the formula.
These combinations are designed independent of the selected base to give a
certain impact by themselves. Once the perfumer has established the initial mix of
accords, it is passed on to the evaluator for assessment. Then the fragrance is put
into a base and evaluated for initial compatibility with the base.
The fragrance is screened to make sure that it satisfies the requirements of
the brief. This screening typically requires some sort of panel testing to ensure
the fragrance is having the desired effect on consumers. Fragrance houses often
use consumer panels to rate the products for sensory attributes. Most also use sensory
testing centers properly equipped to evaluate products. For example, body wash
products can be evaluated in shower stalls specially designed to allow the olfactory
evaluation of the fragrance as it blooms with the warm water.
Depending on the results of these preliminary evaluations the fragrance may
go back to the perfumer for further evaluations. This cycle is repeated until the
fragrance is deemed acceptable. Then it can be tested by a larger group of panelists,
depending on the testing criteria outlined in the fragrance brief.
A common testing criterion is to have 50–100 panelists evaluate the product
versus an identified standard. The standard will, of course, depend on the objective
of the project. For example, if the objective is to cost reduce a fragrance it should be
compared to the original high-cost version. If it is to match or exceed a competitive
product, that product should be the standard. If you are translating a fragrance from
one base to another (e.g., a shampoo fragrance into a hairspray) then the original
product may be used as a standard.
The length of time required for fragrance development varies depending on
the project. As a rule of thumb, at least a month or two is required for development
followed by another four to 12 weeks for stability testing depending on the nature
of the base for which the fragrance is intended. Once the perfumers are satisfied
that the fragrance oil meets the established development criteria, samples are sent
to the client for evaluation. This step requires the formulator to prepare samples
of the fragrance in the client’s product.
Formulating with Fragrance

Formulating a fragrance into a product offers many challenges. A variety of
negative interactions may arise between formula and fragrance—such as compat-
ibility and viscosity issues, appearance changes and destabilization. The solutions
to each problem will depend on the specific formulation.
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Compatibility issues: One issue that can arise when using a new fragrance is
compatibility between formula and fragrance. This incompatibility is not surprising
because fragrances are primarily oily compounds and most formulas are water-based
or emulsions. Fortunately, most cosmetics contain a good amount of surfactant so
fragrances can sometimes be added straight to the formula with no problems.
However, when an incompatibility occurs, a nonionic solubilizing surfactant can
be used; the most common of which are the polysorbates and the oleths. When using
these materials, the fragrance is first mixed into the surfactant before adding to the
final batch. The premix should be sufficiently blended to ensure solubilization.
When using certain nonionic surfactants such as oleth-20, the solubilizer may
need to be heated to make it liquid and easier to use. The amount of solubilizer
needed will vary depending on the formulation. A good starting guide is to use
about three to four times the amount of solubilizer to fragrance. Trial and error
may be needed to find the optimal level.
Effect on viscosity: Since the fragrance generally makes up a small amount of
the total formula, it may seem odd that fragrance can have a significant impact on
viscosity. But it often makes the formula either thinner or thicker, and it will not be
evident which way it will go. This change in viscosity is because fragrances are oily
materials that can affect the surfactant phase and micelle size in the formulation.
One way to deal with this problem is to make viscosity adjustments after the
fragrance has been added. For example, when making a shampoo, salt can be with-
held and added after the fragrance. A salt versus viscosity curve can be created with
the fragranced formula. In formulas that do not have built-in viscosity controls, like
skin creams and conditioners, the levels of thickeners may have to be adjusted to
compensate for the fragrance effect.
Another solution is to give the fragrance house some non-fragranced formula
base and have the fragrance reformulated to better work with the base.
Effect on appearance: Fragrances can affect the appearance of the formula,
often making the product turn yellow or turning clear products like gels hazy. Fra-
grances can also lead to formula destabilization and separation and they can make
an emulsion grainy or even pearlize over time.
Adding the fragrance: Fragrances are typically added at the end of the
formulation process during the cooling phase. Adding them early can have
negative consequences because the more volatile components of the fragrance
will evaporate off when heat is added to the system. Ultimately, the formula
will not smell as expected. The fragrance should be added to the oil phase of
a multiple phase system if heating isn’t required.
Product Stability
Fragrances are reactive because they are made up of organic compounds that
contain reactive groups such as ketones, aldehydes, esters, amides and alkynes.
Fragrance stability testing is helpful to determine formula compatibility. Test-
ing should include storage under conditions of high heat and intense lighting.
Increased heat can drive potential chemical reactions that will change the odor
of a formula. Heat can also increase the amount of fragrance that is lost due to
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the volatility of the compounds. Exposure to light can also have an effect on the
fragrance stability, making the formula turn yellow or smell bad.
If the product is contained in a plastic bottle, it is possible for the fragrance to
migrate into the plastic thus changing the odor of the formula. This problem is why
it is also important to determine stability in the final package.
One solution to problems with heat stability is to incorporate an antioxidant
in the formula. Antioxidants selectively react with free radicals neutralizing
their ability to react with fragrance ingredients. This neutralizing action can
help quench some of the potentially undesired reactions. In the case of light
stability, some help can be obtained by incorporating an ultraviolet filter such
as benzophenone, but this approach is usually inadequate. In cases where a
fragrance is sensitive to light, an opaque package should be used.
Making Modifications for Different Bases

Oftentimes a marketing department will want to create a line of products that
have the same scent. Unfortunately, fragrances do not always smell the same in
different bases. A fragrance used in a shampoo will not likely smell the same when
used in a hairspray. Base odor, fragrance solubilization and fragrance chemical reac-
tions can all have an impact on the final odor.
One potential solution to this problem is to increase the level of fragrance in
the formula. This solution covers any base odor differences between the formulas.
Unfortunately, this trick does not always work and the fragrance will need to be re-
worked by the perfumer starting with non-fragranced base formulas. In this case,
the fragrance house makes a modification of the fragrance so it better matches the
desired end odor.
European Regulations: Now and Future

Now: Europe has been driving many of the regulatory requirements for fra-
grances in cosmetics. And many countries around the world pattern their own legisla-
tive requirements after the European Union EU model. This trend will affect the
labeling requirements and the types of ingredients that can be used. Currently, no
restrictions are posed on the amount or types of fragrance compounds that can be
used in cosmetic formulations. In Europe, the only regulation for cosmetics and
personal care is to put the word “parfum” in the ingredient list.
In the United States, the term “fragrance” is used similarly. Naming the indi-
vidual fragrance ingredients has traditionally not been required because it would
be impractical to list the 50–100 components of a typical fragrance. For people with
chemical sensitivities, this omission has been problematic.
Restrictions and bans in the future: The EU has recently proposed a significant
change. The EU requested a recommendation from the Scientific Committee on
Cosmetic Products and Non-Food Products (SCCNFP) to address this problem.
The SCCNFP provided the EU with three lists that have been incorporated into
recent proposed legislation. One was a list of 26 compounds frequently reported to
cause allergic reactions (Table 18.2). Another list consisted of 78 chemicals that
the committee suggests should be restricted (See Sidebar 18.2).
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Table 18.2. Fragrance allergens
Raw material CAS#

Alpha isomethyl ionone 127-51-5
Amyl cinnamal 122-40-7
Amylcinnamyl alcohol 101-85-9
Anise alcohol 105-13-5
Benzyl alcohol 100-51-6
Benzyl benzoate 120-51-4
Benzyl cinnamate 103-41-3
Benzyl salicylate 118-58-1
Butylphenyl methyl propional 80-54-6
Cinnamal 104-55-2
Cinnamyl alcohol 104-54-1
Citral 5392-40-5
Citronellol 106-22-9
Coumarin 91-64-5
Eugenol 97-53-0
Evernia furfuacea (treemoss) extract 90028-67-4
Evernia prunastri (oakmoss) extract 90028-68-5
Farnesol 4602-84-0
Geraniol 106-24-1
Hexyl cinnamal 101-86-0
Hydroxycitronellol 107-75-5
Hydroxyisohexyl 3-cyclohexene carboxaldehyde 31906-04-4
Isoeugenol 97-54-1
Limonene 5989-27-5
Linalool 78-70-6
Methyl 2-octynoate 111-12-6
Sidebar 18.2. Proposed Restrictions

The list of restricted chemicals provided by the Scientific Committee on
Cosmetic Products and Non-Food Products (SCCNFP) includes compounds
from numerous chemical classes traditionally used in perfumery. For example,
essential oils from pine trees are listed for use at levels that minimize the
amount of peroxides in the fragrance. Natural extracts such as bergamot oil
are listed because they contain furocoumarin-like substances. It is suggested
they only be used as levels below 1 ppm in the final cosmetic product. The
restrictions proposed on the numerous other compounds will certainly have
a limiting effect on the types of fragrances that can be created.
On the other hand, consumers who are sensitive to these types of chemicals
will now have more information when choosing their cosmetics.
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A third list included 36 fragrance materials the committee recommended be

banned from cosmetics (See Sidebar 18.3). Lest we think that everything “natural”
equates to good, there are plenty of naturally derived compounds that have been
shown to cause allergic reactions and that are on the “banned” list. Banning the in-
gredients on the third list could have a significant impact on the variety of fragrances
that are available. The job of the perfumer is getting harder every day.
Sidebar 18.3. Proposed Banned Ingredients

Alantroot (Inula helenium) essential oils and derivatives, e.g., concrete and
absolute
Allylisothiocyanate
Benzyl cyanide
p-tert-Butylphenol
Chenopodium oil
Cyclamen alcohol
Diethyl maleate
Dihydrocoumarin
2,4-Dihydroxy-3-methylbenzaldehyde
3,7-Dimethyl-2-octen-1-ol (6,7-Dihydrogeraniol)
4,6-Dimethyl-8-tert-butylcoumarin
Dimethyl citraconate
7,11-Dimethyl-4,6,10-dodecatrien-3-one
6,10-Dimethyl-3,5,9-undecatrien-2-one
Diphenylamine
Ethyl acrylate
Fig leaf, fresh and preparations (Ficus carica)
trans-2-Heptenal
trans-2-Hexenal diethyl acetal
trans-2-Hexenal dimethyl acetal
Hydroabietyl alcohol
Hydroquinone monoethyl ether
6-Isopropyl-2-decahydronaphthalenol
7-Methoxycoumarin
4-Methoxyphenol
4-(p-Methoxyphenyl)-3-butene-2-one
1-(p-Methoxyphenyl)-1-penten-3-one
Methyl trans-2-butenoate
6-Methylcoumarin
7-Methylcoumarin
5-Methyl-2,3-hexanedione
Musk ambrette
2-Pentylidenecyclohexanone
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4-Phenyl-3-buten-2-one
3,6,10-Trimethyl-3,5,9-undecatrien-2-one
Verbena (Lippia citriodora Kunth.) essential oils and derivatives, e.g., concrete
and absolute
None of the legislation has yet been officially approved, but it is coming. It
is likely that companies will soon be required to list these compounds on their
cosmetics ingredient lists. Many large companies have already begun including
allergens on their lists of ingredients.
Conclusion
While the regulatory environment is making fragrance development more chal-
lenging, perfumers continue to produce unique offerings that can make personal
care products stand out. Even though the number of usable compounds is shrinking,
the creativity of perfumers and formulators has, so far, been able to compensate. In
the future, more odiferous ingredients may be discovered, developed and subse-
quently regulated away, but new fragrances will undoubtedly linger.
Published February 2005 Cosmetics & Toiletries magazine.

Chapter 19
Common “Scents”
Fragrance in Personal Care
Products
A basic review of aromatic material sources and the
fundamental considerations involved in formulating and
evaluating fragrances.
key words: masking odors, unscented, brief, formulation,

consumer testing, stability, safety and regulatory
P ersonal care products are designed to satisfy certain consumer needs. Some of
their ingredients perform specific physical functions, such as skin cleansing or
hair conditioning. Others play more subjective roles in helping the product achieve
consumer satisfaction.
Fragrance is an important part of cosmetic formulations because of the psy-
chological effect it can have. In fact, it often determines a new product’s success
or failure. Therefore, it is vital that formulating chemists learn how and why
fragrances are chosen. It is also important to have a general understanding of the
chemical nature of fragrance raw materials because they often interact—negatively
or positively—with formulations.
Masking Odors
Fragrances are used primarily to change the smell of cosmetic products. This
function is important because many raw materials have an inherently unpleasant
odor that may be detectable in finished products.
Anyone who has smelled a permanent hair-waving product, for example, can
attest to this. In this case, the malodorous culprit is either ammonium thioglycolate
or another thiol compound that breaks the disulfide bonds in hair.
Other raw materials prone to odor problems include:
• Certain quaternized nitrogen compounds, or quats, commonly used in hair-
conditioning products.
• Proteins used in a wide range of personal care products.
• Fats and waxes, surfactants, emulsifiers, and thickeners, used in many skin-
and hair-care products.
• High ethanol concentrations in products like hair sprays.
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188
Common “Scents” Fragrance in Personal Care Products Beginning Cosmetic Chemistry
In all, hundreds of ingredients can potentially affect the scent of a finished

product. Fragrance compounds offset these unpleasant chemical odors, making
products more esthetically acceptable. This process is called “masking” base odors.
Perfumers and fragrance chemists can offset chemical odors with fragrances by
combining aroma chemicals from the thousands available.
Unscented: The effect of these aroma chemicals can be controlled by adjust-
ing their character and intensity. For example, a product’s base odor can be subtly
masked by selecting fragrance compounds that naturally blend with the raw mate-
rial’s odor, a technique that gently offsets the odor.
This approach results in the product having minimal scent and not creating
significant impressions on the user. Such products, though they may contain fra-
grance, are often referred to as “unscented.” Unscented formulations are useful
when it is not desirable to have the product’s fragrance interfere with other scented
products being used concurrently. Since fragrance must appear on the ingredient
label, the claim of “unscented” requires listing the aroma chemicals as separate
ingredients using their INCI names.
For the most part, however, it is desirable to emphasize the presence of fra-
grance in cosmetics. After all, fragrance can do more than simply mask the odor of
a product: it has important psychological influences on consumer perception.
Influencing Purchases
The psychological role of fragrance is subtle but real; fragrance has proven
impact on consumer purchase and intent. Consumer reactions to a product are not
based solely on that product’s technical performance but also on subjective factors,
such as the product’s look, feel and smell. If consumers are given two shampoo
formulas that differ only in the fragrance, they will subconsciously prefer the one
whose fragrance they find more pleasing.
Furthermore, consumers infer certain benefits from a product’s fragrance; spe-
cific fragrances can be associated with better performance—even though laboratory
data shows that fragrance has no measurable effect on performance.
For example, consumers in the United States tend to believe that products
fragranced with certain citrus notes have superior cleaning ability. Chemists
must consider this subjective response to fragrance when formulating consumer
products.
Fragrance shapes perception primarily in three ways: by supporting product
functionality, by reinforcing certain imagery and by drawing attention to specific
ingredients.
Implied functionality: Although most consumers don’t consciously realize it,
smell can actually signal something about a product’s functionality. For example,
a “serious” product, such as a dandruff shampoo, may be fragranced to smell
slightly medicinal instead of overly floral or cosmetic. Such a scent suggests that
the product effectively does what it is supposed to do. Similarly, a baby shampoo
may be softly scented to reinforce the impression that it is gentle and won’t sting
children’s eyes.
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Imagery: Fragrance can underscore specific imagery. For example, a skin-care

product positioned as a botanical treatment might use a fragrance containing so-
phisticated tropical, floral notes to convey that impression, while another intended
as an all-natural product may contain more simple, single-fruit notes.
Specific ingredients: Fragrance can reinforce the presence of specific ingredi-
ents. An apple pectin shampoo may be formulated to smell like a juicy apple, while
a cocoa butter hand lotion might be made as temptingly aromatic as fresh coconut
cream pie. It often helps to sell a product if the formulating chemists choose a
fragrance design that increases consumer awareness of certain ingredients.
Actual Functionality
In addition to psychological effects, fragrances can have real physical uses in a
formula. For example, it is well documented that certain fragrance oils, including
thyme oil, have antimicrobial properties. Such properties may be useful in anti-
bacterial products, such as deodorants, or as a supplement to a product’s preser-
vative system. Other fragrance ingredients are purported to have insect-repellent
properties.
Some evidence even suggests that some fragrances directly affect human be-
havior, such as promoting relaxation or reducing stress. Such claims are historically
the basis of aromatherapy. The fragrance industry favors the term “aromascience”
to describe the temporary effects on emotions or physical performance delivered
through the olfactory system.
Creating Fragrances
Since fragrances have such a strong influence on consumer perception, formu-
lators must select them with care. Most personal care manufacturers do not make
their own fragrances. Instead, fragrances are created by specialty suppliers, known
as fragrance vendors or “houses.” The perfumers and fragrance chemists employed
by these vendors formulate fragrances from component raw materials in a process
analogous to the way a composer builds a piece of music from individual notes.
The process is also much like the one cosmetic chemists use to formulate personal
care products. Both are concerned with performance, stability, cost and safety, and
both delicately balance creative artistry with technical expertise.
Fragrance briefs: To create successful fragrances, perfumers require certain
key information from the product formulator, typically relayed in the form of a
“fragrance brief.” While no industry standard exists for such a document, it typi-
cally includes:
• product description (specific ingredients, physical form and so forth),
• brand image (premium, economy, mass market or drug store)
• special attributes or claims,
• demographics (who will be the target consumer), and
• anticipated competitive products.
Particulars regarding cost, packaging, stability requirements and project com-
pletion time constraints are also important considerations to be addressed. Since
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creating a fragrance is very subjective, several fragrance houses may be given the
same brief and asked to submit samples.
Upon receiving the brief, a perfumer may elect to propose a stock fragrance
that has been previously developed. Most vendors have a large library of such
fragrances for a variety of products.
If a stock fragrance is unsuitable for whatever reason, the perfumer may have
to create a completely new fragrance. This process may take anywhere from a few
weeks to a few months, depending upon the complexity and limitations of the
request. The perfumer’s job is to create a fragrance that satisfies all the conditions
specified in the brief. To accomplish this task, perfumers must rely on their extensive
knowledge of fragrance raw materials.
Raw Material Sources

Raw materials come from a variety of natural and synthetic sources. In the
early days of the fragrance industry, most raw materials were natural derivatives of
plant or animal sources. As the science of organic chemistry developed and chem-
ists isolated fragrant molecules, they produced synthetic ingredients that replaced
many natural materials.
Natural raw materials: Although natural fragrance ingredients have tradition-
ally come from both plant and animal sources, the primary sources today are plants.
We can isolate literally thousands of fragrant materials from all parts of plants to
create fragrances, including the leaves, bark, fruit, roots, berries, seeds, flowers
and wood. Fragrance materials obtained from plants are typically categorized by
the method used to isolate them.
Essential oils: Various types of distillations of plant feedstocks can isolate the
most important type of extract, the essential oils. The simplest of these methods,
water distillation, submerges plant feedstocks in water and heats them with an
external source. The essential oil is then collected as it separates from the water
phase. Similar methods, such as water/steam and steam distillations, result in better
yield and higher quality. Expression is another method for removing essential oils
from plants, in which the plant material is squeezed or scraped.
Essential oils are composed of aromatic oils found in specific plants. They
contain primarily terpenes, a family of chemicals created using isoprene as the
building block. Essential oils may also contain terpenoids, aromatics and hetero-
cyclic compounds.
Although the function of essential oils in plants is not fully known, at least one
is to attract insects for pollination. Essential oils are most likely the byproducts of
fundamental plant metabolism.
Examples of the more important essential oils include cedarwood, citrus, lem-
ongrass, citronella, geranium oil, labiates, clove oil, sandalwood and orris.
Concretes and absolutes: Because of some drawbacks of the distillation
process used to obtain essential oils, other methods can be used, such as volatile
solvent extraction. In this extraction method, plant feedstock is submerged in a
solvent (typically hexane) for several hours. The solvent is then separated from
the plant feedstock and removed by vacuum distillation. The resulting product is
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known as “concrete,” which contains essential oil and some waxes, glycerides and
other similar materials. Volatile solvent extraction is typically used to obtain flower
oils that cannot be isolated through steam or water distillation.
Concretes can be further processed to create absolutes by removing the waxes,
glycerides and other materials. This process involves dissolving the concrete in
alcohol, chilling, and then removing the insoluble material. Concretes and abso-
lutes include jasmine, rose oil, ylang ylang oil, orange blossom (neroli), lavender,
narcissus and oakmoss.
Resinoids: In addition to essential oils, certain plants also produce resins that
can be extracted to produce resinoids. Since these materials have low volatility,
they are used as fragrance fixatives. Fixatives help a fragrance last longer because
they are thought to reduce the volatility of other perfume ingredients. Important
resin types include:
• Gums, which are resinous materials, are usually obtained by boiling the
bark, twigs or leaves of trees and shrubs in water. Consequently, the most
important gums are water-insoluble. Examples include labdanum, olibanum,
opoponax and myrrh, which are used in soap fragrancing.
• Balsams, which are similar to gums except they contain cinnamic and/or
benzoic acids and their derivatives, produce warm, spicy scents. Examples
include balsam tolu, copaiba balsam and Siam benzoin, which is used to
fragrance nail polishes.
Fragrance Chemistry
Chemically speaking, a fragrance is best described as a complex mixture
of ingredients specifically blended to produce specific scents. The chemicals
responsible for the aromatic character of a fragrance can be divided into
three broad categories: terpenoids, aliphatics and benzenoids.
Terpenoids: During the early days of organic chemistry, volatile plant
components were found to have a carbon content in multiples of five (C10, C15,
C20 and so forth). Because many of the earliest known of these compounds
were isolated from oil of turpentine, they became known as “terpenes;” de-
rivatives, including alcohols, aldehydes and esters, are called “terpenoids.”
Terpenoid molecular structure appears to be based on a five-carbon
unit, known as “isoprene.” Different numbers of these molecular units,
creating open and closed rings and levels of oxidation, produces terpenoid
compounds with different scents. These include trans or cis citral, which
smell like lemongrass; linalool, a primary component of lavender; menthol;
and camphor.
Aliphatics: Aliphatic compounds are straight-chain organic chemicals.
Remember from your organic chemistry lab that some, such as acetone,
have strong, distinct scents. Aliphatics are important because they currently
comprise a major portion of modern fragrances. Classified by their molecular
structure, they include the following:
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• Aldehydes, typically containing seven to 12 carbons.

• Alcohols, commonly with six to 12 carbons.
• Esters, characterized by two carbon chains connected by an oxygen
molecule (fruity).
• Ketones are characterized by a specific bond. (Figure 19.1) Methyl
hexyl ketone is used to create lavender.
• Lactones are ring-structure compounds, specifically cyclic esters. An
example is γ-nonalactone (coconut).
Benzenoids: During coal-tar processing, benzenoid compounds contain-
ing fused benzene rings can be isolated. Some important examples include
benzyl acetate, a primary component of jasmine fragrance; phenyl ethyl
alcohol and phenyl ethyl acetate, which both smell like roses; and cinnamic
aldehyde, providing a cinnamon fragrance.
Figure 19.1. Isoprene structure
Figure 19.2. General ketone structure
Synthetic Raw Materials

Organic chemists have long attempted to create synthetics that reproduce the
scent of natural materials. As the field of organic chemistry developed, the use
of synthetic materials became more important. Now, fragrance companies have
developed aromatic materials that have no natural counterparts; the search for
even more continues.
Most synthetic aroma compounds derive from chemical reactions using crude
or turpentine oil as the primary feedstock. They have certain advantages over
natural materials, including less potential for supply problems, better quality and,
often, lower cost. On the other hand, synthetic compounds are mostly single mol-
ecules and are therefore never a perfect match of their multi-component natural
equivalents. Important materials that are primarily derived synthetically include
benzyl acetate, vanillin, musk ketone, citronellol, hexyl cinnamic aldehyde and
phenyl ethyl alcohol.
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Fragrance Formulation
Once perfumers have determined the basic ingredients they will use, they must
combine them in the appropriate proportions. The pioneers of perfumery formu-
lated primarily by trial and error, mixing materials together until they discovered
a pleasant combination.
Over time, they developed a more systematic, scientific approach, based on
the volatility of fragrant materials. In this method, a fragrance is described by its’
top, middle and bottom notes.
Notes: The top note, made of the most volatile materials, is the first ele-
ment smelled when a fragrance is applied. Citrus notes are common top-note
ingredients.
The middle note, or body of a fragrance, is composed of somewhat less volatile
material. These components come more into play after the top notes have dissipated.
Floral scents, such as violet or tuberose, are typical middle notes. The bottom, or
base, note is made from the least volatile materials. Examples include musk scents,
woods and vanillins. This portion is the longest lasting of the fragrance.
In recent years, fragrance suppliers have developed a new technology that
allows them to create fragrances that closely match the aroma of living flowers.
Generically known as “head-space analysis,” this technology analyzes gases in the
air above a living flower to synthetically match a flower’s true scent.
Fragrance Testing
Before submitting their creations, perfumers typically conduct a series of
evaluations. At this stage, the formulator of the personal care product will often
provide the perfumer with an unfragranced product base. The fragrance house
can then perform instrumental analysis, physical product testing and subjective
consumer evaluations.
Instrumental evaluations, such as gas chromatographic or infrared analysis, may
help establish fragrance quality. Physical product testing, such as emulsion stability
testing, ensures that fragrance components do not adversely affect the product,
such as causing separation or discoloration. Conversely, it is important to note that
a product can cause the fragrance to deteriorate, as with high pH formulations that
may be difficult to perfume.
Consumer testing: Subjective evaluations by selected groups of consumers may
also establish whether a fragrance properly masks a product’s base odor and creates
the impressions desired. One way to obtain such information is by “mall intercept
testing,” in which samples are shown to a relatively large number of people (typically
about 50) who fit the consumer profile specified by the formulator. Their responses
provide the perfumer with information on the fragrance’s performance.
Ideal consumer evaluations are done under actual-use conditions. Thus, many
fragrance vendors have specially designed test rooms to mimic the conditions under
which consumers actually smell the fragrance; soap may best be evaluated in a small
shower chamber where the fragrance can interact with warm water.
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When a fragrance has successfully passed all of these tests, a perfumer can have
some degree of confidence that the fragrance and product are working together
properly. The fragrance may then be submitted to a product-development chemist
for further evaluation.
Further Evaluation
Upon receiving fragrance submissions, the formulating chemist determines if
they meet the project requirements. This determination is no small task since a
large number of fragrances may be submitted. While some companies work with
a small number of houses or their own in-house perfumers, others may deal with
a relatively large number of outside houses—as many as eight or 10. If each house
submits multiple fragrances, the total number of samples can be great.
Steps and samples: The evaluation process involves several steps. First, it helps
to determine how well the submissions fit the general profile. For example, those
submissions not meeting cost considerations may be eliminated. Similarly, if the
brief specifies that single-fruit notes should not be included, yet one submission
smells like a strong green apple, the formulator may reject it.
Once the formulator has screened the submissions to a manageable number,
samples of the actual product must be made with the appropriate amounts of fra-
grance. These samples are also evaluated for general acceptance by the product
manufacturer and may be tested to ensure that the fragrance does not negatively
interact with the base.
Finally, some form of consumer evaluation is, once again, helpful to determine
fragrance suitability. To facilitate this process, many companies use employee panels
to screen fragrances. Larger consumer studies may also be conducted to determine
which fragrance best supports the product.
Ultimate fragrance selection is often done in conjunction with other members
of the product-development team, such as the marketing departent. It is wise to
select a backup fragrance in case problems arise with the first choice.
Stability testing: Once a fragrance has been selected, more detailed investi-
gations can take place. For example, stability testing of the fragrance in the actual
product base is a critical step. Whenever possible, testing should be performed
in the final packaging, including caps and labels. Although fragrance houses often
conduct their own (cursory) stability testing, formulators should conduct their own
(more detailed) evaluations. Stability testing at higher temperatures can provide
information about long-term fragrance stability quickly.
An industry rule-of-thumb roughly equates eight weeks at 45°C to one year at
room temperature. In other words, if the fragrance still smells good after exposure
to high temperature and the product shows no significant defects, such as discolor-
ation or separation, the fragrance and the product base are probably compatible.
If negative effects arise, the fragrance house may be asked to revise the fragrance
and correct the problem. If the suitability of the final fragrances is eventually con-
firmed, the product can be produced for the marketplace. Consumers then decide
for themselves if the formulator has done a good job in fragrancing the product.
195
Safety and Regulations

Safety has always been a crucial aspect of fragranced products. The industry has
been self-regulating since the 1960s, but the current regulatory climate has com-
plicated the situation. First, the California Air Resources Board placed significant
VOC restrictions on many products. The European Union mandated labeling of
26 alleged allergens (see Schnuch for a review of the data) making many custom-
ers reluctant to accept them in fragrances (Table 19.1). The simple division of
fragrances products into two categories, leave-on and rinse-off, was elaborated into
11 categories (Table 19.2). Safety testing was historically done on skin, but it is now
evident that little is known about the environmental fate or respiratory effects of
fragrance, issues that are now being addressed. The fragrance industry faces many
new challenges as the world heads to global harmonization of safety standards.
Table 19.1. EU Allergens
Amylcinnamic alcohol Farnesol

α-Amylcinnamic aldehyde Gernaniol
Anisyl alcohol α-Hexyl-cinnamic aldehyde
Benzyl alcohol Hydroxycitronellal
Benzyl benzoate HMPPC*
Benzyl cinnamate Isoeugenol
Benzyl salicylate Lillial
Cinnamic alcohol Limonene
Cinnamic aldehyde Linalool
Citral Methylheptin carbonate
Citronellol γ-Methylionone
Coumarin Oak Moss
Eugenol Tree Moss
* Hydroxymethylpentyl cyclohexenecarboxaldehyde (Lyral)
Table 19.2. RIFM Fragrance Categories
Category 1 Lip Products, Toys, Insect Repellents

Category 2 Deodorants/Antiperspirants
Category 3 Hydroalcoholic Products for Shaved Skin, Men’s Facial Creams &
Balms, Tampons
Category 4 Hydroalcoholic Products for Unshaved Skin, Hair Styling Aids &
Sprays, Body Creams
Category 5 Women’s Facial Cream/Facial Make-up, Hand Cream, Facial Masks,
Wipes/Refreshing Tissue for Hands, Face, Neck, Body
196
Table 19.2. RIFM Fragrance Categories
Category 6 Mouthwash, Toothpaste

Category 7 Intimate Wipes, Baby Wipes
Category 8 Make-up Remover, Hair Styling Aids Non-spray, Nail Care
Category 9 Shampoo, Rinse-off Conditioners, Bar Soap, Feminine Hygiene Pads
and liners
Category 10 Detergents, Hard Surface Cleaners, Diapers
Category 11 All Non-skin or Incidental Skin Contact Products
Conclusion
At first glance, fragrance looks like a simple material that adds esthetic appeal
to a product. Closer inspection shows it to be a complex mixture of chemicals that
demands the close attention of the formulator. The global marketplace has placed
increased emphasis on the technical and regulatory aspects of fragrance. The Green
Movement has also complicated the presence of fragrance in certified products.
With challenges come new solutions, and surely the fragrance industry will evolve
to enable us to continue to add value and pleasure to personal care products.
Recommended Reading
F Buccellato, “Art and Science of Fragrance in Functional Products,” Cosm
& Toil 99(4) (1984)
S Herman, Fragrance Applications: A Survival Guide, Allured Publishing,
Carol Stream, IL (2001)
SJ Jellinek, Use of Fragrance in Consumer Products, John Wiley & Sons, New
York (1975)
J Knowlton and S Pierce, “Perfumery.” In: Handbook of Cosmetic Science and
Technology, 1st ed, Elsevier Science Publishers Oxford
A Kozlowski, ed, Fragrance for Personal Care, Allured Publishing, Carol
Stream, IL (2007)
J Proter, Fragrancing Functional Products, Cosm & Toil 6 (1991)
DH Pybus and CH Sell, “The Chemistry of Fragrances”, RSC (1999)
DJ Rowe, Chemistry and Technology of Flavors and Fragrances, Blackwell
Publishing, (2003)
WH Schmitt and DF Williams, eds, Chemistry and Technology of the Cosmetic
and Toiletries Industry, Blackie Acad and Prof, New York 8 (1992)
A Schnuch et al., Sensitization to 26 fragrances to be labelled according to cur-
rent European regulation, Contact Dermatitis: 57:1–10 (2007)
S Shiffman, New Frontiers in Fragrance Use, Cosm & Toil 6 (1992)
A Vidal, An introduction to perfume technology, Cosm & Toil Manufacturers
Worldwide, Aston Publishing Group, Hertfordshire (1995)
B Willis, Flavor and Fragrances and Functional Ingredients, Perf & Flav 18
(1993)
Chapter 20
Microorganisms and
Personal Care Products
A review of biological contaminants and the chemical
preservatives inhibiting their growth.
key words: bacteria, yeasts, molds, biofilm, parabens,

formaldehyde, phenols, pyridine
I n the time it takes you to read the next few pages, you will encounter millions
of tiny, alien-like creatures. No, this isn’t science fiction, it’s about microorgan-
isms and how they can affect personal care products. These strange creatures are
bacteria, molds and yeasts that hover in the air you breathe, rest on the things you
touch, even live on your skin. Usually, they do not cause problems for cosmetic
chemists. However, if enough of them get into product batches, they may cause
trouble. Further all governemnts require cosmetics to be safe during their normal
and foreseeable use. If these can grow in your product due to inadequate preserva-
tion, they can cause harm to the consumer.
What are these creatures? How do they get into our products? What happens
when they do? Most important, perhaps, is how can we control them? We will
discuss these microorganisms in the general environment, how they can contami-
nate personal care products, their growth and how we can protect against such
contamination.
Microorganism Classification
These microscopic creatures cannot be classified as strictly animals or plants
but according to their cellular structure. Biologists categorize those with a simple,
unorganized nucleus as prokaryotes, members of the kingdom monera. Others
with a well-defined cellular nucleus are eukaryotes—Greek for “true nucleus”—
and belong to the kingdom protista. Certain eukaryotes, like fungi, are grouped
separately in the kingdom mycetae. The main types of microorganisms affecting
personal care products are bacteria, yeasts and molds.
Bacteria: Bacteria are single-cell prokaryotes whose cell walls are, for the
most part, well-defined. They range from 0.5–10 µm in size and exist in a variety
of shapes, such as spherical (coccus), rod-shaped (bacillus), spiral (spirillum) and
comma-shaped (vibrio). Bacteria, which reproduce by cellular division, are classi-
fied as gram-negative or gram-positive, based on their ability to absorb and retain
197
198
Microorganisms and Personal Care Products Beginning Cosmetic Chemistry
a certain type of staining dye named after Dr. Hans Christian Gram, a Danish
bacteriologist who made this discovery, hence the use of “G”.
Yeasts: Yeasts are unicellular fungi that metabolize carbohydrates by fermenta-
tion. Larger than bacteria, they replicate by either a budding process or cell division.
Most cosmetics are hostile to yeast.
Molds: Molds, another subset of fungi, belong to the more advanced class of
eukaryotes. They can be either unicellular or multicellular and range from 1 µm to
several centimeters in size. Molds are often, but not always, aerobic and reproduce
asexually by branching.
Growth and Infection

Microorganisms spread through a variety of transmission substrates, including
water droplets, dust particles, insects, animals and human beings. In small quantities,
their presence may be tolerable. However, if their population increases, so does
the likelihood of a contamination problem. For example, Pseudomonas in sufficient
quantities can cause skin and eye infections, food poisoning, toxic shock, strep throat
and even dental plaque. Bacillus can cause unsightly product contamination. The
yeast Candida albicans can cause infections like thrush.
Whenever microorganisms find the appropriate conditions for growth, these
problems can occur. All it takes to make them feel at home is a little water, an
organic substrate that supplies carbon and nitrogen, and a moderate temperature.
All too often, personal care products provide such comfortable accommodations
for these invaders.
Product Contamination
Usually, low levels of microbial contamination are inevitable and do not pose
a significant threat to carefully formulated products. However, unchecked micro-
bial growth can cause spoilage and other problems. Although most products are
designed to deal with a certain microbial level, they are not disinfectants and can
be overwhelmed. Thus, it helps to limit a product’s exposure to contamination.
Microbes can infiltrate personal care products in several ways:
• Transference to the batch during manufacture from processing equipment
or raw materials.
• Post-manufacture introduction to the product from contact with dirty storage
vessels or packaging.
• Entering a product as a result of consumer usage.
Equipment contamination: Contamination from manufacturing equipment
can occur not only in the production tank, but also in any of the piping and transfer
vessels used to produce the batch. Microorganisms in the form of spores may lay
dormant in nooks and crannies, waiting for the nutrients they need to grow. Be-
cause plastic frequently has ridges and rough surfaces, special care must be taken
with tubing and storage vessels made of this material. However, even the most
thorough sanitization techniques may not adequately eradicate this accumulation
of microorganisms, known as a “biofilm.”
199
Ingredient contamination: Contaminated raw materials may also introduce

microorganisms into a finished personal care product. Water, the most common raw
material, is particularly prone to microbial contamination; care must be taken to
not use water with a high microbial content. Furthermore, ingredients containing
even small amounts of water are potential sources of contamination. These materi-
als include botanical extracts, carbohydrates, glycosides, higher molecular-weight
alcohols, surfactants, fatty acids and esters, proteins and even powders, such as talc
and starches. Contamination can also result from “ingredients” that aren’t supposed
to be in the batch, such as foreign objects that accidentally find their way into the
mixing kettle. An uncovered batch is an open invitation to invading organisms.
Post-manufacture contamination: Even when a product is compounded and
processed under aseptic conditions and manages to escape contamination during
manufacture, it may still encounter microorganisms when placed into containers.
These include piping that the product flows through on its way out of the batch
tank, as well as any storage tanks it may be kept in before filling. Of course, contact
with its final packaging may introduce contamination as well.
Consumer contamination: Even after successful manufacturing and packaging,
a product may still become contaminated during consumer usage. To illustrate, a
cream or lotion is packaged in a wide-mouth jar. A consumer’s non-sterile fingers
dip into the jar, allowing transfer of organisms. Similarly, a consumer could un-
knowingly contaminate shampoo by adding water (no tap water is sterile) to make
it last longer or easier to pour out the last bit.
Tracking and Controlling Microorganism Growth

As we have shown, microbial contamination can come from many sources over
the life of a personal care product. Formulating chemists must be aware of this
problem and understand how it can affect their formulations.
Plate counting: A simple procedure, known as a plate count, is useful for
detecting and quantifying microorganisms living in tanks, equipment, bottles, raw
materials and finished products. This method involves observing a sample on a
plate of nutrients for evidence of microbial growth. To help control microbiological
problems, many companies have trained microbiologists on staff to conduct such
procedures; others rely on outside testing agencies.
Sanitizing measures: Controlling microbial growth is a critical factor to con-
sider when formulating and manufacturing most personal care products. Preserva-
tion efforts really begin before the batch is even made because if the equipment
is contaminated, the batch will probably end up contaminated as well. To prevent
this problem, equipment, tanks and piping must be sanitized with steam or biocidal
agents. Similarly, finished products may be kept clean by ensuring that incoming
raw materials are free from high levels of contamination.
Preservatives
Because the product is likely to be exposed to some contamination, it is wise
to provide some built-in resistance to microbial growth. To inhibit the growth of
residual organisms and prevent the growth of any further contamination the product
200
might encounter, chemical biocidal agents, known as preservatives, may be added.

In 1993, more than 80 compounds were used to preserve personal care products
in the United States. Although we cannot list each one, it is useful to examine their
general groupings.
Parabens
Currently, the most common preservatives
in the industry are parabens, which are alkyl
esters of p-hydroxybenzoic acid (Figure 20.1).
Parabens were first used as drug preservatives
in 1924 and have been permitted as food pre-
servatives for more than 50 years. They are
prepared primarily by reacting the desired
alcohol—methyl, ethyl and so forth—with
p-hydroxybenzoic acid in the presence of an
Figure 20.1. General chemical
acid catalyst, such as sulfuric acid. Parabens are
structure of paraben esters
typically supplied as small, crystals or powders, (R is a methyl, ethyl, propyl or
either colorless or white. They have limited butyl group)
water solubility, which decreases as molecular
weight increases.
Paraben activity: Paraben antimicrobial activity comes from its interaction
with key metabolic pathways in target organisms, which is affected in various ways
by many raw materials. For instance, antimicrobial activity is enhanced by either
ethylene diamine tetraacetic acid salts (EDTA), which weaken the cell wall to al-
low penetration of the paraben, or propylene glycol that helps solubilize it. Some
factors affecting paraben activity include the amount of oil present, the pH of the
final product, and certain materials, such as nonionic surfactants.
Paraben characteristics: Parabens have many characteristics that make them
ideal preservatives in personal care products:
• minor negative side effects on finished products because they are essentially
colorless, odorless and stable;
• effective against a broad spectrum of microorganisms, including most fungi
and gram-positive bacteria;
• low cost relative to the amount used; and
• generally regarded as safe with low toxicity and accepted for use in most
countries.
Unfortunately, parabens also have limitations, including ineffectiveness in
some systems, limited pH effectiveness, and low activity against certain bacteria—
particularly Pseudomonas. Because of these limitations, other preservatives are used
in conjunction with parabens. Finally parabens have been under attack based on
faulty science, which has resulted in consumers believing that parabens are bad
for them and want products formulated with other preservatives or even free of
all preservatives.
201
Formaldehyde
After parabens, the most widely used
chemical preservatives are formaldehyde de-
rivatives (Figure 20.2), which are active over
a broad spectrum of bacteria and fungi. Their
effectiveness is a result of their ability to cause Figure 20.2.
Formaldehyde structure
irreversible folding of membrane proteins by
forming methylene bridges between amino
acids. Formaldehyde derivatives are compatible with most surfactants but incom-
patible with ammonium salts, proteins, heavy metal salts and hydrogen peroxide.
Although formaldehyde has been used for many years in shampoos, condition-
ers and other rinse-off products, its safety remains questioned. Some studies have
shown the anhydrous gas to be a carcinogen in rats. However this gas reacts almost
irreversibly with water to form methylene glycol, which has not been shown to be
carcinogenic. Also, it is extremely volatile and its vapors may cause irritation in the
mucous membranes. Its primary use in cosmetics today is as a nail hardener,
not as a preservative.
Formaldehyde donors: Other compounds, known as formaldehyde donors
and other aldehyde derivatives, were developed to provide most of the benefits
of formaldehyde without its negative side effects. They may release formaldehyde
when placed in an aqueous solution, and have many advantages over straight form-
aldehyde, including less irritating vapor, lower toxicity and better compatibility with
more raw materials. Common formaldehyde donors include DMDM hydantoin,
quaternium-15, diazolidinyl urea, sodium hydroxymethyl glycinate and imidazolidinyl
urea. It should be noted that the last compound may or may not be considered a
formaldehyde donor, depending on the test methods used to analyze them.
Formaldehyde donors are relatively inexpensive yet highly effective against bac-
teria and fungi. Although many countries allow their use in personal care products,
concerns over formaldehyde toxicity have had an impact on their acceptance. In
Japan and some other countries, their use is restricted.
Phenol Derivatives
Phenols have been used as biocides since the late 19th century. These com-
pounds contain at least one benzene ring substituted with an alkyl or aryl group.
Most phenols are barely water soluble and used at levels below 2%.
Phenols inactivate bacteria in two ways, depending on their concentration. They
can associate with bacterial cell walls, thereby disturbing cell biological activity and
preventing reproduction. In higher concentrations, they cause irreversible leakage of
materials through the cell wall. Many phenols, including chloroxylenol and thymol,
are effective against bacteria and fungi but find limited use because of their odor.
Phenoxyethanol, the most extensively used phenolic derivative in personal care
products, is particularly effective against gram-negative bacteria and is frequently
used as a solvent for parabens.
202
Influences on phenol activity: Most phenols are negatively affected by the

presence of some surfactants, especially cationic and nonionic surfactants. Their
activity is also highly dependent on the pH of the system. Although the parent
phenol molecule is toxic, its derivatives used in personal care products are generally
nontoxic. Thus, use of phenols is accepted in many countries.
Quaternary Compounds
Certain quaternary compounds,
or “quats,” have antimicrobial ac-
tivity. These molecules are surfac-
tants with at least one quaternized
nitrogen group (Figure 20.3). In
general, quats have a benzyl group, Figure 20.3. General chemical structure
are present in salt form, are soluble of quaternary compounds (R, R1, R2 and
in water and used at levels of 0.5% R3 represent short chain hydrocarbon
or lower. groups and X– is a Cl– or Br- ion)
The exact mode by which quats
destroy microbes is unknown. Since they possess a positive charge, they are probably
attracted to the negatively charged cell walls and somehow interfere with natural
biological processes. Benzalkonium chloride is effective against bacteria, particularly
gram-positive ones. Benzethonium chloride is more effective against fungi and
algae. Methene ammonium chloride is active against the broadest spectrum, killing
bacteria, molds and yeasts. Solubility in water makes them good preservatives for
water-based formulations. However, they are cationic, so most are incompatible
with anionic surfactants. They show the best activity above a pH of 7.
Alcohols
Certain alcohol groups are commonly employed for their antimicrobial proper-
ties. These include ethanol, benzyl alcohol, chlorobutanol, dichlorobenzyl alcohol
and phenethyl alcohol. Although propylene glycol is technically a diol, it is also
classified in this preservative group. Alcohol antimicrobial activity may be a result
of an interaction with the cell wall, where they may induce cellular destruction by
increasing cell wall permeability, causing vital materials to leak out.
Alcohol effectiveness: Alcohol preservatives are most effective against bac-
teria but have limited activity against fungi. Alcohol effectiveness as a preservative
generally depends on the specific type and concentration of the material used. For
example, neither ethanol nor propylene glycol are effective as preservatives unless
used at levels above 15%. Significantly lower amounts of benzyl alcohol (1–3%) and
chlorobutanol (0.5% maximum) are required. Alcohols are generally more effective
in acid pHs. As with parabens, their antimicrobial activity is negatively affected by
the presence of certain surfactants.
Organic Compounds
Many organic compounds exhibit antimicrobial activity. These include organic
acids and their salts, such as benzoic acid, sorbic acid, sodium benzoate and potassium
203
sorbate. They are mostly active against molds and yeasts, showing only minimal ef-
fectiveness against bacteria. The mechanism by which organic acids and their salts
prevent microbial growth requires undissociated acid molecules to interact with
the cell wall. Thus, pH is a major limitation, with optimal effectiveness in acidic
pHs. Salts are used for ease of incorporating the preservative and the pH is than
lowered to release the free acid.
Effective organic mixture: Another important organic preservative is a mixture
of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-isothiazoline-3-one.
This mixture is widely used in personal care products, providing effective control
of bacterial and fungal growth. Its maximum use levels are—7.5 ppm for leave-on
products and 15 ppm for rinse-off applications—and remains active over a pH range
of 2–9. It is compatible with most surfactants but can be inactivated by materials,
such as bleach and amines, sulfites or a high pH. Although some studies suggest
that this mixture causes sensitization, it is generally considered safe for product
use at recommended levels. The 2-methyl-4-isothiazoline-3-one is now sold alone
and is active against bacteria.
Higher Molecular weight Diols

As previously mentioned propylene glycol (C-3 diol) finds use as a solvent but
only when added at high concentrations. It makes products self-preserving. Unfor-
tunately, the higher the concentration, the more skin burning and irritation occurs.
Many “hypoallergenic” cosmetics have substituted butylene glycol (C-4 diol) as the
higher molecular weight has less safety concerns. Pentylene glycol (C-5) at levels
of 2.5% is effective in controlling bacterial growth. As you increase the molecular
weight, the antibacterial activity increases, the solubility in water decreases as does
the irritation. Recently the C-6 (1,2- hexanediol) and C-8 (caprylyl glycol), both
alone and in combination, have found use as cosmetic preservatives. All of the 1,2
diols show poor activity against fungi and must be used with other preservatives.

Acknowledgments: The authors thank staff research microbiologist Rich Mulhall for his help in
preparing this chapter.
Additional Reading
A Balows, et al, Manual of Clinical Microbiology, 5th ed, American Society of
Microbiologists, Washington, DC (1991)
MS Balsam and E Sagarin (Eds.), Cosmetics Science and Technology, John
Wiley & Sons, New York (1974)
Cosmetic Preservatives Encyclopedia Antimicrobials, Cosm Toil 105(3) 49–60
(1990)
Donald, Orth and S Marcel, Handbook of Cosmetic Microbiology, Marcel
Dekker, Inc., NY (1993)
J J Kabara (Ed.), Cosmetic and Drug Preservation: Principles and Practice,
Marcel Dekker Inc., NY (1984)
204
J Knowlton and S Pearce, Handbook of Cosmetic Science and Technology,

Elsevier Science Publishers, Oxford (1993)
N Kriegand R Krieg (Eds.), Bergey’s Manual of Systemic Bacteriology, Williams
& Wilkins. Baltimore, MD 1 (1984)
Preservative Frequency of Use, Cosm Toil 108(10) 47 (1993)
III. Product Development:
From Beaker to Bottle

Chapter 21
Lab Notebooks:
The “Write” Stuff
Successful record-keeping can separate a mediocre scientist
from a great chemist.
key words: beginning chemists, record-keeping, notebook, lab
O ne of the essential qualities required of a successful cosmetic chemist is the

ability to accurately and efficiently record data. Novice chemists, as well as
seasoned scientists, can fall prey to the dangers of bad record-keeping. One famous
example involves the discovery of the planet Uranus. In the 1760s, the planet was
observed several times by astronomer Pierre LeMonnier, but his data was scrawled
in obscure places (like paper bags) instead of properly recorded in notebooks. This
sloppy recordkeeping prevented him from seeing a pattern that would have indicated
that the nocturnal light was actually a planet. It was not until decades later, when
Sir William Herschel carefully reviewed data based on his own observations, that
the eighth planet was officially “discovered.”
As a cosmetic chemist, you may not feel like your mistakes are of such an
astronomical nature; however, you have many down-to-earth reasons for keeping
a good laboratory notebook. This chapter explains why it is important to keep a
proper notebook, what the important features of the book are and how to use them
to your advantage.
The Tool
Although the physical structure of the book is important, what really matters
is the “write” stuff that you put inside. This section will focus on what kind of in-
formation to include as well as what not to include, how to deal with mistakes, and
what to do with a completed notebook.
The lab notebook is as important a tool as the pH meter, mixer, viscometer,
or any other piece of laboratory equipment. It allows you to record data, repeat
experiments, retrieve information and document ideas. Ideally, the lab notebook
is utilized as an effective method to record information which is important to this
industry: observations of empirical properties, such as viscosity, pH, color and odor;
and how such properties vary as changes are made to a product. The notebook is
invaluable for ensuring that, if necessary, a colleague will be able to continue your
work.
207
208
Lab Notebooks: The “Write Stuff” Beginning Cosmetic Chemistry
Certainly, one of the best reasons to make good use of your notebook is to make
things easier on yourself. Rest assured that at some point, your boss will ask you for
some piece of information that you long ago decided was trivial. If your habit was
to scratch this type of information down on a legal pad, you can bet your Maison
G deNavarre Award (the cosmetic industry/IFSCC equivalent of a Nobel Prize)
that you will never find that particular piece of paper again. A properly held lab
notebook can be an easily traceable repository for all your recorded data.
Aside from the requests to produce trivia, you may actually need to reproduce
some of your own experiments, too. A detailed notebook is, again, invaluable in
this regard. In the case of cosmetic science, much of the investigative work takes
the form of repeated batch preparation with small variations in raw materials or
manufacturing procedures. Apparently insignificant changes in processing tem-
peratures or order of addition of raw materials can drastically alter the outcome of
your final product. How can you track these seemingly endless variations? Write
them down!
In fact, much of what you do in the lab should be written/recorded in your
notebook. Even that germ of an idea you have had for that new product should
be recorded. Recording and dating your thoughts ensures a permanent record of
them. In that sense, lab notebooks are like the police: they serve and protect. The
ideas you save may relate to new product development, or to refinement of existing
analytical methods or manufacturing procedures; however, in either case, your note-
book serves as an excellent place to keep a record of invention. Since the granting
of patents often hinges upon the date of “discovery,” recording each new concept
and each step of the new invention can provide your company with the legal legs
it needs to stand on in the event of litigation. Of course, you should consult your
supervisor(s) for company procedures regarding patent protection; however, lab
notebooks are considered appropriate legal documents in all legal cases. Therefore,
lab notebooks must be treated with a certain amount of respect.
Finally, having all your information in one place can be helpful to visualize pat-
terns in data and make connections which might have otherwise gone unnoticed
(remember Pierre).
What to include: Almost any piece of information relevant to your work is
acceptable for inclusion in your book. Many of the rules you learned in school
regarding academic notebooks apply to the industrial book, too. You should begin
with an Objective statement at the top of the page. This statement is followed by a
description of the Procedure employed in the experiment. This description should
include details of the formulation and batching, including processing times and
temperatures; and identification of raw materials, including CTFA names, trade
names and supplier lot numbers. The Results of your experiment should be care-
fully detailed. Such results may take the form of simple observations or complex
data tables. Of course, your Conclusions should be duly noted and future actions
recommended.
One of the most important things to remember is to honestly record data if it
is to be of any use to you in the future. A lab notebook that does not contain an
honest reflection of observations is useless.
209
What not to include: What not to enter may be nearly as important as what
to enter. Nonrelevant information, such as phone messages and stock reports,
are forbidden! Only data regarding the experiments at hand or other information
related to the project should be written down—remember, these notebooks are
legal documents. Furthermore, pasted-in results, such as analysis charts and copies
of memos do not belong in a well-kept notebook. One reason is simple common
sense: if you refer to data from a chart glued to page 17 and that attachment falls
out, the data is lost. In a strict legal sense, such attachments are not considered
admissible evidence, just as the unattested blank pages are not, and they could
damage the strength of your company’s argument if the notebook is ever called
into court as evidence.
Obviously, illegible entries are bad form. Your notebook does not have to be
the neatest piece of artwork you have ever created. However, it certainly must be
legible, if it is to have any value. Any mistakes should be crossed out with a single
line (use of liquid paper is punishable by death) and a brief explanation noted next
to it. By the same token, use of pencil is considered a cardinal sin (from both a
permanence and legal standpoint). Black ink is preferred; blue or red is problem-
atic because it does not copy well (which is important when microfiching books
for long-term storage).
When a page is finished, do not leave any large blank areas. Fill up the space by
drawing a line through empty areas to prevent subsequent addition to, or tamper-
ing with, data. As mentioned above, you should avoid recording important data on
blank pages. These pages are not numbered and are not equipped for witnessing.
Use them for scratch calculations or doodling only.
Storing Completed Notebooks

Upon completion of the entire book, finalize the index and make sure each page
is full, signed and witnessed. The book is then typically transferred to a central stor-
age area. Most companies make provisions for someone to be Keeper of the Books;
this individual may be a librarian or department head. He or she is responsible for
ensuring that your notebook adheres to all company rules.
Companies with a large number of chemists make arrangements to have their
completed notebooks microfiched or microfilmed to reduce storage space. In such
a case, it is critical that your index is as detailed as possible to ensure that your
original data can be easily retrieved.
Electronic Lab Notebooks

The methods of data storage described above are rapidly being obsoleted be-
cause of a shift away from handwritten notebooks toward electronic lab notebooks
or ELNs. The Collaborative Electronic Notebook Systems Association defines
ELNs as “a system to create, store, retrieve, and share fully electronic records in
ways that meet all legal, regulatory, technical and scientific requirements” but you
can think of it as essentially a direct replacement for the paper lab notebook. It
serves all the same basic functions including creating patent evidence, cross dis-
cipline collaboration and general record keeping. But in addition, ELNs offer the
210
opportunity to include much, much more. For example, ELNs can incorporate data
from other software systems that provide chemical structure drawing, structure
and sub-structure searching, compound registration, and so on.
While still far from perfect, ELNs are becoming increasingly important in a
world that relies on rapid dissemination of electronic information. While ELNs can
provide gains in productivity and better management of scientific knowledge, they
also raise concerns about legal and compliance issues, cost, security of data storage,
and how easily scientists will adapt to a new way of record keeping.
In broad terms, two types of ELNs are available to choose from: discipline-
specific and generic. The generic type is built on software that provides the structure
and tools to create and search content in a way that satisfies the needs of almost
any science-related industry. Discipline-specific ELNs are custom designed for
a particular speciality such as chemistry, biology or analytical. Many commercial
ELNs offer a combination of these two approaches.
As your organization is considering moving to ELNs you’ll have to carefully
consider cost. Determining return on investment of ELNs is more complicated
than just evaluating the cost of the software. In addition to thinking about the cost
of purchasing and archiving paper notebooks, you have to factor in the cost of
the time scientists spend hand writing, and cutting and pasting data. The cost of
time associated with the passing around hard copies to be witnessed must also be
calculated. And while the start-up costs are high for ELNs, adding new users and
additional storage space is much more modest.
Benefits of ELNs
• Time savings (some companies have experienced approximately 10–15%
reduction in time spent in data entry. Therefore, scientists can spend more
time in the laboratory
• Information is easier to store, search, retrieve, and share.
• Efficiency is increased by eliminating paper
• The need to repeat experiments is reduced
• Improved data quality (better legibility)
• Better transition of information when people join/leave the Company
• Increased collaboration through on-line use in meetings
• Ability link to instrument data
Data preservation issues

Data storage is one of the fundamental issues that face every type of electronic
notebook media. This same issue applies to government records, medical records,
and scientific records as well as personal collections of digital data. In all cases
the problem is how to ensure the data will still be accessible far into the future.
File formats and associated applications must be carefully chosen to ensure fu-
ture compatibility—this task is not simple! Current thinking indicates that open
data formats and open source code could be a solution, but the matter is far from
settled.
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Patent related Issues

The US patent system works on a “First to Invent” principle and therefore, it is
in your company’s best interest to create and preserve evidence of new inventions.
Lab notebooks provide essential proof of who created what first and most companies
require that the authors as well as a witness sign each notebook page. As you make
the move from paper to electronic documentation you’ll have to consider how to
use digital signatures to ensure patent protection. A digital signature is a specific
type of electronic signature that encrypts information to confirm the identity of
the author, using a password and time stamp for each record.
Regulatory compliance issues

Several criteria must be met in order to ensure your ELN meets the necessary
regulatory requirements. Of course these will vary based on local regulations, but
in general the ELN system should:
• Be validated
• Produce human readable output
• Have security/access control
• Have an audit trail
• Have version control
• Have data validity checks
• Have provide an electronic signature process that includes name of signer,
date and time, and meaning of signature
• Establish corporate internal policies and guidelines for regulatory
compliance.
• Develop a clear, comprehensive migration strategy.
• Include records, signatures, audit trail
• Establish retention policies based on current predicate rule requirements.
Embracing electronic lab notebooks

Because switching to ELNs can be a dramatic change in the way scientists work,
the move from paper to electronic is not always smooth. How easily companies
adapt to using ELNs depends on factors like perceived usefulness (“the degree to
which a person believes that using a particular system would enhance his or her job
performance”) and perceived ease-of-use (“the degree to which a person believes
that using a particular system would be free from effort”). In addition, emphasizing
ELN adoption as a “laboratory” project, as opposed to an “IT” project can make it
easier for scientists to accept the switch.
Even though the move to ELN is for the benefit of the scientists, your IT
department must understand and support the technology switch to make it suc-
cessful. Therefore you should look for a system that will work in your existing IT
infrastructure. You’ll want IT to explore integration across not only multiple desk
tops, but mobile devices such as tablets, laptops, and palmtops. They should also
ensure that adequate data storage is planned for and confirm that the storage system
has the ability to search and retrieve information.
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Choosing the best ELN

To close this section, here are some factors to consider when choosing an
electronic lab notebook.
• Are you planning on using an ELN as a direct replacement for paper? Or, will
you be adding additional functionality to support specific types of research
(e.g., chemistry, biology), and to interface with other software systems (e.g.,
LIMS, document management, instrumentation)?
• What is your budget?
• What will your record retention policy be?
• How will your IT department be involved in the process?
• How will corporate legal council be involved?
• What are the relevant regulatory requirements and how will you take them
into consideration?
• Have all parties (lab, IT, legal, quality, regulatory, records control and of
course management) given input/approval?
Notebook format
Just as with every other laboratory tool, lab notebooks come in many styles.
However, the various types of notebooks have certain universal characteristics
involving book structure and format. Nearly all books include an index (or table of
contents) and various individual page elements that identify what was done, when,
how, why, as well as who was involved with the work.
Paper notebooks follow a basic arrangement: they consist of either 100 or
200 bound pages, which are printed with a grid-style format. It is common for
the 200-page book to have the grid printed on both sides of the page; but, in the
smaller version, the back side of each page is left blank. This blank area is useful
for scratch calculations. However, since this blank page lacks a designated space
for legal signature, neither data nor other significant information should ever be
recorded there.
The front of the book contains a section to be used as an index or table of
contents which, when the book is completed, should list each item in the book
by page number. This list can be a simple chronological listing of each page. Or,
pages related to specific projects can be grouped together to facilitate tracking the
progress of your work. Such an index can be compiled while you are working in
the book or after its completion. In either case, when the index is entered into a
database, this information simplifies data retrieval.
Page format
The most basic elements of the book are designed to identify the work done,
help track the work and ensure that the data will be legally recognized.
Notice the first of these items across the top of each page—the four-digit
Notebook Number. It is imprinted on the notebook spine and stamped on each
individual page. This fingerprint uniquely identifies each lab notebook. This number,
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along with the page number, will become your trail of bread crumbs, enabling you
or your colleagues to retrace the work you have done on any project.
Notebooks also have a space to indicate when the work is Continued From
so that you can note the most recent page that contains information on the same
project. If this particular page is the first place the project appears it should be
indicated accordingly (i.e., Start of Project).
The top line also includes a blank for the Title. It should give the reader some
inkling as to what is going to happen on this page. This spot is a good place to
include the project name.
In most lab notebooks, the page format also includes a Project Number, which
provides you with an additional way to track projects. This number may be important
for internal bookkeeping, and it can help when you assemble the index. Format for
this number will vary according to your companyís procedures.
The body of the page, where the actual data will be entered, is marked by a
grid. Avoid writing outside of the margins to ensure that none of the entry is lost
if the page is photocopied or microfiched.
At the bottom of the page, in the Invented By/Signed By section, you will be
asked for your autograph. This section is important for legal reasons. Furthermore,
the work you do must be Witnessed By and signed by another individual. Some
companies prefer that a manager witness and sign lab notes; others allow a signature
from another chemist. Consult with your supervisor regarding specifics of notebook
witnessing at your company. Finally, the bottom of the page also has a Continued
To space to designate the page number where this work is continued.
Conclusion
Although the future will bring more advanced methods of information storage,
you still must take responsibility for entering your data properly. If not, you take
the risk of reducing the value of your work or, as the old adage states, “garbage in/
garbage out.” Just ask Pierre LeMonnier.
References and Further Reading

1. CENSA: The Collaborative Electronic Notebook Systems Association www.censa.org
2. Atrium Research www.atriumresearch.com/
3. The Gartner Hype Cycles www.gartner.com
4. D McCotter and P Wilcox, “Using Electronic Records in Patent Proceedings.” In
Managing Intellectual Property’s World IP Contacts Handbook, 14th edition(2007)
Available at www.mondaq.com
5. IP Expert Advice: Tips on creating a lab notebook that contains “convincing evidence”
www.edn.com/article/CA6445886.html?industryid=47048
6. Admissibility of Electronic in Interferences, Bruce H. Stoner Jr., Chief Administrative
Patent Judge, www.uspto.gov/web/offices/com/sol/og/con/files/cons119.htm
7. EM Rogers, Diffusion of Innovations, The Free Press. New York
8. GA Moore, Crossing The Chasm, Capstone Publishing
9. RP Bagozzi,. FD Davis, and PRWarshaw, Development and test of a theory of
technological learning and usage, Human Relations 45(7) 660–686 (1992)
214
Further Reading
Writing the Laboratory Notebook, Howard M. Kanare, An American Chemical
Society Publication
Why Innovation Fails, Carl Franklin, Spiro Press
The Myth of the Paperless Office, Abigail J. Sellen and Richard H. R.Harper,
The MIT Press
Laboratory Notebook Guidelines: www.bookfactory.com/, BookFactory, LLC,
2302 S. Edwin C. Moses Blvd, Dayton, OH 45408
Websites
Atrium Research: www.atriumresearch.com
CENSA, The Collaborative Electronic Notebook Systems Association:
www.censa.org
phaseFour Informatics: www.phasefour-informatics.com
Scientific Computing World: www.scientific-computing.com
Chapter 22
Laboratory Notebooks:
Valuable Indicators of
Intellectual Property
Laboratory notebooks are important corporate records that
should clearly show tests performed in the lab, materials used
and when they were used. They can provide essential evidence
to the Patent Office in the event that questions of patent
rights arise.
key words: intellectual property, interference, inventorship,

recordkeeping, laboratory notebook, patent office
I n the keeping of good laboratory records, it is important to be both earnest and

diligent, as this article shows with references to a famous play by Oscar Wilde
(see Sidebar 22.1 The Importance of Being Ernest—and Diligent). Sometimes
the success of a patent challenge can depend on the pages of a well-kept labora-
tory notebook.
The Importance of Laboratory Notebooks

In the real world of industry, the well-being and economic success of a company
or university can sometimes hinge on the ability to prove it has rights to intellectual
properties—such as inventions and trade secrets. Thus when chemists, research
scientists or technicians are called upon to produce actual proof of their work, they
will quickly realize the value of having been earnest and diligent in maintaining good
laboratory testing and research records. A well maintained laboratory notebook, in
particular, can be not only a vital business record of research performed, but also
can be vital for proving who did what, when and why. The laboratory notebook also
can be invaluable for proving that a trade secret was developed in-house, and, in
the case of a new employee, can prove that some critical information or invention
was not improperly appropriated from a former employer.
Notebook entries must be credible and complete or the notebook won’t be given
much weight by a Court or by the US Patent and Trademark Office (the Patent
Office). Notebooks must be maintained in earnest (i.e., for a serious purpose) and
in a diligent (i.e., continuing, non-lackadaisical) manner.
215
216
Lab Notebooks: Valuable Indicators of Intellectual Property Beginning Cosmetic Chemistry
Sidebar 22.1. The Importance of Being Earnest—and Diligent

The Oscar Wilde play, “The Importance of Being Earnest,” illustrates
the importance of written records, the preservation of evidence, and in
the absence of self-authenticating records, the need for corroboration by
credible witnesses for proving one’s case. The future happiness of the main
character depended on his being able to prove, not only who he was, but that
his Christian name was, in fact, Earnest (i.e. not Jack). The play illustrates
the importance of not only being earnest, but also diligent, in keeping good
laboratory records.1
Assuming an inventive idea is patentable, in the United States a patent is granted

to the first inventor, unlike all other countries where patents are granted to the first
person (or entity) to file a patent application. Sometimes two or more inventors will
file a patent application that claims substantially the same invention in the United
States at about the same time. In such cases, the Patent Office may resolve who is
entitled to the patent for that invention by declaring an administrative proceeding
called an “Interference.” The key issue during an Interference proceeding is not
to determine who is the inventor, but who was the first one to invent.
An Interference proceeding is an evidentiary battle. To be declared the first
inventor, the winning party must be able to prove that the critical date of when the
party first conceived the invention was earlier than the date of the other party, and
in certain cases, to prove it worked diligently in pursuing the invention from the
date of conception of the idea to the date of “reduction to practice” in the United
States. These proofs depend primarily on laboratory notebooks or diaries—properly
dated, properly corroborated and properly authenticated.
Evidence Preservation
Up until Dec. 31, 1995, evidence preservation programs were not needeed in
countries having a first-to-file system because non-US applicants could not use
work performed outside of the United States to prove priority. Such applicants
were limited to claiming priority based on the filing date of their foreign applica-
tions filed in countries that were members of reciprocal treaties with the United
States.2 Records of research activities taking place outside the United States and
dated before Jan. 1, 1996, still cannot be used to prove inventorship during US
Interference proceedings.
Now, however, a party can prove inventorship based on research activities in
laboratories outside the United States, so long as records were dated and activi-
ties were performed on or after Jan. 1, 1996. This change in US law has raised the
importance of earnestly and diligently keeping laboratory records even in non-US-
based corporations and offshore divisions/subsidiaries of US corporations; if written
records were not routinely kept in these non-US-based facilities in the past, their
use should be implemented now to take full advantage of the US law. Policies for
keeping proper notebooks and diaries and for archiving of the notebook should be
217
instituted, taught, maintained and enforced in foreign and multinational compa-

nies and by inventors on a global basis. Failure to create and preserve records that
prove conception, reduction to practice, diligence, etc., could result in losing an
Interference in the United States that would otherwise have been won.
Diligence in Recordkeeping
Even if the issue of inventorship fortuitously escapes being the subject of an
Interference proceeding, diligence in keeping good records, especially in a labora-
tory notebook or diary, can be important, among other things, for:
• Resolving internal disputes of inventorship in a research and development
facility.
• Proving the in-house origin of proprietary formulas, processes, and trade
secrets.
• Supporting the reproducibility of experimental data.
• Establishing priority rights to patents.
• Supporting the validity of patentable inventions.
• Providing detailed invention disclosures to patent counsel during the prepa-
ration of patent applications.
• Providing support for the defense of patents in court.
• Confirming the accuracy of data in articles reporting research.
• Avoiding accusations of misappropriation of trade secrets.
• Avoiding accusations of research negligence or academic misconduct.
• Avoiding accusations of alteration or fraud
If an individual or an organization does not have policy guidelines for what
should or should not be entered in notebooks, advice from legal counsel, preferably
a patent attorney, is suggested. In addition, a number of publications are available
that describe proper laboratory notebook keeping, and some of them are listed in
the Reference section of this chapter.3–10
Notebook Guidelines
In general, all references agree that:
• Laboratory notebooks preferably should be bound books with sequentially
numbered pages.
• Entries should be made in ink and not pencil.
• Entries should be dated in chronological sequence.
• Blank portions of the pages should have a line drawn through them to indicate
no further entry was made.
• Each page of entries should be signed by the person entering the data on a
frequent, preferably daily, basis.
• Each page should be witnessed by someone who has read and understood
the information recorded.
Recordkeeping policies may differ slightly between corporate, university or
research facility settings and these policies should be reviewed with appropriate
legal counsel to ensure that they conform with current law.
218
Disputes about inventorship sometimes arise even within an organization. After

a patent issues, an individual who asserts that he or she should have been listed as
an inventor in an issued patent must prove inventorship by clear and convincing
evidence. This burden is a tough one. If the evidence consists exclusively of the
testimony of the allegedly “omitted” individual (termed the putative inventor) and
his or her laboratory notebook entries, that evidence may not be enough to pinpoint
a critical date of invention, even if the notebook is dated, signed and witnessed.
Simply proving that someone was working hard at “something” doesn’t prove that
the person was hard at work reducing an invention to practice.
Hypothetical
Let’s consider the hypothetical case of a cosmetic chemist named Earnest
Moncrieff who has invented a great new anti-aging beauty mask for his employer,
Hallward Cosmetics. Hallward filed a US patent application for the new product,
naming Earnest as the inventor. At about the same time, Wilde Industries also filed
a US patent application on the same invention. Earnest has just received notice
from Hallward’s patent attorney that the Patent Office has declared an Interfer-
ence between his application and the Wilde application. The Wilde application
was filed six months before Earnest’s, so Wilde, as the first to file, was declared
the “senior party” in the Interference. Hallward, for filing later, was declared the
“junior party.” To win, Hallward must prove that Earnest invented the anti-aging
beauty mask before Wilde’s inventor (G. Garbo) invented it. Hallward must provide
written evidence that proves Earnest had the idea of the invention (conception)
before Garbo and diligently worked to make the invention a reality or to at least
file a patent application (reduction to practice).
Wilde’s inventor, G. Garbo, is a loner. She distrusts her co-workers; she’s afraid
they will steal her ideas. Garbo does not keep a bound laboratory notebook. She
only keeps loose leaf notes with cryptic, undated, unsigned and unwitnessed entries.
Garbo just wants to be left alone in the lab and never talks about what she has done
until she meets with the patent attorney to put together the patent application. An
example of Garbo’s notes is shown in Figure 22.1, and is the only evidence she
can produce. Because of Garbo’s poor records, Wilde cannot establish any date of
invention earlier than the filing date of its application, Feb. 24, 1996. This lack of
diligence makes Hallward’s job of proving prior invention much easier. All Earnest
must do now is show that he conceived of the anti-aging beauty mask and reduced
it to practice before Wilde’s filing date.
As part of his evidence to prove reduction to practice, Earnest provided Hall-
ward’s attorney with his notebook page shown in Figure 22.2. Earnest’s notebook
page clearly shows the basic formulation was actually prepared 10 days before
Wilde’s application was filed. Earnest’s notebook is bound, the pages are sequentially
numbered, the entries are dated and signed, and each page was witnessed within a
day or two of each entry. Earnest regularly discussed his work with colleagues, so
Hallward had plenty of witnesses available to corroborate Earnest’s notebook. As
a consequence, Hallward won the Interference and was awarded the patent, even
though Garbo actually invented the formula 10 months before Earnest! Garbo
219
Figure 22.1.
Figure 22.2.
220
learned the hard way about the vital importance of being earnest and diligent in
her recordkeeping.
An inventor, like Earnest, must provide evidence corroborated by evidence
independent of his own. Laboratory notebooks, in and of themselves, generally are
not sufficient corroborating evidence (i.e., are not self-authenticating). Addition-
ally, the evidentiary weight of notebooks is negatively affected if the state of the
notebooks is unreliable and a long time has passed between the entry of the record
and the attempt to offer it in evidence. Courts do not recognize a putative inven-
tor’s lab notebook as sufficient corroboration of the inventor’s testimony especially
where the contents of the lab notebook are not witnessed, or are not consistently
or reliably dated.
If Earnest ordered an ingredient or material that was used in the ultimate in-
vention, a notation of that order in his notebook, standing alone, would not prove
that the inventive use of that ingredient or material was his idea, without further
corroborating evidence. Merely suggesting an idea of a result to be accomplished
rather than a means of accomplishing it does not make an individual an inventor
or a joint inventor. Earnest will need independent corroboration by a credible
witness who, like Miss Prism in the Wilde play (see excerpt in Sidebar 22.1), can
fix a critical time period and corroborate evidence by association with some con-
temporaneous event, preferably an unusual one. A practice of regularly discussing
research results and goals with co-workers can be very useful by providing a ready
source of corroborating witnesses. Of course, such discussions should be kept
confidential to preserve patentability or trade secret status.
As in Wilde’s play, a combination of circumstances and credible witnesses may
be needed to authenticate evidence even with a well-kept notebook. For example,
if the evidence is a rough pencil sketch on scratch pad paper or is partly in ink
and partly in pencil, an authenticating explanation will be needed from a credible
witness who remembers what was in the sketch or can explain when the penciled
portion of the sketch was added. Written records are essential, such as notes of
laboratory experiments, field tests, market tests, as well as the recollections of
fellow employees, supervisors, custodians of records, suppliers, customers, and in
some cases, relatives. The notebook can be critical for refreshing the memory of
the witnesses who are called upon to corroborate the notebook entries. The clearer
the entries, the easier it will be for a witness to place themselves back in time and
credibly testify about the content and context of a given notebook page.
Notebooks
Traditionally, laboratory notebooks preferably have been bound books, with
sequentially numbered pages. Bound books are particularly good for preserving
contemporaneous records and evidence. Bound books have the advantage that
some evidence, such as photographs, charts and tracings from analytical instru-
ments, etc., can be preserved by fixing them permanently onto a page (i.e., glued or
stapled). In one example of preservation of the evidence, a moth that had caused a
computer malfunction at Harvard University was taped in a notebook!2 In my own
221
experience, I have seen a case where an insect was found in a source of oatmeal
powder ingredient and it was taped to a notebook page.
Increasingly, in the wired world of today, electronic laboratory notebook systems
(e-notebooks) are used as an alternative to bound books (see Sidebar 22.2 The
Market for E-Lab Notebooks). The e-notebooks have the advantage that findings
of the researcher can be electronically captured, searched, retrieved, displayed,
and made available to members of a team. Problems such as poor penmanship are
also avoided by using an e-notebook, however, typing errors are not. Electronic
records also are susceptible to corruption; data can be overwritten or deteriorate
during storage. An e-notebook must be carefully managed and stored, particularly
if it ever has to meet the rigorous evidentiary standards imposed in an Interference
proceeding or litigation.
Sidebar 22.2. The Market for E-Lab Notebooks

With an increased demand for data in an easily accessible format, the
electronic version (e-version) of information has spread into many industries.
In R&D, the classical spiral-bound, hard copy lab notebook has been given
an “e-vamp” as software companies devise means of formatting, recording
and storing research data in electronic formats. Electronic lab notebooks
(ELN) based on a scientific word processor platforms allow researchers to
format electronic pages that replicate paper-based notebooks. In today’s
marketplace, scientific companies must dramatically improve productivity
so their researchers spend more time doing science and discovery rather
than collecting and interpreting results on paper. According to one software
company, several scientific companies are already using ELNs but the entire
industry will soon have to adopt their use as the company’s bottom line, the
market, and regulators demand it.
Source: Yahoo Financial News. Available at: http://biz.yahoo.com/bw/050302/25730_1.html.
Accessed Mar.14, 2005.
The computer, as a witness, can establish that a notebook entry existed as of

the date electronically “stamped” on the record. But the computer cannot estab-
lish that the person making the entry actually carried out the test described in the
notebook as of the date of the record, or corroborate a reduction to practice of an
invention as of that date. Electronic notebook systems should provide for date or
date/time stamping capability, for audit trail features to ensure the entries are reli-
able, by making any alterations apparent or at least detectable, and should include
electronic signature and electronic witness features to verify that at least one or
more persons were aware of the record’s existence besides the record’s creator (the
witnessed-by feature of bound books).
If you are working on a commercially important product or process and rely-
ing solely on e-notebook records, you might want to consider a dual system for
222
preserving important entries. You can set up a bound notebook containing securely
attached hard copy printouts of the critical record entries, and having the printouts
signed, dated and witnessed. Subsequent revisions and updated entries can be
similarly preserved.
Look at Figures 22.1 and 22.2 and consider whether you are an Earnest Mon-
crieff who diligently and properly dates and signs your notebook, asks a colleague to
read and sign your notebook as a witness, works with others who can testify when
your experiments were done, and who memorializes your work on an ongoing
basis? Or do you work in a Garbo-esque manner—secretive, working alone, not
letting anyone else see your experimentation, never having anyone witness your
work or your notebook, never discussing your work with others, or using a loose-leaf
notebook? If you are working on a potentially valuable product or process, would
your laboratory notebook be self-explanatory? Does your notebook clearly show
what was done, what was used, and when it was used? Does your notebook show
the source of the materials used, the identity and characteristics of the ingredients,
how data was obtained, how the process was performed, etc.? If not, you are doing
yourself and your company a great disservice.
Summary
Laboratory notebooks are important corporate records that can provide essential
evidence to the Patent Office or a court if properly maintained. Evidentiary records
may be called upon over a period of up to 20 years or more for proving rights to
a patent, and for an unlimited period for proving rights involving trade secrets.
Almost all records require some form of corroboration but the clearer the record,
the easier the task of providing the necessary corroboration.
If you had to testify about the accuracy of entries made perhaps as long as 20
years ago, and the diligence of the activities leading to a patentable invention or
important product/process based on your notebook records, could you? What’s in
your laboratory notebook? We all forget things over time. Remember, your note-
book is not just a place to jot down weights and calculations that you make on the
fly in the lab. It should be a record that you or anyone else in your field can pick
up, years after the work was performed, and understand what was done, when it
was done, and why.
Talk with your patent attorney about your recordkeeping system and whether
it is adequate for protecting your valuable intellectual property. You don’t want to
find yourself in the position of Jack in the Oscar Wilde play, who had to learn the
hard way about “the vital importance of being Earnest” (and diligent).
Published May 2005 Cosmetics & Toiletries magazine.
References
1. O Wilde, The Importance of Being Earnest, Act III, Barnes & Noble World Digital
Library, NY 137–138, (2002)
2. Title 35 of the United States Code, Section 104 (Dec. 8, 1994)
223
3. R Schueller and P Romanowski, “Lab notebooks: The ‘write’ stuff.” In:, Beginning
Cosmetic Chemistry, 2nd edn, Allured Publishing Corporation, Carol Stream, IL, Ch 2
7–11 (2003)
4. HM Kanare, Writing the Laboratory Notebook, Washington, DC: American Chemical
Society (1985). (The author provides a picture of the moth taped in a notebook in on
page 138.)
5. Keeping a Laboratory Notebook, web publication available at: http://www.btgplc.com/
btguploads/ BTG_LabNotebook_Jul02.pdf
6. Guidelines for Keeping Laboratory Notebooks, University of Oxford (2004). Available
at: http://www.admin.ox.ac.uk/rso/policy/finguide.html. Accessed Aug. 27, 2004
7. W Wilson, Keeping a Lab Notebook, Web publication available at http://www.physics.
ucok.edu/~wwilson/PHY4264/lab/lab_notebook.pdf
8. Recordkeeping Procedures, Office for Technology and Trademark Licensing,
Cambridge, Massachusetts: Harvard University (2004). Available at: http://www.
techtransfer.harvard.edu/RecordKeeping.html. Accessed Aug. 27, 2004
9. HF Ebel, C Bliefert and WE Russey, “The laboratory notebook, in The Art of Scientific
Writing” In: The Laboratory Notebook, 2nd edn, Weinheim, Germany: Wiley-VCH
GmbH & Co KgaA 15–30 (2004)
10. LA Dolak, Patents without paper: Proving a date of invention with electronic evidence,
Houston Law Review 36 471 (Summer 1999)
Chapter 23
Laboratory Batching of
Cosmetic Products
Preparing laboratory batches of personal care products is a
significant part of a chemist’s job.
key words: preparation, manufacturing procedure, packaging,

specifications, storage
P reviously we have dealt with the chemistry of common cosmetic raw materials
and reviewed how a beginning cosmetic chemist might formulate such chemicals
into finished personal care products. This chapter focuses on how bench chemists
prepare for laboratory batching of these products by using the information con-
tained within the formula and accompanying batching instructions. We introduce
the underlying principles of the batching process and review basic equipment and
techniques involved in preparing laboratory quantities of cosmetic products.
Preparatory Steps
Proper preparation is one of the secrets of producing successful personal
care products. During this time, you familiarize yourself with key elements of the
formula and the batching process. This investment in time significantly improves
your chances of success.
Familiarize yourself with the formula: Perhaps the most important pre-
liminary step is to read through the formula. When first beginning as a cosmetic
chemist, you typically are given starting formulas to work from. These could be
internal formulas that need to be modified slightly or supplier formulas that need to
be adapted to your systems. To learn the craft of cosmetic chemistry, it is essential
to know the ingredients you will be working with. We encourage you to seek out
information from the following sources prior to working with new raw materials.
These ingredients may be identified in several ways:
• By trade name (the supplier’s “brand” name)
• By the official INCI name as published in the “International Cosmetic
Ingredient Dictionary” (published by the Personal Care Products Council—
formerly the CTFA).
• By the chemical name as designated by the International Union of Pure and
Applied Chemistry (IUPAC).
225
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Laboratory Batching of Cosmetic Products Beginning Cosmetic Chemistry
The following sources contain other helpful chemical information:

• INCI dictionary provides the chemical structure, names of suppliers and
Chemical Abstracts Service number,
• Material Safety Data Sheets (MSDS) contain information related to specific
hazards and precautions associated with those chemicals.
• Merck Index and CRC Handbook offer information on physical properties,
mode of manufacture and other uses.
Manufacturing Procedure: Once you are familiar with a formula’s ingredients,
review the manufacturing procedure. We discuss the principles behind each pro-
cedure later, but there is great value in reviewing the instructions before batching.
This knowledge helps you prevent mistakes during batching and ultimately aids the
development of your own formulations and manufacturing procedures. It is similar
to the college lab experience where you were required to read the instructions for
an experiment prior to doing it.
Document the Batch: After you have the proper background information,
enter the formula and batching information into a laboratory notebook. Be sure
to explain why the batch will be made, the procedure to be followed and the size
of the batch. Identify the formula components by name and lot number, as well as
the percentage and calculated weight of each ingredient. Allow enough room to
record the actual weight of each item added, the time and temperature of addition
and any notable observations.
Your lab notebook is not just an aid in later reproducing your work. It also
provides a legal record, which may be especially important in situations involving
potentially patentable technology. See Chapter 22, “Laboratory Notebooks: Valu-
able Indicators of Intellectual Property,” for more information.
Assemble the raw materials: Another important preparatory step is gathering
the necessary raw materials before beginning a batch. It could be disastrous to get
to a critical step in the process and find an ingredient is not available in sufficient
quantity. When gathering chemicals, be careful they are not “too old.” This step is
important because many cosmetic raw materials have a limited shelf life. As they
age, they may lose effectiveness, become contaminated, or change color or odor.
It is important to use raw materials that meet the specifications established for
the formulation you are producing. If you must use “old” chemical components
(typically more than one year old), confirm that these materials are still within
specifications.
Prepare packaging: Check availability of appropriate packaging before making
a batch. Some products cannot be left in the batching kettle for very long because
they can react with air or the batching vessel. Protein containing products, for
example, can darken when exposed to oxygen for too long. Such products should
be transferred to their final packaging or appropriate storage vessels soon after
manufacture.
Select and prepare equipment: The equipment required for a given product
depends on the formula type. In general, a cosmetic chemist’s basic equipment list
includes mixers, mills, filters, heating and cooling equipment and miscellaneous
laboratory equipment, such as weighing devices and thermometers.
227
Most cosmetic products are combinations of ingredients and, therefore, re-

quire mixing. The type of mixer required varies with the product. Some products
require simple stirring to dissolve materials. As an example, “baby oil” is a mixture
of mineral oil, fragrance and preservative. Here, the mixer’s role is to blend the
components in a controlled manner.
Other products, such as creams and lotions, may require special homogenizing
mixers or mills that provide the high shear needed to produce emulsions. Particu-
larly thick products, such as ointments or toothpastes, may require special mixers
designed to mix without aerating.
In general, mixers with variable-speed motors and fitted with propellers or
paddle-type blades are sufficient for the mixing problems you will routinely en-
counter. Commonly used brands include Lightnin’a and Glass-Col.b
Thermometers or electronic thermostats are helpful in measuring and regulat-
ing a batch’s temperature. Most chemists prefer metal thermometers rather than
glass ones which can break. You can heat or cool small batches of many cosmetic
products with nothing more than a hot plate or water bath.
Whenever you heat chemicals on a hot plate be careful to avoid burning or
scorching the material. When you require greater control over the heating condi-
tions or are heating volatile compounds, you may choose to use a water bath. This
device is simply a container filled with water put directly on the hot plate. The
mixing beaker is put inside the water container. With this set-up, the temperature
of your batch will never exceed the boiling temperature of water. It also gives you
greater control when it comes time for cooling.
Additional equipment, including balances (electronic or otherwise), spatulas,
weighboats, pipettes and laboratory glassware are also important in batching cos-
metic products.
Before beginning the batch, carefully clean selected equipment to prevent
product contamination. Fortunately, you can readily remove many cosmetic ma-
terials with detergent and water. Thoroughly rinse all vessels and mixing blades
with water since residual detergent can contaminate your next batch. To remove
certain polymers, you may need to use an organic solvent, such as alcohol. To make
future cleaning easier, wash all equipment immediately after use to prevent any
residues from hardening.
Batching Considerations
Manufacturing procedure: Once you have completed preparation, you can
begin to make your batch. Combine the ingredients in a set sequence, according
to a series of instructions much like a cookbook recipe. The “recipe” for a cosmetic
product includes not only the names and proportions of ingredients (the formula),
but also how the product is put together (the manufacturing procedure). A procedure
should specify, step-by-step, all aspects of batch preparation, including the order
of chemical addition, mixing conditions and temperature control.
While making a batch, you may wonder why ingredients must be added in a
specific order or mixed in a certain way. The way chemicals are combined can af-
fect the final product’s quality (Table 23.1).
228
Table 23.1. Combination Problems
Problem Solution
Addition of fragrance causes Premixing the fragrance with the solubilizing
product to be hazy surfactant improves the finished dispersion of
the fragrance and thus the product’s clarity
Powdered raw materials, such Sprinkle powders in slowly to avoid clumping.
as cellulosics or gums, clump Special equipment, such as an eductor, may be
on addition to the batch, helpful in some cases.
dissolving only slowly
High viscosity of gel-based Change the order of addition of chemicals. Add
products impedes the addition the neutralizing agent later so the batch’s
of the final ingredients viscosity remains low until all components are
added.
Certain ingredients, such as Add heat-sensitive materials during the cooling
fragrances and preservatives, stage (once the temperature is below 50°C)
degrade
Oils and waxes take a long time Combine and heat oil-soluble components in a
to melt and disperse when separate phase before adding to water
added to the water
The key point is to ask questions and learn why specific procedures are neces-
sary instead of following procedures blindly. This knowledge will not only help you
make batches of existing formulas but also improve your ability to develop manu-
facturing procedures for new products. And when you see unexpected changes in
your batch, be sure to write them down. This information will be valuable when it
comes time for scale-up.
Adjustments to specifications: Once you have finished the manufacturing
procedure, you may expect the batch to be done; however, it may not be. Even
after adding exact amounts of the required ingredients in the proper order, the
batch may not conform to the proper specifications. One reason batches vary is
that the quality of raw materials varies from lot to lot. These changes may affect
the finished product. In such cases, you may need to adjust certain characteristics
of the batch, such as its pH, viscosity or color.
The manufacturing procedure details the maximum allowable adjustments but
may not specify how to quantify those adjustments. Therefore, adjusting a batch
to meet specifications can be something of a guessing game. As you become more
familiar with a formula you will gain a “feel” for what adjustments produce the desired
effect (Table 23.2). Until you reach that point, however, draw off a small portion
of the master batch as a test. Add the chemical you think will solve the problem.
This way, you will not ruin the entire batch if you add the wrong ingredient or add
too much. Once you have confirmed that the batch will react appropriately to your
proposed adjustment, you can adjust the remainder of the batch accordingly.
229
Table 23.2. Formulation adjustments
Problem Solution
pH is wrong. Add acids or bases as specified in the proce-
dure. Keep track of the amounts you add. You
can then extrapolate the amount required for
the remaining batch. Remember changing the
pH may alter other product characteristics, such
as viscosity, therefore, you should make this
adjustment first.
Viscosity of anionic surfactant If the procedure allows, add salt in 10%
systems like shampoos or bath increments until the batch has the correct
gels is too low. viscosity. Again, keep good records of the
amount you added, to determine the right
amount to add to the remaining batch.
It is important to note that you may not be able to adjust some characteristics
of a batch. For example, the viscosity of an emulsion is not easily changed because
further stirring may irreversibly break the emulsion and ruin the product. In such
cases, you may have no choice but to remake the entire batch. When you determine
that the batch meets all target specifications, it may be considered successfully
completed.
Storage of Finished Product

The decision of how to store a completed batch depends on its purpose and
the nature of the product.
If the objective is to conduct finished product evaluations, you probably want
to put the product into its final package. After all, the container’s size and shape
may affect how the product dispenses. For example, highly viscous products may
dispense better if the bottle is of a certain shape. Also, the appearance and func-
tion of the package may influence consumer perception of the product. Whenever
possible, try to put the product into its specified package. Cosmetic packages are
typically plastic (polyethylene, PET or polypropylene), glass or, for aerosols, metal
(aluminum, or tin-plated steel).
When the objective is to prepare bulk quantities of material to be filled later,
you may choose to transfer the product to a suitable storage container. For small
batches, 5-gallon plastic (usually HDPE) pails or glass jars are commonly used.
For larger quantities of bulk products, 55-gallon drums are useful. Depending
on the product, you may prefer to use plastic drums or steel drums lined with
polypropylene.
Regardless of how the product is stored, it is important to carefully label each
container so the contents can be readily identified. In most cases, the label should
indicate the product’s identity, the batch and formula numbers and production date.
If the brand identity must be kept secret during testing, you may just identify the
230
product generally (“shampoo,” for example). You should still indicate the date and
any appropriate code numbers. The code number should refer to a notebook page
containing critical batch information.
Preparing laboratory batches of personal care products is a significant part of
a cosmetic chemist’s job. Therefore, it is important that you develop the ability to
successfully produce such batches. We hope this chapter provides information that
will help you develop these skills.
References
1. International Cosmetic Ingredient Dictionary, 12th Ed., Personal Care Products
Council (formerly CTFA), Washington, DC (2008.) (Formerly the CTFA dictionary)
2. S Budavari, Rayway, Merck Index 14th Ed., Merck & Co, NJ (2006)
3. D Lide, CRC Handbook of Chemistry and Physics, 88th Ed., CRC Press Inc, Boca
Raton, FL (2008)
4. M Grayson, Kirk-Othmer Encyclopedia of Chemical Technology, V 15, John Wiley and
Sons, NY (2001)
5. J Oldshue, Fluid Mixing Technology, McGraw-Hill Publications, NY (1983)
6. R Schueller and P Romanowski, “Lab Notebooks, the “Write” Stuff,” Cosm & Toil,
108(4) 59–62 (1993)
Chapter 24
Successful Product
Development
The cosmetic chemist draws upon many disciplines and
resources to successfully develop products.
key words: product concept, formulation, test batches
A formulating cosmetic chemist is really a jack of all trades: mechanic, copywriter,

technical liaison, marketing guru as well as “cook.” Of course, he or she must
be a competent chemist in order to understand the nature of the chemical raw
materials dealt with in the cosmetic industry. In addition, a formulator must act as a
production compounder, analytical chemist, salesman and regulatory affairs officer.
In other words, one must be able to deal with a diverse array of product development
issues. This chapter provides some insight into the formulation process, to help you,
the beginning formulating chemist, gain an appreciation for these issues.
The Idea
The first step in the creation of any new product is the development of the idea.
Depending on your corporate culture, ideas for new products can come from many
directions—not only marketing and R&D, but other departments or individuals
may participate in new idea generation. Marketing has access to consumer product
usage information that indicates potential consumer wants and needs. R&D has
data on new functional raw materials. Packaging presents new packaging elements
that allow for a new product type to be prepared. Regardless of where the idea
originates, once the product development gauntlet has been thrown down, the
real work begins.
New Product Concept

Defining the parameters: The formulation process actually begins by establish-
ing a direction for the new product. The last thing you want to do is complete several
months of development work on a hair spray, followed by two or three months of
stability testing, and then present the product to marketing only to hear someone
say, “I thought you were making a nonaerosol hairspray!” The point is that product
description parameters must be decided on before formulation begins, not after the
product has been developed. This way the chemists have parameters against which
to compare and contrast the success of their product development efforts.
231
232
Successful Product Development Beginning Cosmetic Chemistry
Such a list of descriptive product parameters should encompass a variety of

product attributes. Working from these:
• Evaluate esthetic factors, including color, appearance, viscosity, texture and
dispensability.
• Establish performance targets to provide a measure of how well the product
should, for instance, foam, clean, condition, or color.
• In advance, consider packaging attributes, such as the size and shape of the
container, type of closure, and even materials of construction.
• Consider financial concerns, which may affect your choice of raw materials,
packaging components, or even mode of manufacture.
• Marketing claims may raise regulatory concerns, necessitate use of special
ingredients, or require the product to produce specific results—all of which
may impact the formulation process.
Ideally, all of these parameters should be established before any actual formula-
tion work begins. In reality, all these decisions often cannot be made at the onset
of the project; therefore, some degree of compromise may be required. It is useful
to make the product description process a joint effort between all departments
involved—preferably as a team effort.
The Product Development Process

Once the product description is completed, actual formulation can begin. The
product development process may be outlined as follows:
• Collect and evaluate information regarding raw material functionality and
safety to help determine an appropriate starting point for formulation
efforts.
• Prepare prototypes using this information and evaluate them for stability
and functionality.
• Based on these evaluations, refine prototypes until a satisfactory formulation
is achieved. Safety considerations should also be reassessed.
• Consumer test leading prototype(s), and modify the product as necessary.
• Finalize the formulation, and confirm stability and production feasibility.
Research: Raw material and formula information can be collected from a variety
of sources. You can and should draw upon the experience of your peers whenever
possible—perhaps a similar project was explored in the past, and you may be able
to benefit from a coworker’s efforts. Or, you may research technical literature for
formulation information. The following are a few of the many sources of informa-
tion available for starting formulations:
• Suppliers’ formularies are available from most major suppliers of surfactants
and specialty chemicals. Many of these vendors also provide technical sup-
port through their applications laboratories. These resources should not be
overlooked.
• Several excellent reference texts are available to the cosmetic chemist. Two
of the best known texts are the de Navarre and Bennett formulary series. The
advantage of such texts is that they are very thorough, and often combine
233
a discussion of cosmetic theory with practical formula information. The

disadvantage is that they are published infrequently and may not contain
the most up-to-date information. Some additional references are provided
at the end of this chapter.
• Reviewing patent literature and performing patent searches can reveal a
wealth of information related to specific raw materials and formulation ap-
proaches. In addition to helping you find out how others have made similar
products, they help you ensure that your work does not infringe upon existing
patents.
• Several monthly technical trade journals are available. These journals are
extremely up to date, and often focus on issues of specific interest to the
formulator. They also provide information on new product releases and
trends in the marketplace.
No matter which source(s) you use to gather information, this initial research
phase is helpful in two distinct ways. First, fundamental research can provide
background information about chemical mechanisms and processes, which may
be essential to understand before developing products that are based on novel or
innovative technology. Second, such research can help in the establishment of a
“master list” of interesting raw materials and potential starting formulations. You
can then tailor that list to fit the requirements of your specific project. Thus, your
research provides information from which you can pick and choose the elements
that best fit your proposed product description.
Working around Product Constraints

This “master list” must be pared down to eliminate raw materials and formula-
tions that are unacceptable. For example, certain raw materials may be too costly,
some formulations may not be manufacturable with conventional equipment, or
regulations may prohibit usage of certain chemicals.
Cost: Ideally, you could choose the most effective ingredients available without
consideration of cost. However, in the real world, you must meet the cost constraints
established in the product description. Using only the most expensive raw materials
at high levels could break your “budget.” Of course, keeping formula costs down
does not mean you must use “cheap” materials. Remember, expensive ingredients
are often functional at very low levels. For example, the fragrance mix is often
the most expensive ingredient in cosmetic products, but it is generally used at a
relatively low level.
Manufacturing: Production capability is yet another important consideration,
even though commercialization of your new product may be months (perhaps years)
away. If you anticipate the product having any special production requirements, you
should give them attention early in the development process, in order to decide
how the product ultimately will be manufactured. If your new product requires
specialized equipment for production, now is the time to find out—not when you
attempt to manufacture the first production batch. For example, high-shear mixing
may be required to produce certain emulsions. To this end, it is also helpful for the
234
Successful Product Development Beginning Cosmetic Chemistry
cosmetic chemist to be familiar with mixing equipment and processing conditions

for commercial scale preparation of cosmetic products.
Also, you may be required to evaluate alternate manufacturing facilities, per-
haps a contract manufacturer. For example, many companies do not fill their own
aerosols, but instead rely on contract packagers. You should consider the capabilities
of your current manufacturing equipment to ensure your product can be produced
using your existing facilities, if this is a requirement.
Regulations: Government and industry regulations are considerations that may
affect formulating decisions. For example, the FDA regulates over-the-counter drugs
(such as antiperspirants and dandruff shampoos) and issues documents known as
monographs, which define active raw materials for these products.
Recently, certain US states have passed legislation which requires reduction
of volatile organic compounds (VOCs) in consumer products. This regulation has
forced many companies to reformulate major products. An awareness of regulations
regarding hazardous waste handling and disposal is also important for products which
involve such materials. For example, nail polishes contain organic solvents, and per-
manent wave products and hair colors contain hydrogen peroxide. In general, you
should try to be aware of current and impending regulations that might affect your
products. Of course, you may have to return to any or all of these issues throughout
the product development process, but consideration of these factors even before
you begin to prepare prototypes may help you avoid future problems.
Test Batches
Once you have a comfortable starting point for prototype development, you
can prepare lab batches. Although a detailed discussion of the process by which
such batches are made is beyond the scope of this chapter, you should be aware
that you may need to make many small batches to explore the effects of formula
or processing condition variations. If your first attempts are successful and the
product behaves as you intend, consider yourself lucky. In most cases, your first
formulation efforts are not going to pass the standards you have set—with regards
to either stability or performance. Thus, you will have to refine certain elements
to achieve the desired characteristics. Experience and knowledge of raw materials
will guide you in this process.
Keep on testing: During this development phase you should evaluate your
prototypes to ensure they are stable, functional and safe to use. Informal testing,
such as storing a few preliminary samples at elevated temperatures, can help ensure
that your products are free from gross stability problems. Ultimately, stability testing
should be conducted on samples manufactured under production conditions.
Chemical suppliers will provide you with basic toxicological and irritation test
data, but additional medical safety testing of the finished product may be required.
At the very least make sure that the raw materials you are using are safe.
Performance testing of the product is required to establish formula functionality.
Such evaluations may be relatively simple, such as curl retention studies to ensure
the holding power of a hairspray, or Ross-Miles testing to evaluate foam properties
235
of a shampoo or bubble bath. However, you may be required to conduct extensive,

costly clinical studies to ensure compliance with governmental regulations.
Eventually, if you have done your job correctly, you will have created a product
that meets all the technical benchmarks of the program. It is stable, functional,
safe, cost-effective, manufacturable and compliant with relevant regulations. That
just leaves one big question—will the consumer like it?
Consumer response to fragrance, color, consistency, or performance cannot
necessarily be anticipated by R&D or marketing. However, consumer testing can
provide information on the intended users’ perception of these attributes. Suc-
cessful completion of consumer panel testing is the final hurdle your new product
must overcome.
Summary
When creating a new product, the formulating cosmetic chemist should be
aware of a host of issues, including chemical raw materials, packaging components,
test methods, manufacturing concerns, sensory evaluation techniques, patents,
regulatory issues and hazardous waste requirements, consumer expectations, and
market trends. Perhaps more than anything else, the cosmetic formulator is an ex-
peditor. After all, it is the chemist who must juggle the various elements that keep
product development on track. From requesting raw material samples, to evaluat-
ing fragrance submissions, to ensuring microbiological and medical safety tests are
conducted when necessary, the cosmetic chemist draws upon many disciplines to
successfully develop products.
Published in 1993 Cosmetics and Toiletries magazine.
Further Reading
MG de Navarre, The Chemistry and Manufacture of Cosmetics, v 1–4, D Van
Nostrand Co., Princeton, NJ
HW Hibbott, Handbook of Cosmetic Science, The Macmillan Co., NY (1963)
Dr JS Jellinek, Formulation and Function of Cosmetics, Wiley-Interscience,
NY (1970)
Bennett’s Cosmetic Formulary, Chemical Publishing Co., NY (1993)
W Umbach, Cosmetics and Toiletries Development, Production, and Use, Ellis
Horwood, NY (1991)
EW Flick, Cosmetic and Toiletry Formulations, v 1 & 2, Noyes Publication,
Park Ridge (1989)
JB Wilkinson, The Principles and Practice of Modern Cosmetics, Chemical
Publishing, NY (1962)
Surfactant Science Series, Marcel Dekker Inc., NY
Chapter 25
Formulating Cosmetic
Emulsions:
A Beginner’s Guide
Emulsions that act as a delivery system for beneficial ingredients
such as aloe, vitamins, plant extracts, etc., must also be safe,
stable and cost-effective. This chapter discusses the ingredients
that go into emulsions and why they are used.
key words: emulsion, phase, humectant, preservative, thickener,

active, silicone
T o most consumers, cosmetic emulsions are just “stuff” that comes in tubes, jars,
pumps or bottles intended to make the consumer look, feel or smell better,
but usually costing too much. The claims on the front of the package often promise
miracles—and they achieve this end very cleverly, I must add! Consumers often
don’t understand that those words are used by marketers to ensure that the US
FDA (Food and Drug Administration) leaves the manufacturer alone. Greeted
with a long list of totally unpronounceable “chemicals,” consumers search for the
ingredients reported to have benefits. Among these “beneficial” ingredients are aloe,
vitamins, minerals, jojoba, plant extracts, tea, things from the sea, and others from
an endless list.
Cosmetic chemists must be concerned with formulating an emulsion that acts
as a delivery system for these beneficial ingredients while being safe, stable and,
need I mention, cost-effective (cheap). This chapter discusses those ingredients
that go into emulsions and why they are used.
Definition of an Emulsion
An emulsion is a system of two (or more) immiscible materials (usually liquids)
in which one material—the dispersed/internal phase—is suspended or dispersed
throughout the other material (the continuous/external phase) in separate droplets.
Most emulsions we will encounter will be designated as oil-in-water (o/w); thus the
oil phase is dispersed in the water phase as droplets. In the United States approxi-
mately 95% of all emulsions are of this type. Water-in-oil emulsions are used in night
creams, makeup remover creams and zinc oxide ointments for babies and sunscreens.
Historically, they have had a greasy skin feel, but more recent advances in emollient
chemistry, more specifically silicone chemistry, have changed this perception.
237
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Formulating Cosmetic Emulsions: A Beginner’s Guide Beginning Cosmetic Chemistry
A final comment before we delve into the ingredients used in emulsions: Many
years ago my good friend and mentor, Graham Barker, told me that all emulsions
are inherently unstable. He said that all we can do is postpone the day when emul-
sion separation occurs and hope that in the meantime the product will have been
purchased and used. One exception to this “rule” comes with microemulsions (very
small particle sizes) that form spontaneously and are thermodynamically stable.
Typical O/W Emulsions

Table 25.1 shows a typical o/w emulsion. Let’s go over each of the “ingredients”
in some detail to discuss their functions and a bit about their chemistry.
Table 25.1. A typical o/w emulsion
Ingredient Typical use level (%)

Water phase
Water (aqua) 60.0–85.0
Humectant 2.0–5.0
Preservative 0.05–1.0
Emulsifier 0.5–1.5
Thickener 0.1–2.0
Emollient 0.5-2.0
“Whiffle dust” as desired
Chelating agent 0.05–0.2
Oil phase
Emollient(s) 5.0–10.0
“Actives” as per FDA
Antioxidant 0.05–0.2
Emulsifier (primary) 1.0–3.0
Emulsifier (secondary) 0.5–1.0
Thickener 0.1–0.5
Wax 0.5–2.0
“Whiffle dust” as desired
Miscellaneous phase
Preservative 0.05–1.0
“Actives” as per FDA
Fragrance (parfum) 0.1–0.75
Color as needed
Water: This is of course the diluent/external phase. We like to use as much of

it as possible because it lowers the cost of our product.
Humectant: Humectants serve several purposes in emulsions. They can bind to
water (through hydrogen bonding) and are thus considered to be “moisturizers.” Good
examples of humectants are: glycerin, propylene glycol, m, p-diol, butylene glycol and
sodium hyaluronate. Humectants can act as solubilizers for paraben preservatives
and “actives.” They can also help improve the rub-out characteristics of emulsions
239
by altering spreading effects, a technique used in liquid makeups to reduce streak-

ing. Humectants can also improve the cushion (richness during rubout) of many
emulsions. Lastly, humectants can improve the freeze/thaw stability of both o/w
and w/o emulsions. If you use them at too high a concentration, a sticky emulsion
can be the result. As you can see they are very versatile materials.
Preservative: As the saying goes, “if there is (available) water…there should be
a preservative.” The list of preservatives is very long but a few of the more popular
ones are: methylparaben, propylparaben, DMDM hydantoin, quaternium-15,
imidazolidinyl urea, diazolidinyl urea, phenoxyethanol, benzyl alcohol, potassium
sorbate and iodopropanyl butylcarbamate. Care must be taken when choosing
preservatives in regards to packaging interaction, pH, interaction with other raw
materials and other considerations.
Emulsifier: Generally speaking, formulators should use several emulsifiers to
make a stable emulsion. One should be put into the external phase and one or two
should be put into the oil phase. Emulsifier types include the following:
• Nonionic (uncharged). These are often ethoxylated.
• Anionic (negatively charged hydrophobe). These are usually soap (trietha-
nolamine stearate).
• Cationic (positively charged hydrophobe). An example is dicetylmonium
chloride.
Thickener: Many thickening agents are used in emulsions. At first glance it
would seem that their function was to thicken emulsions. However thickening is
usually not the reason for their use. Their primary function is to improve high tem-
perature stability, but among their other functions are thickening, suspending particulate
materials, and affecting rubout characteristics. Among thickeners most often seen
are polyacrylates, xanthan gum, cellulosic gums, guar gum, magnesium aluminum
silicate, carbomer and bentonites. Great care must be taken to use them at low use
levels, because they often impart stickiness to the finished product.
Emollient: Emollients serve several functions. They impart lubricity to the
skin and can help to solubilize drug actives such as sunscreens. They can be es-
ters, ethers, fatty alcohols, hydrocarbons or silicones. Often they are combined to
achieve unique skin feel as required by marketing. Care should be taken to insure
that they are compatible/stable in the system chosen.
“Whiffle dust”: Here we have an almost limitless list of ingredients from which to
choose. Your choice will be controlled by marketing, the latest trends and cost.
Chelating agent: Most emulsions, and most cosmetic products in general,
should contain a chelating agent. Their function is to complex with metal ions (iron,
copper, etc.) to prevent them from negatively affecting your product. They can
improve/help maintain color, odor and preservation. Typical of this category are the
salts of EDTA.
Waxes: Waxes are used to thicken the oil phase of w/o emulsions and thus im-
prove stability. Additionally they can reduce syneresis (oil bleeding) often seen in
high oil systems by making the oil phase more coherent. They can also affect/improve
the rubout characteristics of emulsions. Typically seen waxes include carnauba,
ceresin, paraffin, fatty alcohols, candelilla and beeswax.
240
Formulating Cosmetic Emulsions: A Beginner’s Guide Beginning Cosmetic Chemistry
Actives: These materials have been labeled as drugs by the FDA. As such, we
must use them at approved use levels and make claims that follow the appropriate
FDA monograph. Typical of this category are octinoxate (sunscreen), oxybenzone
(sunscreen), zinc oxide (sunscreen or skin protectant), petrolatum (skin protectant),
benzoyl peroxide (anti-acne agent), hydroquinone (skin lightener) and dimethicone
(skin protectant).
Silicones: While silicones have appeared in emulsions for many years, their use
has greatly expanded over the last five years. At first glance their function seems to
be emolliency, but in reality they have much broader usage than that. Dimethicones
can indeed function as emollients but they also reduce skin whitening (soaping)
often seen when high levels of fatty alcohols, GMS or stearic acid are employed.
Additionally, when used at 1%, they can be claimed as a Category I skin pro-
tectant (i.e., a drug)! When using dimethicones, care must be taken to insure they
are coupled into the oil phase due to their limited solubility profile. Additionally, they
can present some difficulty in regards to emulsification (i.e., they don’t follow the
HLB rules). Most used are the 100–50 cs versions. When solubility/compatibility is an
issue, you should consider using one of the many alkyl modified dimethicones.
Other silicones include the cyclic versions. These silicones impart a silky skin feel
and are less volatile than water. Since their heat of vaporization is quite low (they
don’t take much energy from the skin to volatilize), they feel very dry to the skin.
It must be pointed out that these materials have come under attack for potential
safety issues, particularly with the tetramer version.
Other silicones are modified by adding EO/PO (ethylene oxide/propylene oxide)
that will allow them to function as emulsifiers, solubilizers or emollients. Lastly,
there are a series of new silicone elastomers that can act as delivery vehicles or
dramatically improve skin feel. The world of silicones is truly amazing.
Fragrance: Almost all emulsions will contain a fragrance. Often it is the main
reason a consumer repurchases the product. Care must be taken to not use them
at too high a use level or discoloration and/or irritation may result. Additionally, they
will have a significant effect on the raw material cost of the product.
Color: While many emulsions are white, quite a few have added color. The
purpose of the color may be to mesh with the product function. A cooling after-
shave balm may be colored blue or light green. Or, color may be added to hide a
discoloration due to the inclusion of a needed ingredient (i.e., green tea).
Conclusion
This chapter has provided a short introduction to the world of emulsions. To
become an expert in this most difficult field does indeed require many years of
hard work and many failed emulsions.
Chapter 26
The Aging of Polymer-

Stabilized Creams:
A Rheological Viewpoint
Five o/w creams were prepared using four natural oils and
hydrocarbon-based mineral oil. Data showed the rheology of
creams was related to the polarity of the oil used.
key words: rheological parameters, flow, oscillation, polymeric

emulsifier, ageing, natural oils, mineral oil, polarity index
A series of five o/w creams were prepared, using a polymeric emulsifier and dif-
ferent emollients. The four natural oils used in a simple o/w formulation were
olive (Olea europaea), avocado (Persea gratissima), peanut (Arachis hypogaea) and
apricot kernel oil (Prunus armeniaca). The fifth oil was a hydrocarbon-based mineral
oil (Paraffinum liquidum). The oils used feature different chemical compositions,
polarities and iodine values. It was of interest to learn whether and to what extent
these variables affect rheological profiles of the test creams, based on acrylates/
C10-30 alkyl acrylate crosspolymer. It was also important to evaluate the changes
that occur during aging of these products.
Rheological parameters (yield value, viscosity and hysteresis area) were fol-
lowed for 10 months. Both continuous flow and dynamic tests were performed on
10-month old samples, in order to determine complete viscoelastic status. The data
obtained revealed that the rheology of creams was related to the polarity of the oil
used. The mineral oil-containing sample showed a different pattern of structure
change during aging, falling behind in the rank order of creams as time progressed.
All samples revealed a structure build-up during this observation period, indicating
a long-term stability.
Introduction
The rheological profile of a cosmetic product is one of its most important fea-
tures, in both technical and esthetic terms. Rheological properties are often directly
related to the product sensory attributes and to its performance1,2. The relationship
between rheology and product stability, especially in the case of emulsions, has been
recognized as an important parameter in product formulation3,4.
241
242
The Age of Polymer-Stabilized Creams Beginning Cosmetic Chemistry
Demand for natural cosmetics: In recent years, cosmetic oils of plant origin
have been reintroduced into the market, following consumers’ demand for “natural”
cosmetics. Known to be less occlusive than petroleum-derived emollients and with
better safety record than their synthetic relatives, natural oils are increasingly used
in all types of cosmetic and toiletry products. However, they are also known to be
inconsistent in their chemical composition and to cause stability problems. It was of
interest to compare the performance of different plant-derived oils with a mineral
oil in a simple o/w cream base, using rheological parameters.
Two pairs of natural oils were chosen for this study: olive and avocado oil, as a
relatively “polar pair”and peanut and apricot kernel oil, as a less polar pair. Their
polarity indices (measured as the interfacial tension against water), together with
other relevant parameters, are presented in Table 26.1.
The nominal value of polarity index for each oil differs, depending on the source
of information.5,6,7 However, it shows the same trend of decrease from a nonpolar
mineral oil, to a relatively polar olive/avocado pair (Table 26.1). The oils also
vary in their chemical composition and iodine value, with olive/avocado pair being
significantly more stable. All five oils were within the same viscosity range, hence
allowing the comparison of the effect of their structure on the cream rheological
properties.
Table 26.1. Characteristic parameters of selected oils
Polarity Iodine Chemical

Oil Index (mN/m) value8 structure8 Cosmetic uses9
Olive oil 16.95 84 C18: 84% Skin care, sun protection,
14.76 shaving aids
Avocado oil
18.35 84 C16 22% Skin care, hair conditioners,
11.56 C18:1 62% bath products, make up,
face powders
Peanut oil 20.55 98 C18: 59% Skin cleansing, hand and
C18:2 23% body products
Apricot kernel 21.66 102 C16 44% Skin care, bath oils,
oil C18:1 40% hair products
C18:2 11%
Mineral oil 38.35 – Hydrocarbon Skin care, skin cleansing,
32.87 mixture make up removers
Benefits of cold emulsification: A polymeric emulsifier was chosen for the

formulation of the test creams, mainly because it allows for a “cold” emulsification
procedure and the avoidance of the heating/cooling stress. In addition, it was of
interest to follow the rheology profiles of fresh and aging o/w creams stabilized
with this relatively new class of emulsifiers, which are used in very low concentra-
tions (0.1–0.5%)10.
243
Continuous stress (flow) tests were employed on the freshly made (one day old)
and aged (three and 10 month old) samples. To get a more comprehensive picture
of the rheological status of the test samples, dynamic (oscillatory) tests were also
performed on the aged creams. Our aim was to determine whether and to what
extent oil polarity affects the consistency of the polymer-stabilized creams and to
follow these changes during storage.
Materials
Acrylates/C10-30 alkyl acrylate crosspolymera was used as a primary emulsifier
to make a series of o/w creams by cold emulsification. This polymeric resin belongs
to a family of copolymers of acrylic acid, with minor levels of long chain (C10–C30)
alkyl acrylate co-monomers, crosslinked with a polyalkenyl ether.10 Four natural oils
have been employed: olive oilb, Avocado oilc, peanut oilc, and apricot kernel oilc,
alongside with a hydrocarbon-based mineral oild. The viscosity of the five oils was in
the range of 59–65 mPa, as measured by Brookfield LTV viscometer, spindle 1, at
the room temperature. Triethanolamine (TEA, Sigma, UK) was used as a neutral-
izing agent, and preserved purified water as an external phase of the creams.
The composition of test samples is presented in Table 26.2.
Table 26.2. Test formulation
Ingredient % w/w
Acrylates/C10-30 alkyl acrylate crosspolymer 0.4
Oil 20.0
Triethanolamine (10% aqueous solution) 6.0
Preservative (in a propylene glycol solution) 1.0
Purified water 72.6
a
Pemulen TR–1Ç BFGoodrich, Cleveland, Ohio
b
Fisons, UK
c
SNOI International, USA
d
Fisher Scientific, UK
e
Carri-Med CSL2 500, TA Instruments, UK
Emulsion Preparation Method

A “direct method”10 was used in the production of the test samples. The emul-
sion was obtained by dispersing a polymeric emulsifier in the mixture of water
and propylene glycol-based preservative at the room temperature, by means of an
overhead stirrer. After a 20-minute stirring period, the oil phase was added and
the stirring continued for another 30 minutes. The acidic dispersion obtained was
then neutralized with triethanolamine 10% w/w aqueous solution to the pH value
of approximately 6.0. A resulting o/w cream was packed in an opaque container
and tightly closed.
244
Rheological Studies
A controlled-stress rheometere with a cone-and-plate measuring system was
used in all the experiments. Continuous flow tests were performed by increasing
a shear stress from 0–200 Pa and decreasing it back to 0, each stage taking one
minute. Five runs were carried out on each sample, with the coefficient of varia-
tion less than 15%.
Oscillatory (dynamic) measurements were performed over a frequency range of
0.1–10 Hz. In the case of cream samples, the standard frequency sweep procedure
with a fixed torque value was not applicable, as it produced poor wave forms and
inconsistent results. Therefore, in our procedure, the deformation of the sample
was kept at the fixed level of 10–3 radians, which corresponded with a 2.8% strain,
leaving the rheometer to adjust the torque accordingly. Three repeat oscillatory
runs were performed on each sample. Both flow and dynamic measurements were
carried out at 20°C.
The first measurement was performed on 24-hour-old samples, which were
then stored at the room temperature (20±2°C) for another two tests in a three- and
10-month period, respectively.
Results
The flow data of the fresh samples are shown in Figure 26.1 and Table 26.3.
Lower values for shear rate under the same shear stress indicate a higher viscosity
for the sample. It is evident that the mineral oil cream exhibits the highest viscosity,
followed by the olive, avocado, apricot kernel and peanut oil cream, respectively
(Figure 26.1).
Figure 26.1. Flow curves for the fresh creams (after 1 day.)
245
Table 26.3. Flow parameters (yield value τγ, viscosity ηand hysteresis area H)
after 1 day, 3 months and 10 months of storage
Sample After 1 day After 3 months After 10 months

0τY η at H τY η at H τY η at H
(Pa) 200 Pa (P/s) (Pa) 200 Pa (P/s) (Pa) 200 Pa (P/s)
(mPa s) (mPa s) (mPa s)
Olive oil cream 20.53 1360 53.9 20.51 1400 248.5 25.63 3010 513.5
Avocado oil cream 20.55 1205 31.65 20.51 1240 236.7 25.67 1880 265.0
Peanut oil cream 20.53 1010 62.27 15.40 1080 270.3 20.51 1530 648.1
Apricot kernel 20.54 1120 27.65 15.42 1150 201.6 20.54 1490 384.7
oil cream
Mineral oil cream 20.50 1460 23.58 15.38 1275 64.58 20.53 1570 493.6
Elasticity levels: All the samples possess yield stress value τY (Table 26.3),
indicating that their networks exhibit a resistance to an external force before they
start flowing (plastic behavior). In the previous study12, we found a good correlation
between yield values and elastic parameters of semisolids. Based on those find-
ings, the almost identical yield values of the cream samples reveal the same level
of elasticity in all fresh samples, regardless of the oil used.
It is noticeable from Figure 26.1 that the up and down parts of flow curves do
not overlap completely, creating a hysteresis loop area, which is commonly used as
a measure of thixotropy. The olive oil cream has shown considerably larger thixot-
ropy at this stage (Table 26.3), indicating the presence of structures that are more
susceptible to breakdown under shear than the other samples.
Aging data: After three months of storage, the mineral oil cream fell in the
rank order of viscosity (Figure 26.2), followed by a further fall after 10 months
(Figure 26.3 and Table 26.3). This result indicates different types of structural
changes during aging, compared with the natural oil creams. The latter followed
the same pattern throughout the observation period, with the olive/avocado oil pair
having higher viscosity and yield stress values than the peanut/apricot kernel oil
pair (Table 26.3). The general increase in viscosity upon storage in all the samples,
however, shows a favorable internal structuring and indicates a long-term stability of
the test samples1, 3. An increase in the level of thixotropy was also apparent (Table
26.3), showing a prominent time-dependent flow behavior.
Many materials, especially semisolids, possess rheological properties of both solids
and liquids, i.e., viscoelasticity. Dynamic (oscillatory) studies provide information
on both elastic and viscous components of creams and other semisolid products.
The behavior of the sample is expressed in terms of a storage (elastic) modulus,
which is a measure of energy stored and recovered per cycle of deformation, and
a loss (viscous) modulus, which reflects the energy lost per cycle13. Figures 26.4
and 26.5 show the viscous and elastic moduli of the test creams, respectively.
246
Figure 26.2. Flow curves for the 3-month old creams.
Figure 26.3. Flow curves for the 10-month old creams.
The information gained from oscillatory studies complemented the flow data in
terms of behavioral patterns for the cream pairs. Both viscous and elastic moduli
for the olive/avocado oil pair were higher than the corresponding values for the
peanut/apricot kernel oil creams (Figures 26.4 and 26.5).
247
Figure 26.4. Viscous (loss) moduli for the 10-month old creams.
Figure 26.5. Elastic (storage) moduli for the 10-month old creams
A stable network structure: Figure 26.6 shows the values of parameter tan δ
over a frequency range studied. Tan δ is the ratio between viscous and elastic moduli
and is commonly taken as a measure of the overall viscoelasticity of the sample13,
with the lower tan δ showing higher elasticity. Unlike corresponding polyacrylic acid
gels studied previously12, which show relatively constant tan δ values throughout the
frequency range used, the cream samples exhibit an increase in this parameter at
higher frequencies, indicating a fall in network elasticity under rapidly oscillating
248
forces (Figure 26.6). A departure from the high-frequency pattern in tan δ values
is evident in the case of mineral oil cream, confirming an assumption on the struc-
tural differences made on the basis of flow data. Generally, however, tan δ values
of all test samples are relatively high (between 0.1–0.3), revealing a dominance of
elastic over viscous properties and indicating a stable network structure.
Figure 26.6. Tan δ values for the 10-month old creams.
Discussion
When first introduced in the early 1990s, polymeric emulsifiers (associative
thickeners) showed a great promise for emulsion formulation. Being hydrophobi-
cally modified water-soluble polymers, they have no HLB and PIT constraints of
conventional emulsifiers. They have been proven to act as primary emulsifiers and
even to structure the continuous phase of the emulsion more consistently than
lamellar gel or liquid crystalline phases4. “Steric stabilization” was identified as a
main stabilizing mechanism, with the hydrophobic tails of these molecules being
adsorbed at the oil/water interface and the hydrophilic portions swelling in water
and forming microgels around the oil droplets11. Exceptional emulsion stability
and triggered release upon application are claimed to be distinct advantages4,10–11.
It was recognized, however, that certain oils need a co-emulsifier to stay dispersed
in a polymer-stabilized emulsion and that oil polarity may play an important part
in it10,14–15.
Interboundary interaction: The composition and polarity of the oil phase is
known to have a large influence on the design, properties and stability of cosmetic
emulsions14,16. The main factor in structure formation is the interboundary interac-
tion of the hydrophilic and lipophilic phase16,17. The lipids differing mostly in terms
of emulsion preparation are “easy-to-process” paraffin oils on the one hand and
249
the “problematic” triglycerides, in particular vegetable oils17, on the other. The

strength of the interboundary interaction may correlate with the polarity of the
oils14,16,17. The mechanism of this interaction is complex and particular to the oil/
emulsifier system used.
In the case of polymeric emulsifier, it is known that it must bond to the emulsionís
internal phase through dipole-dipole interactions, hydrogen bonding and hydro-
phobic interactions4. It is the balance of these forces that determines the overall
interfacial interaction, which in turn has an impact on the rheological properties of
the sample, as shown in this study. It was revealed by both flow (Figures 26.1–26.3)
and oscillatory tests (Figure 26.6) that the changes in internal structuring during
aging for the mineral oil cream differ from the natural oil creams. It is reasonable to
assume that the balance of forces acting at the mineral oil/polymer interface varies
from that present in the natural oil/polymer boundary. Among the natural oils used
in the study, there was a distinct difference in rheological properties between a
“polar” olive/avocado oil pair and a less polar peanut/apricot kernel pair. It is pos-
sible that polar interactions play more important roles in the structure build-up
than hydrophobic interactions in the case of polymer-stabilized creams.
Examining elastic properties: Rheological profile of all test samples was
characterized by plastic flow with thixotropy. Yield stress value is widely considered
the most reliable indicator of the stability in a mixture, in fact “the best and only
realistic approach” in many cases3. The presence of relatively high yield values in all
test samples throughout the observation period (Table 26.3) is taken as an indica-
tor of high emulsion stability. This study provided further support to the statement
that yield value is directly related to elastic properties of the sample12. Both yield
stress and elastic moduli values for olive and avocado oil creams were found to be
higher than for the three remaining samples (Table 26.3 and Figure 26.4).
An increase in thixotropy with aging was found to be a prominent trend in this
study. Thixotropy (a time-dependent and recoverable sheer thinning) is a favorable
rheological property, which offers not only a technical storage stability benefit, but
also increases consumer appeal6. Aging induced increase in viscosity and thixot-
ropy in these emulsion systems is based on the formation of additional inter- and
intramolecular bonds, some of which break reversibly under shear.
Conclusion
The results obtained in this study showed the chemical composition and the
polarity of the oil play a significant role in the structure of polymer-stabilized emul-
sions. A nonpolar mineral oil caused a different pattern of aging-induced structural
changes in a cream sample, compared with the more polar natural oils (olive, avocado,
peanut and apricot kernel) when studied by rheological parameters.
All cream samples revealed plastic flow with thixotropy in both fresh and aged
states. High yield values derived from flow tests and favorable tan δ values from os-
cillatory studies both indicate good internal structuring and a long-term stability.

250
References
1. PE Miner, “Emulsion Rheology: Creams and Lotions.” In: D Laba (ed.), Rheological
Properties of Cosmetics & Toiletries, Marcel Dekker 313–369 (1993)
2. GH Dahms, “The impact of the emulsion structure on adsorption and release of
actives on skin.” In: Emulsions: Technology, Structures, Ingredients, Formulations,
Verlag für chemische Industrie, H. Ziolkowsky GmbH, Augsburg 15–24 (1998)
3. CD Vaughan, “Predicting Stability in Rheologically Modified Systems.” In: D Laba
(ed.), Rheological properties of Cosmetics & Toiletries, Marcel Dekker 371–401 (1993)
4. RY Lochhead, Emulsions, Cosmet &Toil 109 93–103 (1994)
5. KF De Polo, A Short Textbook of Cosmetology, Verlag für chemische Industrie, H.
Ziolkowsky GmbH, Augsburg 149–166 (1998)
6. ICI Surfactants, Emulsifiers for oil-in-water Emulsions Brochure 41-1E (1996)
7. U Zeidler, The Tactile Properties of Cosmetic Oils, Henkel—Referate 29, 91–96 (1993)
8. AJ O’Lenick and DC Steinberg, Primary Ingredients, Hansotech Inc. (1998)
9. M M Rieger, Cosmetic Use of Selected Natural Fats and Oils, Cosmet & Toil 114 33–40
(1999)
10. Lubrizol, Noveon Consumer Specialities, TDS-114, 2002 (available from www.
personalcare.noveon.com/literature/techdata.asp#pemulen)
11. K Schrader and A Domsch, Cosmetology—Theory and Practice Vol III, Verlag fur
chemische Industrie, H. Ziolkowsky GmbH, Augsburg117–118 (2005)
12. S Tamburic and DQM Craig, Rheological Evaluation of Polyacrylic Acid Hydrogels,
Pharm 1 107–109 (1995)
13. JD Ferry, Viscoelastic Properties of Polymers, 2nd ed., Willey, New York (1970)
14. T Dietz, Basic Properties of Cosmetic Oils and their Relevance to Emulsion
Preparations, SÖWF Journal 125 2–9 (1999)
15. M-F Bobin, V Michel, E Journet and M-C Martini, Study of formulation and stability of
emulsions with polymeric emulsifiers, 2nd World Congress on Emulsions, Bordeaux,
1 1-175 (1997)
16. A Taleb and I Eros, Rheological Studies of creams. III. Effect of lipophilic phase
consistency, Acta Pharm Hung 66 77–81 (1996)
17. P Hameyer and A Bungard, “The Viscosity Behaviour of w/o Emulsions with a High
Dispersed Phase Content.” In: Emulsions: Technology, Structures, Ingredients,
Formulations, Verlag für chemische Industrie, H. Ziolkowsky GmbH, Augsburg
234–248 (1998)
Chapter 27
Gels and Sticks

These forms of delivery allow formulators to generate new
product ideas by making novel versions of existing products.
key words: gelatin, colloid, antiperspirants, deodorants, sticks, gels
I n classical scientific terms, gels are defined as solid or semisolid materials in

the colloidal state; for example, a solution of gelatin in water. However, in the
cosmetic industry, the term gel is more loosely interpreted. In general, cosmetic
chemists and marketers use “gel” to describe semiliquid products that are usually
dispensed from squeezable packaging.
Following this definition, many products that are not true colloidal suspensions
are called gels to increase consumer appeal. For example, a thickened surfactant
solution can be called a bath gel even though it is not a colloid. Thus, through modern
marketing, virtually any product can be called a gel. This rather bold observation can
be easily confirmed simply by checking out a store that sells styling gels, sculpting
gels, spray gels, freezing gels, suntan lotion gels, toothpaste gels, deodorant gels,
post-foaming gels, ringing gels, shaving gels, aerosol gels and so on.
Gel Chemistry
Shear thinning: For the sake of this discussion, we propose that cosmetic gels
can be characterized by their clarity and shear thinning rheology. Shear thinning is
the tendency to spread easily with applied pressure or friction. In simplest terms,
these gels are water or water/alcohol solutions thickened with a gelling agent or a
combination of gelling agents. The chemistry of these gellants varies with the specific
application. For example, acrylic polymers are commonly used to thicken hair- and
skin care gels. Carbomers are the most commonly used synthetic polymers.
Other gel thickeners include natural gums (such as tragacanth, guar, carrageenan,
xanthan and locust bean) and cellulose derived polymers (like hydroxyethylcellu-
lose and hydroxymethylcellulose). In addition, starches from corn, oats and other
sources are used to thicken gels.
In addition to water based gels, anhydrous gels are occasionally used in cosmet-
ics. These primarily solvent systems are thickened with organomodified clays. Fox
describes a variety of gelling agents in his review of United States and International
patents.1
The inexperienced formulator should be cautious when selecting gelling agents
for two key reasons. First, gelling agents should be used at very low levels to avoid
leaving an objectionable residue on hair or skin. This consideration is important
because gels are often formulated as leave-on products. Second, care must be taken
251
252
Gels and Sticks Beginning Cosmetic Chemistry
to avoid making the gel too stringy or pituitous; stringy products are less appealing
and may negatively impact consumer response.
Clarity: Another important aspect of gel chemistry is product clarity. Gels are
clear because they are single phase systems. In other words, they are composed of
either all water soluble or all oil soluble materials. In an emulsion, oil and water
soluble ingredients are mixed together; one phase is dispersed in the other. The
dispersed phase is in the form of tiny droplets that scatter light and render the
product opaque. The so-called “ringing gel” is an exception, as it is actually an o/w
microemulsion. In this case, the dispersed particles are so small that they do not
scatter light and, therefore, the emulsion is clear. Ringing gels are named for how
they vibrate when shaken or struck. Ethnic hair care products are often based on
this type of formula because of its high concentration of oil, which is beneficial for
hair that has been severely damaged by relaxing and straightening.
Gel Applications
Hair care: An exhaustive review of all gel formulations is well beyond the scope
of this chapter, but we will briefly mention some important applications. Gels are
widely used in hair care to provide conditioning or styling properties. In addition
to the thickening agents described in the previous section, these products contain
emollients, to make the hair more combable, or resins, to hold the hair in place.
Lochhead and Hemker et al have written an excellent, detailed review of hair gel
chemistry.2 (See Example Formula #1 hair gel.)
EXAMPLE FORMULA #1
Flexible Hold Hair GelCompany:

Kemira Specialty Inc.
The following formula is a hair gel that provides hold while remaining flexible…
Ingredient w/w
1 Water (aqua) 50
2 Carbomer (Carbopol, BF Goodrich) 0.5
3 Triethanolamine (TEA, 99%, Dow Chemical) 0.6
4 Water (aqua) 39.9
5 PVP (Luviskol K 30, BASF) 2
6 Polyquaternium 11 (Triquat 11N-CC, Kemira) 4
7 DL Panthenol (DL Panthenol, Kemira) 0.5
8 Propylene glycol (and) diazolidinyl urea (and) methylparaben
(and) propylparaben (Tristat D2, Kemira) 1
9 Hyrolyzed wheat protein (Wheat-tein NL, Kemira) 0.5
10 Hydrolyzed keratin (Kera-tein V, Kemira) 1
Procedure: Disperse item #2 in #1. Mix. Once hydrated, add #3 to the solution and
mix until uniform gel is obtained. Separately, dissolve #5 in #4. When dissolved, add
#6. Mix well. Combine both solutions and mix until a uniform gel is formed. Add the
remaining ingredients individually to batch. Mix until uniform.
253
Body care: Gels are also widely used in body and facial care. Shower gels were
first popular in Europe and are now hold a significant market share in the United
States. These products are not true gels but are surfactant systems thickened with
a material like guar. An article by RS Rounds discusses the rheology of these gel
systems and how the viscosity of a product can contribute to its perceived quality
and value.3 Facial moisturizers, toners and eye makeup removers are also available
in gel form. Even facial masks and sunscreens have been produced in gel form.
Rounds also points out that gels have an interesting esthetic for skin care products:
gels that have the appropriate rheology can suspend particles, such as small gelatin
beads. This formulation approach can dramatically enhance a product’s appear-
ance, and is often used for premium skin care products. (See Example Formula
#2 body wash gel.)
EXAMPLE FORMULA #2
Body Wash Gel

Ingredient w/w
1 Hydroxypropyl guar (Jaguar C-162, Rhodia) 0.3
2 Water (aqua) 54.7
3 Citric acid qs
4 Sodium laureth sulfate (Rhodaplex ESB 3/A2, Rhodia) 33.6
5 Sodium cocoamphoacetate (Miranol Ultra C32, Rhodia) 6.3
6 Coco glucoside (Plantacare 818, Cognis) 3.9
7 PEG-120 methyl glucose dioleate (Antil 127, Degussa) 0.5
8 Methylisothiazolinone (Neolone 950, Rohm and Haas) 0.1
9 PEG 40 hydrogenated castor oil (Alkamuls CRH-40/C, Rhodia) 0.3
10 Fragrance (parfum) 0.3
11 Citric Acid qs
12 Sodium chloride qs
Procedure: Disperse #1 into #2 and mix until completely dispersed. Hydrate with #3
(pH4). Add #4, #5, & #6. Then add #7, #8 and mix until completely clear. Pre-mix #9
& #10. Add to batch. When completely clear, adjust pH (5.7–6) with #11 and modify
viscosity with #12.
Facial care: Shaving gels are another important example of skin care gels. This
type of product is typified by Edge shaving gel, the first commercial post-foaming
gel. Post-foaming gels combine aerosol and gel technology and are surfactant solu-
tions with dissolved isopentane. A special aerosol package maintains pressure so the
isopentane cannot escape. When dispensed onto wet, warm skin, the isopentane
quickly evaporates and the product changes from clear gel to copious foam. Post-
foaming gels can be found in a number of shaving products and shower gels.
Oral care: Toothpaste gels consist primarily of water, a humectant (such as
glycerine or sorbitol), surfactant, flavoring agents and hydrated silica. High-viscosity
254
toothpaste gels can be made by thickening the system with 20 or 25% silica. The
silica also provides the product with the abrasives needed to function as an effective
dentifrice. However, the silica alone does not bind water well enough to form a
stable gel; therefore, additional gums must be added to stabilize the system. These
gums include carboxyvinyl polymers, cellulose derivatives, xanthan gum and car-
rageenan.4 In addition to toothpastes, other examples of gels used in or around the
mouth include gum care products, lip glosses and moisturizers.
Manufacturing of Gel Products

Most gels primarily consist of a liquid phase and are processed in a similar man-
ner to other liquid products, with a few exceptions. Like liquid products, gels are
prepared in large stainless steel kettles designed for heating and cooling. Depending
on the viscosity of the final product, special high-torque mixers may be required to
proper batch mixing. Some gel products require special batching equipment that
allows a vacuum to be drawn while the product is mixing. This type of equipment
may be used in gel toothpaste manufacture.
Batching process: The batching process typically consists of mixing and, if
necessary, heating all ingredients except thickening agents, which are added late
in the process to keep the batch thin. Once a batch thickens, it is more difficult to
mix, tends to trap air and takes more time to cool. Some thickening agents, such
as some acrylic polymers, can be dispersed in the water phase early in the manu-
facturing process because they do not appreciably thicken until after adjusting the
pH of the batch. This formulating tip is useful because these thickeners are often
supplied in powder form, and they are easier to disperse when added early in the
manufacturing process. As the remaining ingredients are added in the later stages
of manufacturing, care must be taken to avoid trapping air in the batch.
After completing the batch and meeting all relevant specifications, it can be filled
into its final package. A plastic tube standing upside down on its cap is a classic gel
package. Because gel products are typically quite thick, storing the packing upside
down eases dispensing. These tubes are not filled through the dispensing orifice,
as bottles are, but instead they are filled through the opposite end of the tube. The
empty tube travels on a conveyor line and passes under a nozzle that dispenses the
product into the package’s open end, which is later crimped and sealed by applying
heat or ultrasonic vibration.
Cosmetic Sticks
While gel formulations are excellent for many products, consumers do not
want to directly handle some products. For these applications, sticks are an at-
tractive delivery vehicle. In the personal care industry, a stick is a solid delivery
vehicle cast in an elongated form. When a stick is rubbed onto skin, it delivers a
variety of cosmetic ingredients, such as fragrance, coloring agents, emollients and
more. Sticks are useful because their solid nature allows them to deliver insoluble
materials, like pigments.
255
Chemistry of Sticks
Examples of well-known cosmetic sticks include lipsticks and antiperspirant/
deodorant sticks. These two types of products exemplify three categories of stick
chemistry. Lipsticks consist of a mixture of waxes and oils. The waxes (such as
beeswax and carnauba) and the oils (such as mineral and castor oil) are mixed with
pigments and cast into solid form. Deodorant sticks, aqueous solutions of propylene
glycol, are solidified with a soap, usually sodium stearate.5 Antiperspirants consist
of a volatile silicone (for example, cyclomethicone) gelled with fatty alcohols (such
as stearyl alcohol).
A fourth type of stick chemistry uses dibenzylidene sorbitol (also known as
dibenzaldehyde monosorbitol acetate or DBMSA) as the gelling agent to form
clear sticks.
Applications for Stick Formulations

APDs: As noted above, antiperspirant/deodorants (APDs) are common applica-
tions for stick technology. In fact, APDs are largely responsible for the development
and growth of the stick category. This fact is due, in part, to the demise of aerosol
antiperspirants in the mid-1970s that occurred following health and environmental
concerns links to such aerosols. Between 1974 and 1992, aerosols declined from
82% of the market to only 22%. Stick products have steadily increased in sales as
aerosols have fallen.6
It is important to note the difference between deodorants, which are cosmetic
products that only reduce body odor, and antiperspirants, which are OTC drugs
that reduce perspiration. By these definitions, every antiperspirant is a deodorant,
but not every deodorant is an antiperspirant.
In the past few years, clear sticks have gained popularity in APDs. Although the
first clear stick products appeared as early as 1979, these early products had stability
problems and did not have significant market impact. Since the late 1970s, chem-
ists for various companies have struggled to advance clear APD stick technology.
They improved processing by adding small amounts of organic solvents and other
materials that improved heat stability. Jungermann provides an excellent overview
of the chemistry of these early sticks.6
It wasn’t until 1993, when Bristol Myers introduced Ban for Man, that clear
stick products achieved significant commercial success. Today a number of clear
sticks are on the market. One interesting approach is Gillette’s Cool Wave clear
APD gel-stick. This product was actually a gel but it was dispensed from a stick-
type package. The long-term market impact of clear APD sticks and gel-sticks
remains to be seen.
Other applications: Other important applications for stick technology include
lipsticks and makeup. Lipsticks are waxy sticks containing oils and a high pigment
load. Moisturizing sticks for lips are also common. Wax based pigment sticks,
similar to lipsticks, can be formulated to cover facial blemishes and are sometimes
medicated with antiacne or other OTC drug ingredients. Color cosmetics for the
face can also be made in stick form.
256
Blush, foundation and eye shadow sticks are not commonly marketed, but patents
can be found for such compositions. These products are challenging to formulate
because high levels of talc, starches and other powders make the product crumble
more easily. Finally, fragrance sticks (also known as cologne sticks) were at one time
a popular way to deliver fragrance. Formulating these products was challenging
because the high fragrance level tended to discolor the base.
Stick Manufacturing
Depending on the type of formulation and the style of packaging, two primary
techniques are used to make sticks. One approach is to first mold the sticks in the
proper shape and insert them into the package. The other is to pour molten stick
material directly into the package, and let it solidify into the shape of the package
upon cooling. Both these methods require expensive manufacturing and filling
equipment and, therefore, most marketers rely on contract manufacturers to pre-
pare sticks on a commercial scale.
Premolding method: The pre-molding method is usually used to manufacture
products like lipsticks. The heated wax mixture is poured into a multi-cavity stainless
steel mold. After cooling, the mold is opened and the individual sticks are removed
and inserted into containers. After insertion, each lipstick requires careful finishing
to give it an attractive appearance; gently heating the lipstick, melting the outer
layer to obscure mold defects and improve surface gloss, will usually do the trick.
This process can be done in an automated heating tunnel or by passing individual
lipsticks over a flame by hand.
Manufacturing makeup sticks that contain high levels of powder requires another
type of premolding procedure. In this case, the sticks are cast by solid compression
techniques. The solids are then mixed with water or another volatile solvent and
extruded in stick form. After the solvent evaporates and the mixture hardens, it
can be cut into lengths and inserted into the packaging.
Hot-Fill methods: Molding sticks directly into packaging is the most common
stick manufacturing process; this technique is also used to manufacture APD sticks.
After ingredients are combined in a jacketed stainless steel kettle, applied steam
heat melts the ingredients while mixing the batch. During the blending process,
the temperature must be carefully controlled to avoid scorching the waxy or fatty
ingredients. After blending is complete, the batch can be filled. Stick packages are
typically hollow tubes with an elevator platform inside that moves up and down
to dispense the product. In some packages, this platform is pushed up by hand.
In others, the platform moves up by turning a screw that causes it to travel along
a central threaded post.
Empty containers move along a conveyor belt where the molten product is
dispensed through a filling nozzle. The exact process varies depending on whether
the package is designed to be filled from the top or bottom. In general, the product
is filled slightly above its congealing temperature so that it flows easily. If it is filled
too hot, the dispersed solids may settle to the bottom; if it is filled too cold, air
bubbles will be trapped in the stick.
257
Sticks may then go through subsequent finishing operations to ensure the surface
is smooth and the product is free of air pockets. This step usually involves heating
the tops of the sticks slightly by passing them under an infrared lamp. A probe can
be stuck into the center of the stick for air to escape. Heating the surface again
melts the product, eliminating any hole created by the probe.
Finally, the sticks pass through a refrigeration tunnel to rapidly lower the
temperature for a solid form. Depending on the package design, a top or bottom
piece will seal the container. The finished sticks may pass through cleaning stations
before being placed in shipping cartons.7
Future Challenge
Gels and sticks are interesting because they represent areas where formulators
can generate new product ideas by making novel forms of existing products. For
example, shower gels were almost unheard of in the US market until a few years
ago. Likewise, no one thought that a clear antiperspirant stick could be made until
recently, and consumers are showing interest in this vehicle. The challenge is to
apply gel and stick technologies to the development of innovative new products.
References
1. C Fox, Sticks and Gels—Patent and Literature Update, Cosm & Toil 102(10) 33–63
(1987)
2. RYLochhead et al, Hair Care Gels, Cosm & Toil 102(10) 89–100 (1987)
3. RS Rounds, Bath Gels: Rheology and Consumer Perceptions” Cosm & Toil 110(4)
52–73 (1995)
4. M Pader, Toothpaste Gels, Cosm & Toil 102(10) 81–7 (1987)
5. G Barker, Sodium Stearate-Based Sticks: Proposed Structure, Cosm & Toil 102(10)
71–80 (1987)
6. E Jungermann, Clear Antiperspirant Stick Technology: A Review, Cosm & Toil 110(2)
49–56 (1995)
7. N Geria, Manufacturing and Packaging Technology of OTC Cosmetic Sticks, Cosm &
Toil 102(10) 65–70 (1987)
Chapter 28
Aerosols for Apprentices

A brief look at the four principal components of a typical
aerosol, some popular physical forms, and conventional
manufacturing methods.
key words: valve, packaging, actives, solvents, propellants,

foaming gel, quality assurance, pump
F urthermore, these regulations, which started in California, have now blos-

somed to become US EPA regulations. With the more stringent regulations
in California of 2000, we now contend with additional Ozone Transportation Com-
missions such as the Mid-Atlantic, the Northeastern States, and the Midwest States
Commissions. CARB continues to review their regulations to further reduce VOC
emissions due to population growth and un-attainment of stringent Federal EPA
Clean Air Standards. Discussions are underway to measure VOCs on a reactivity
basis in California.
Abroad, Canada had adopted VOC limits on a “voluntary” basis. The European
Union is still evaluating what to do about the situation. In 2008, Canada is expected
to pass mandatory regulations based on the most stringent CARB regulations of
record. Of equal importance, California is drafting the first North American restric-
tions on Global Warming Compounds.
From a technical standpoint, little has changed. HFCs remain the propellant of
choice for anhydrous systems. However, while a number of water-containing formulas
can still be found on the market, they are losing share. Interestingly, acetone was
granted an exemption so it can be used without adding to the VOC content, but it
has other issues such as odor and toxicity that make it difficult to use.
Keep these changes in mind as you read the following chapter.
Compliance with this multitude of regulations takes careful planning and
patience.
What is an aerosol? Physical chemists might define the term as “a gaseous suspen-
sion of colloidal particles.” They might even cite fog, which is water dispersed in the
atmosphere, as an example. A cosmetic chemist, on the other hand, might define an
aerosol as “a self-contained, pressurized spray system designed to dispense various
solid, liquid and gas products.” While both definitions are technically correct, the
latter describes a US$3 billion-plus segment of the cosmetics industry.
Background: Aerosols were developed during the early years of WWII to de-
liver pesticides. As the benefits of this new technology became apparent to other
industries, a landslide of marketers, including personal care manufacturers, began
259
260
Aerosols for Apprentices Beginning Cosmetic Chemistry
to make aerosol versions of their products. In the late 1940s and early 1950s, aero-
sol hairsprays, colognes and shaving creams were introduced in the United States.
Today, personal care aerosols include a variety of hair-styling sprays, antiperspirants,
skin oils, breath fresheners and many other products. Over a billion units are sold
annually in the United States alone.
The cosmetic chemist’s definition can also be expanded to include descriptions
of an aerosol product’s four essential components:
• A package, or can, that is able to contain relatively high pressures—as high
as 130 pounds-per-square-inch gauge (psig).
• A valve that seals the can and controls how the contents are dispensed.
• The ingredients that provide functionality.
• A compressed or liquefied gas propellant that forces the contents from the
can.
This chapter discusses each of these key components as well as the physical
forms and manufacturing methods of aerosol personal care products. It is a balance
of all four of these essential components that defines the aerosol. Any change to
one of these components affects the overall performance of the product.
Regulatory References
US EPA (Environmental http://www.epa.gov
Protection Agency)
US DOT http://www.dot.gov/
(Department of Transportation)
CARB http://www.arb.ca.gov/homepage.htm
(California Air Resources Board)
CPSC (US Consumer Products http://www.cpsc.gov/
Safety Administration)
Personal Care Products Council http://www.personalcarecouncil.org/
(formerly: CTFA)
CCTFA (Canadian CTFA) http://www.cctfa.ca/en/cctfa/index.htm
Health Canada http://www.hc-sc.gc.ca/index_e.html
CSPA (Consumer Specialty http://www.cspa.org/
Products Association)
Aerosol Packaging
Historically, aerosols have been packaged in either metal or glass. Glass con-
tainers have some utility in low-pressure systems, such as cologne sprays, but they
are not widely used because of safety reasons. Metal has long been the primary
261
choice for aerosol packages because it is strong enough to contain high-pressure

propellants. Metal containers are available in basically two types: tin-plate steel
and aluminum.
Tin-plate cans: Tin-plate cans usually consist of three separate pieces of tin-
coated steel, collectively referred to as a “base plate.” This tin coating keeps the
steel from reacting and, thus, corroding. The largest of these three metal pieces is
formed from a flat sheet of metal rolled and welded into a cylinder that becomes
the body of the can. The top of the can, known as the “crown” or “dome,” and the
bottom, or “base,” are formed separately, usually from slightly heavier base plate
metal. They attach to the formed cylinder. These pieces are crimped onto the can’s
body and sealed with special caulk, known as “sealing compounds.”
The designs of the dome and base are such that they invert or bulge if pressure
increases. This distortion, in turn, increased the can volume and relieves pressure
without bursting the package. The precise construction of the can is critical to ensure
that no microscopic fissures or weak spots exist that could leak during pressurization.
Can construction is regulated; see US DOT Code of Federal Regulation, CFR49.
Can selection is always made by proper selection related to pressure generated by
your product as prescribed in the regulations.
The dome has a circular opening—the standard diameter is 1 inch—through
which the can is filled. Tin-plate cans are produced in a variety of sizes; height ranges
from a few inches to 10–12 inches, diameters from about 2–3 inches.
Before the cans are formed, the interior of the components may be coated with
a variety of epoxy-type materials to reduce potential interaction between the prod-
uct and the metallic can surface. Similarly, the outside of the can may be treated
to resist weathering. Tin-plate cans are commonly used because of their superior
strength, relatively low cost and ease of high-speed handling on filling lines. Some
disadvantages are that they can be less elegant looking than aluminum cans and
are more reactive to water-based products.
Aluminum cans: Aluminum cans, also widely used as aerosol containers,
come in a wider variety of sizes than their tin-plate counterparts, ranging from a
few inches to about one foot. They are made from a slug of malleable aluminum
that is extruded into a tube of desired dimensions. Because of their one-piece
construction, aluminum tubes have no seams that can leak. Also, aluminum is less
reactive than steel; therefore, it is preferred for aqueous formulations. Unfortu-
nately, aluminum containers are more expensive than tin-plate cans and cannot
be handled on-line as quickly or as easily. As growth in recycling and consumer
awareness of the Green Movement increases, it is important to note that aluminum
aerosol cans have extremely long lead times in the supply chain. Often these lead
times can be as long as 26 weeks. The aluminum package used for aerosols must
be made of virgin aluminum; no tolerance for impurities can exist. This package
however is very malleable and moldable into a multitude of shapes often making
it the package of choice for prestigious marketers.
Two Piece Steel Cans: Relatively new to the United States, this can design
consists of a two-piece polymer-coated steel can—the first consumer package of
its kind in the United States. The can is made of steel but lacks the usual side seam
262
and weld associated with three piece designs. The cans are drawn from a flat stock
of PET coated tin free steel to form a continuous shaped can body. Bottoms are
similarly drawn and seamed onto the body to form the aerosol container. Advan-
tages exist due to the continuous PET coating on the interior and exterior surfaces
allowing for a wide variety of corrosive and non-corrosive products. The result is
a stronger can construction with less surface defects. Sizes are limited restricting
many uses today. This container technology is one to keep your eye on.
Top 10 Advantages of Aerosol Products

1. No evaporation.
2. No contamination from bacteria, dust and so forth.
3. Ready for instant use at anytime. No heating, thawing, mixing, or blend-
ing is necessary.
4. Application is clean and even.
5. Very long shelf life—three to 30 years.
6. Dispensers are portable and easily stored.
7. Very small amounts can be dispensed.
8. Unique and desired dispensing methods are available, such as sprays or
foams.
9. Can dispense powders, liquids, gases, gels, foams, paste and so forth
with equal facility.
10. No skills or tools required to operate.
Specialty Containers: Aluminum and tinplate cans are available with barrier
technology to keep products and propellants separated. These containers have been
widely used in the foods industry and are crossing over into the personal care arena.
Of these various technologies, bags can be formed into the container for separation.
Similarly, pistons can be inserted during the forming process to achieve the same
separation. A bottom hole is made and fitted with a plug for facilitating propellant
filling and insure separation of the contents.
Valves
Another key packaging component of an aerosol system, the valve, has the dual
task of sealing the pressurized contents in a can and controlling the dispensing of
these contents (Figure 28.1). Valves have three sections:
• The diptube that feeds the product from inside the can to the valve body.
• The valve body, a complex network of micro-orifices and chambers designed
to optimally mix product and propellant.
• The button, or actuator, that is depressed to open the valve and release the
contents.
263
Figure 28.1. Valve assembly systems
Diptubes: The diptube is a plastic—usually polyethylene—tube of a specific

diameter and wall thickness that extends from the bottom of the valve body/tail-
piece to the base of the can. It acts as a straw, drawing the product up to the valve.
Its bottom tip must remain in the liquid portion of the contents or it will draw
propellant instead of product. Because the diptube helps dispense the product, its
diameter is carefully controlled. Special valves, known as “360º valves” or “spray
anyway systems,” are designed to spray even in inverted positions. For an example
of the use of 360º valves, see the Nexxus 360º Volume Bodifying Finishing Mist
recently introduced employing this unique feature.
Valve body: The valve body is the main—and most complex—section of a
valve. It consists of several subsections:
• A tailpiece (on most valves) that serves as an attachment point for the
diptube.
• A body housing, or mixing chamber, where the propellant/liquid concentrate
combination is metered into the valve stem area. For difficult to atomize
sprays, a vapor tap may be incorporated into the body to mix in extra gaseous
propellant into the product stream.
• The stem, through which the product enters the attached actuator and exits
the can. The top of the stem serves as the attachment point for the actuat-
ing mechanism. For “male” valves, the stem is the uppermost portion of
the valve; on “female” valves, it is located on the button that inserts into the
valve body.
• The stem gasket seals the container. This disk of rubber effectively seals the
exit from the can until the consumer depresses or tilts the stem creating a
break in the seal forming an exit path from the container. Proper selection
of the rubber material is important to guarantee reliable function of the
system.
264
• A spring is used to apply the appropriate pressure to create the seal between
the stem gasket, valve housing and stem.
Actuator: The third part of the valve is a separate piece that attaches to the stem
and is known as the “actuator.” Types of actuators, known as “buttons” or “spray
caps,” are available in many styles and sizes to suit various esthetic and technical
needs. The inside may be designed with plastic inserts that, being equipped with
specially designed swirl channels, break the spray up into fine particles. When the
actuator is depressed, it pushes the stem opening away from the gasket. This design
allows the contents to flow up the diptube, into the valve body, through the stem
and out the actuator’s main orifice. By combining the appropriate actuator with
the right valve system, you can create a variety of spray effects, from a fine-mist
spray to a powerful stream.
Valve Housing: Valve components are housed in a valve cup, a ring-shaped
piece of either aluminum or tin-plate steel. The bottom valve assembly is inserted
into the opening of the dome and machine-crimped to lock it in place and seal in
the contents. Various gasketing materials, such as polyethylene films, are used to
ensure a tight seal between the valve cup and the can body.
A high degree of precision is required in the manufacture of aerosol valve com-
ponents. In fact, accuracy on the order of 1/1,000 of an inch is critical to ensure
proper valve functioning. Furthermore, both the valve and the can must be carefully
selected to ensure that they are compatible with the chemical composition of the
formula; all components must work together.
Aerosol Concentrate Chemistry

A product’s intended functionality determines the chemical composition of an
aerosol concentrate. This concentrate is formulated to perform a specific function,
such as hold hair, control body odor or freshen breath. Its chemistry will, in part,
dictate the type of propellant and valve system to be employed. For example, water-
based and alcohol-based concentrates may require different propellants. Similarly,
highly viscous concentrates may require much wider, or macro, dip tubes; less viscous
ones may only need capillary dip tubes. Typically, concentrates are composed of
actives, solvents and secondary ingredients.
Actives: In many ways, the product concentrate is formulated just like any
other personal care product. The formulator first identifies the desired benefits of
the end product and then chooses the raw materials and actives that will produce
those benefits. Many conventional formulations, such as styling gels or skin creams,
also use the same ingredients in aerosol concentrates. These include surfactants,
polymers, fatty acids, silicones, aluminum salts, fragrance materials, humectants,
proteins, dyes and emollients. The actives perhaps most used in aerosols are the
polymeric resins common to hairsprays and styling products. Because most were
specifically designed to take full advantage of spray systems, these resins are not
commonly found in conventional formulations.
Solvents: The solvent is an ingredient or mixture that serves multiple functions
in an aerosol formulation. It frequently makes up the largest portion, by weight,
of the product concentrate.
265
Top 10 Disadvantages of Aerosol Products

1. Mist can be irritating if inhaled.
2. Package can over-pressurize and rupture under extreme heat.
3. Some are flammable.
4. Clogging or sustained streaming can occur.
5. In rare instances, aerosols can depressurize and become inoperative.
6. Relatively high packaging costs.
7. The term “aerosol” may have environmentally negative connotations to
consumers.
8. Disposal is perceived as a possible problem.
9. With minor exceptions, containers must be cylindrical.
10. Higher-than-average energy consumption required to produce, particu-
larly for aluminum cans.
Solvent functions: A solvent’s primary function is to reduce the incompat-

ibility often found between actives and the typical propellant; the concentrate and
the propellant must usually exist in a homogeneous solution to ensure a sprayable
product.
The solvent may also modify the system’s delivery characteristics because it can
affect the concentrate’s viscosity. Low-viscosity concentrates (3–7 cP) are gener-
ally easy to atomize; high-viscosity concentrates may be hard to break up into fine
droplets.
Another function of the solvent is to improve the final product’s effectiveness.
By influencing spray characteristics, the solvent changes the behavior of the ac-
tives on the surface. As examples, the right solvent can help a product dry faster—
particularly useful in hairsprays and deodorants—or improve an active’s ability to
adhere to the surface to which it is applied.
A solvent can have additional benefits of its own. It can adjust the pressure of
the overall system, which affects product performance. Controlling the pressure
is also important because of safety concerns. If the pressure inside an aerosol con-
tainer exceeds a certain level, the container may rupture and create a potentially
hazardous situation.
Popular solvents: Ethanol is one of the most commonly used solvents for per-
sonal care products. It is particularly effective in hairsprays and deodorants because
of its high compatibility with many propellants and actives. It also has relatively high
vapor pressure, which minimizes drying time after surface application.
Water is used as a solvent because of its low cost and nonvolatile organic com-
pound (VOC) status. Drawbacks of formulations that use water are longer drying
times and reduced hydrocarbon solubility. Still, numerous formulating techniques
can minimize these drawbacks. Other solvents used in personal care products
include glycols, silicones and fatty esters.
Other ingredients: Besides the actives and solvent, you can add other com-
pounds to the product concentrate. Some materials improve the characteristics of
266
the primary actives. For instance, propylene glycol, silicone, purcellin oil or other
such plasticizer is often added to hairspray to modify the flexibility and adhesive-
ness of the resin on the hair.
If an emulsion is desired, you must include emulsifying surfactants. Similarly,
suspending agents are needed for powdered actives. Other materials can optimize
the pH and viscosity of the product concentrate. Because some ingredients have
corrosive properties that can compromise the integrity of the container, you may
need to add anticorrosion agents, such as ammonium hydroxide, AMP, morpholine,
cyclohexylamine or borate esters.
Propellants
The propellant is what sets an aerosol apart from other formulations. It often
serves the purposes of producing the pressure that forces the concentrate from
the container and converting the actives into the desired physical form, such as
droplets, a thin film or foam matrix.
The majority of propellants used in personal care products are liquefied gasses
that have both a low boiling point and a sufficiently high vapor pressure to expel the
concentrate from the container. Ideally, they should also have low flammability, low
toxicity, good compatibility with many raw materials and good chemical stability.
They should also be inert and cost-effective.
In the past, chlorofluorocarbons (CFCs) were the most common type of aero-
sol propellants because of their low flammability and good solvency. However, in
the late 1970s, environmental concerns led to the eventual ban of these materials.
Today, manufacturers use hydrocarbons and other CFC alternatives.
Hydrocarbons: Commonly employed propellants include propane, butane
and isobutane (In the United States, aerosol grade propellants are an Isobutane/
Propane mixture designated as an “A” blend—aerosol blend—followed by the
approximate vapor pressure in psig. It should be noted that in other parts of the
world, the industry generically uses “butane” as a standard name for these various
hydrocarbon mixtures as they are richer in butane, followed by a number indicat-
ing the approximate vapor pressure of the mixture. For example, Butane 40 is a
propane/butane mixture with a vapor pressure of 40 psig).
Hydrocarbon propellants have certain advantages and disadvantages that should
be considered before using. On one hand, they are highly compatible with organic
solvents and have low toxicity and good chemical stability. The major drawback to
using hydrocarbon propellants is their flammability and explosive potential. This
is of particular concern during manufacturing.
Another problem with hydrocarbon propellants is their status as VOCs. In the
United States, the amount of VOCs allowed in consumer products is limited. These
restrictions complicate the formulation of a complying aerosol product that uses
hydrocarbon propellants. It is difficult to formulate a single-phase product with
hydrocarbon as the lone propellant because of its limited solubility in water—a
non-VOC ingredient. Please be aware of the ever changing state of regulations.
Hydrofluorocarbons: Hydrocarbon propellants that contain at least one
fluorine molecule are hydroflourocarbons. They share many properties with CFCs,
267
including good stability, solvency and compatibility with many raw materials. They
also have low toxicity. Unlike CFCs, hydrofluorocarbons are not thought to destroy
the ozone layer. Common hydrofluorocarbons include 1,1-difluoroethane (Propel-
lant 152a) and 1,1,1,2-tetrafluoromethane (Propellant 134A). The low reactivity of
hydrocarbons exempts them from VOC legislation—although they are technically
VOCs. However, these seemingly ideal propellants are significantly costlier than
hydrocarbons, a factor that will limit their use. Be aware that these compounds
have a global warming potential and may by limited pending restrictions.
Dimethyl ether (DME): DME has many characteristics of a good propellant,
such as adequate vapor pressure and a good toxicity profile with no penchant for
destroying the ozone layer. Traditional drawbacks of DME are its flammability and
high cost. One important property is its miscibility with water in most ratios. This
tolerance for water not only allows for formulation of aerosol sprays with low flam-
mability but also makes DME important in the formulation of low-VOC aerosols.
By using DME as a propellant, water can replace some of the organic solvents in
a spray, which reduces its overall VOC content.
Compressed gas: Unlike the above materials, compressed-gas propellants,
such as carbon dioxide, nitrous oxide or air, remain gaseous inside aerosol con-
tainers. They are nonflammable and odorless with very low toxicity. They are also
practically benign to the environment and can be manufactured at a very low cost.
Unfortunately, compressed gases have many disadvantages that severely limit their
use. The most difficult to overcome is a drop in pressure in the container as the
product is used up. This drop can lead to undesirable spray patterns and particle
sizes as well as depleting the propellant before the entire product is expelled.
Another problem is the limited solubility of most materials. Because compressed
gases are typically insoluble in the liquid concentrate, it is difficult to achieve good
spray characteristics. Sprays also tend to be wetter because the gases are not very
soluble in typical aerosol concentrates. In time, these problems may be overcome
and compressed gases may represent the future of aerosol propellants.
It is important to note that aerosol products can dispense particles small enough
to travel into the lungs, reside there and cause potential respiratory problems.
Therefore, any raw material used should be tested for the biological effect of
inhalation.
Product Forms
When an aerosol is expelled from the container, the physical form exhibited is
a function of the interaction between product concentrate and propellant. Aerosols
can dispense as solutions, emulsions, dispersions or pastes.
Solutions: When the propellant and concentrate are miscible, a solution forms
inside the aerosol container. Such solutions are emitted as sprays when the aerosol
valve is activated. Spray results from simultaneous propellant and concentrate
expulsions and the propellant’s violent evaporation, leaving only the concentrate.
Depending on the types of solvent, propellant and valve system used, formulators
can control the spray characteristics of products, the most common examples of
268
which are in hairsprays and deodorants. Examples include Tresemme II Extra Hold
Hairspray, Pantene Ultra Firm Classic Hairspray, and AXE Body Spray.
Emulsions: An emulsion is another form into which an aerosol system can be
formulated. The most common type used for personal care products is oil-in-water
that dispenses as foam, such as in mousses and shaving cream. A foam needs the
propellant—which makes up a small portion of an emulsion—to be soluble in
the oil phase but immiscible in the water phase. When dispensed and exposed
to atmospheric pressure, it rapidly expands. This expansion in the presence of
surfactants is responsible for the foaming action. Foam characteristics can be af-
fected by varying the concentration or type of propellant, surfactants and auxiliary
materials used. Examples include Tresemme Mousse Extra Hold and Clairol Herbal
Essences Mousse.
Powder dispersions: Some aerosols spray out as powders. These systems are
neither solutions nor emulsions but dispersions of a powder in a solvent and/or
propellant, often requiring an oily suspending agent. Antiperspirants containing
aluminum salts are the most common types of powder-dispersion aerosols. Examples
include Right Guard Sport Antiperspirant, FDS Feminine Deodorant Spray, and
Bumble and Bumble Powdered Shampoo.
Foaming gel: Another important alternative aerosol form is one in which the
product concentrate and propellant do not physically interact. In these systems, the
product concentrate is placed in a bag or other barrier system within the aerosol
container that is surrounded by propellant. The product is dispensed as the propel-
lant presses against the walls of the bag. This technology has created a novel form
known as a “foaming gel.”
In these systems, a gel with a small amount of low-pressure solvent or propel-
lant dissolved within it is placed in the bag. A primary propellant dispenses the
product as a gel, and a secondary propellant creates the characteristic slight foaming
effect. Both of these approaches are commercially available; each has advantages
and disadvantages, depending upon the specific application. This technology was
pioneered for applications in which contact between the product and propellant is
not desirable, such as sprayable cheese and other aerosol food products. Gel shave
foams are the dominant personal care product using this technology.
Examples include Gillette Satin Care Shave Gel for Women and Skintimate
Shave Gels.
Manufacture of Aerosol Products

Contract manufacturers: Modern aerosol manufacture requires highly
automated equipment. This requirement involves significant capital investment.
For this and other reasons, many marketers of personal care products choose to
have their aerosols produced by outside, specialized vendors, known as “contract
manufacturers.”
Manufacturing process: Empty cans are fed onto a conveyor line. A jet of
compressed air cleanses them of dust and debris and a filling head injects them
with a metered amount of concentrate, usually in liquid form. The cans then pro-
ceed down the conveyor to the next station, valves are inserted. From there, the
269
cans usually move to an outside gassing facility, where three actions occur almost
simultaneously: vacuum is drawn to remove air from the system, the propellant
is injected into the can under high pressure and, a fraction of a second later, the
valve is crimped into place. This system is known as “under-the-cup-filling” since
both the concentrate and the propellant are filled before the valve cup is crimped
on. The advantage of this operation is filling through the 1 inch opening of the can
before the valves are attached. Very fast filling is achieved. The downside is related
to emissions of small amounts of propellant at the end of the system that failed to
enter the can before the operation was completed.
In another common filling system, known as “pressure filling,” the valve is
vacuum crimped into place after filling with the liquid contents. The propellant
is then pressure-filled through the valve stem opening. This later method is more
popular in Europe than in the United States As the propellant must travel through
the very small openings in the valve hardware, the process is very slow but offers
much less waste of propellant.
In either filling method, after gassing, the units travel through a long trough
containing hot water. As the cans traverse this waterbath, they are checked for
escaping bubbles, which would indicate a propellant leak. The high temperature
of the waterbath also raises the internal pressure of the can, which is intended to
cause any weak spots in the can to fail. Waterbathing is required by the US DOT and
many other governmental bodies globally to protect workers and consumers from
defective containers. After exiting the waterbath, the cans are dried by high-pressure
air jets. Finally, overcaps are placed on top of the cans and the finished units are
packed into boxes and stacked on pallets. Other waterbathing options are available
but not mentioned here, for more information see literature references.
Quality assurance testing: Samples are taken off the production line for
testing to ensure that the products meet all specifications. Frequently monitored
parameters include proper levels of actives, pressure, spray rate (expressed as
grams of product delivered per second) and spray pattern (the physical shape and
size of the spray). Additional testing is conducted to ensure that the cans evacuate
properly. Long-term stability studies should be done to establish that the cans don’t
show undue signs of corrosion.
Aerosol Alternatives
It is interesting to note that, despite the convenience and benefits of aerosol
systems, consumer demand has prompted the industry to develop alternatives to
the classic aerosol systems described above. These alternative systems, generically
known as “non-aerosols,” take advantage of different technologies that mimic the
effects of a propellant-driven system.
Pump sprays: The pump spray, the most well-known of these alternatives,
requires the consumer to depress an actuator button that strokes the pump. This
physical force, generated by compressing the spring inside the pump, creates a
fine spray.
Others: Other non-aerosol spray systems employ a package with a built-in
pump that the consumer must stroke several times. This pumping action fills the
270
package with compressed air. When the valve is opened, the compressed air forces
the product out, thereby approximating the effects of a continuous-spray aerosol.
Similarly, a type of bag-in-a-can technology uses the physical force of a stretched
rubber bladder to expel a continuous spray. Both of these approaches are com-
mercially available and again have specific advantages and disadvantages.
Conclusion
In recent years, US government agencies have enacted legislation limiting the
amount of VOCs in certain aerosol products. These measures are intended for
clean air control, even though the industry maintains that aerosols have minimal
environmental effect and, in many instances, do less damage than their alternatives.
We anticipate that this trend will have serious impacts on the future of aerosol for-
mulations. Nonetheless, despite the environmental concerns, personal care aerosols
continue to enjoy high-volume sales. In fact, they comprise nearly one-third of all
aerosol products sold in the United States.
Published in Beginning Cosmetic Chemistry, Second Edition,
Reference
1. MA Johnsen, The Aerosol Handbook, Wayne Dorland, Mendham: (1982)
Recommended Reading
CN Davies, Aerosol Science, Academic Press, London (1966)
J Knowlton and S Pearce, Handbook of Cosmetic Science and Technology,
Elsevier Science Publications, Oxford: (1993)
HR Shepherd, Aerosols: Science and Technology, Interscience Publishers,
New York: (1961)
Additional Packaging Sources:

Seaquist Perfect Dispensing www.Seaquistperfect.com
Precision Valve Company www.precision-valve.com
Ball Container Corporation www.ballamericas.com
Exal Packaging www.exal.com
DS Container www.dscontainers.com
CCL Container www.cclcontainer.com
Author’s Note: While fundamental aerosol technology hasn’t changed much since the original
printing of this chapter in 1998, significant changes have occurred in the regulatory area. In 1998,
the California Air Resources Board (CARB) began limiting volatile organic compounds (VOCs) in
aerosol hairsprays to a maximum of 80%. Since 2002, that limit has been lowered to 55%, which
means that it is even more difficult to formulate efficacious, consumer-acceptable products.
Chapter 29
Encapsulation
Technologies: Tailored
Solutions for Delivery
A variety of microencapsulation techniques can help formulators
create innovative personal care product forms with stable
cosmetic actives and long-lasting fragrance. This technology
summary of microencapsulation serves as an introduction to its
potential for high performance personal care products.
key words: antiaging, cosmetic actives, delivery, microcapsule,

microencapsulation, millicapsule
W ith more consumers entering middle age than ever before,1 personal care
products are evolving to meet changing market needs. In response to this
trend, formulators look for innovative ways to enhance the appearance of skin and
encourage a more youthful, healthy appearance. Use of botanical extracts and other
potentially unstable cosmetic actives continues to rise.2 At the same time, competi-
tion in the marketplace favors products with novel, appealing sensory attributes
such as fragrance, a component that can also be unstable.
Ingredient instability drives the need for delivery systems that combine perfor-
mance with cost efficiency. Because delivery technologies differ widely, selection
of an appropriate system depends on individual formulation parameters as well as
the expertise of the delivery system provider.
Encapsulation Technology
Microcapsules and millicapsules are composed of a polymeric skin, wall or matrix
that encloses a liquid, solid or gaseous core. Microcapsules range in size from ap-
proximately 1–1000 µm, with most falling between 3 and 100 µm. Millicapsules are
usually larger, at up to 5,000 µm, and are used in formulations mainly for aesthetic
effects such as suspended beads with glitter or capsules with pearlescent coatings.
The capsule wall is typically nonreactive to the substance it contains. It is generally
strong enough to allow normal handling without rupture, and the shell or matrix
is sufficiently thin to permit a high-core-volume to polymer ratio. The contents of
the capsule typically are contained until the capsule shell is broken, melted, dis-
solved or otherwise removed.
271
272
Encapsulation Technologies: Tailored Solutions for Delivery Beginning Cosmetic Chemistry
Microcapsule and millicapsule technologies offer a variety of processes based

on scientific principles related to polymerization, surface energy and reaction kinet-
ics. Although microencapsulation is based in the science of physical and chemical
processes, the application and manufacture of microcapsules remains more an
art than a science. This classification is due to the nature of macroemulsions, and
the limitations of analytical methods and instrumentation. These limitations place
more responsibility on the skill of the operator than to defined in-process testing
methodologies. The following sections provide a general technology overview of
the processes used to produce microencapsulated materials.
Complex coacervation: This method involves complexation of positively and
negatively charged colloids in an aqueous environment to induce a polymer-rich
phase. This phase can be induced to deposit on a hydrophobic substrate based on
its borderline solubility in the liquid being used. Following adsorption onto the
substrate, the coacervate is chemically cross-linked to form the finished micro-
capsule, which has a hard outer shell. Gelatin is the primary positively charged
component in this type of microencapsulation system. In addition, the complex
coacervation process is carried out in a dilute solution containing the gelatin as
well as a negatively charged colloid. 3
Polymer precipitation: In situ polymerization is a process in which the capsule
shell is formed by the polymerization of monomers added to the encapsulation sys-
tem. Polymerization occurs exclusively in the continuous phase and at the interface
formed by the dispersed core material and the continuous phase. Polymerization of
reactants located in the continuous phase produces a low molecular weight prepoly-
mer. As this prepolymer grows in molecular weight, it deposits on the surface of the
dispersed core material. Continued polymerization, with cross-linking, continues
to generate a solid capsule shell. This process is ideal for protecting hydrophobic
materials. The most common process of this type employs aminoplast polymers,
which typically consist of either a polyoxymethylene urea or methoxymethyl meth-
ylol melamine pre-condensate.
Extrusion and spheronization: Preparation of solid, matrix-type microcap-
sules can differ dramatically from those of standard membrane systems, although
the uses and benefits of the matrix-based systems are similar. The production of
matrix-encapsulated microcapsules by an extrusion and spheronization process is
based more on mechanical methodology rather than chemical processing. Spher-
onization is a process in which extrudate material is formed into spherical shaped
particles using friction and centrifugal forces. Therefore, the type of extrusion
equipment and the choice of high-speed spheronization equipment are paramount
to the success of creating a suitable beadlet or prill. The physical properties of
the internal phase and the matrix such as rheology, solubility, surface tension and
thermal stability also play a key role.
Absorption or adsorption: The methods for incorporating an internal phase
material into an absorptive or adsorptive substrate are varied. They include basic
blending, solvent evaporation and molecular complexation based on charge dif-
ferentials. The basic premise behind all methods involves use of a substrate with
the capability of absorbing, based on pore capacity; or adsorbing, based on surface
273
area; a liquid vehicle that is 100% of the material to be encapsulated or that carries
the material to be encapsulated.
The internal phase can be either hydrophobic or hydrophilic, although the
choice of substrate determines this feasibility. Typical examples of substrates include
silica, cellulose, nylons, cyclodextrins and some natural clay. These systems also
produce materials that can be used in combination with other microencapsulation
systems, in which the loaded substrate can be overcoated to further protect the
internal phase.
Thermosetting matrix systems: A number of methods can be used to pro-
duce thermosetting, matrix-type microcapsules. The process used depends on the
polymer, but some common elements may affect the final properties. The spheres
are generally made from o/w emulsions. During manufacture, the polymers are
solubilized in water. Next, the active materials to be encapsulated are emulsified
into the aqueous, polymeric solution. The resulting dispersion can be transformed
into spheres by a variety of methods including mechanical dispersion, submerged
nozzle extrusion and high-pressure atomization.
Fragrance Management
Managing or extending the life of fragrance notes in both personal and household
care formulations continues to be an area of focus for formulators in both industries,
and laboratory studies can provide insights that are valuable in both markets.
Researchersa, investigating the potential for fragrance management using
encapsulation technologies, encapsulated several fragrance notes (Figure 29.1)
in a gelatin microcapsule delivery system and exposed the microcapsules to an
environment of 50°C for an extended period of time. The microcapsule samples
were measured for weight loss during a two-week period (Figure 29.1). Initially, a
minimal amount of fragrance was released, and it leveled off in two weeks. Even a
very volatile tissue fragrance that contained a 1:1 blend of menthol and eucalyptus
retained greater than 95% of its original fragrance within the microcapsule after
the two-week period.
Figure 29.1.
274
Absorbent substrates such as porous nylon or a cyclodextrin matrix also provided

improved fragrance benefits. In a second study, conducted by researchers at Lipo
Technologies Inc., menthol crystals were complexed into a cyclodextrin matrix
and compared against uncomplexed crystalline menthol in a 50°C oven over one
week. Results showed that the cyclodextrin matrix, while releasing some of the
menthol, was able to retain a portion of the original volatile material compared to
the unprotected menthol (Figure 29.2).
Figure 29.2.
The physical characteristics of the microcapsule shell used to encapsulate

fragrance oils can also play a significant role in the longevity of the consumer per-
ceivable fragrance notes. Investigations into this phenomenon were conducted by
researchers at Dow Corning Corp. using two similar encapsulation technologies,
M1 and M2, with M2 having a more cationic character. Similar menthol fragrance
oils were encapsulated, and these capsules were incorporated into a non-fragranced,
commercial, rinse-cycle fabric softener at a concentration of 2% fragrance. Control
formulations were also prepared using the unencapsulated menthol fragrance oils
for comparison.
Fabric ballasts containing cotton terry cloth washcloths were treated with the
fragranced, commercial, rinse-cycle fabric softener formulation during the normal
rinse cycle and line-dried overnight. Standard US top-loading washers were used
for the treatment of the ballasts. The treated washcloths were subjectively evaluated
by trained panelists for fragrance intensity in a double-blind paired comparison
evaluation. Each panelist took a pair of washcloths—one a control and the other
with the encapsulated fragrance—folded the washcloth in half, applied shear to the
washcloth by rubbing two sides together four times and evaluated the fragrance
concentration. Each panelist compared the respective washcloth with encapsu-
lated fragrance to the control washcloth having free fragrance oil and selected the
washcloth that had greater fragrance intensity (Figure 29.3).
The results of the study show an interesting effect of M2, the more cationic
capsule. Two different sets of ballasts were evaluated (Figure 29.3). The first was
representative of a typical consumer wash, rinse and dry cycle. The second set of
275
ballasts was subjected to two additional wash and rinse cycles without the addition
of the rinse-cycle fabric softener. As Figure 29.3 shows, the ballast treated with
the fabric softener containing the M2 microcapsules showed a statistically different
result compared to the free oil ballast. This outcome demonstrates the possibility
of enhanced fragrance longevity due to the encapsulating shell.
Figure 29.3.
Using the same encapsulation technology, an additional evaluation was conducted

at Dow Corning Corp. to investigate fragrance management in a personal care
formulation. In this evaluation, fragrance oil was encapsulated and incorporated
at 0.5% concentration into a rinse-off hair conditioner formulation. A formulation
containing free fragrance oil was also prepared to serve as the control. Slightly
bleached European hair tresses were washed with a simple shampoo formulation
(Formula 29.1), treated with the rinse-off hair formulation (Formula 29.2) and
rinsed again. After the rinse, the hair tresses were shampooed an additional two times
without a conditioner treatment and left to dry overnight at ambient conditions.
Formula 29.1. Shampoo

% w/w
A. Water (aqua) 58.1
PEG-150 pentaerythrityl tetrastearate (Crothix, Croda Inc.) 1.5
B. Sodium laureth sulfate (Standapol ES-3, Cognis Corp.) 30.0
Cocamidopropyl betaine (Velvatex BK 35, Cognis Corp.) 7.0
Cocamide DEA (Standamid KD, Cognis Corp.) 3.0
C. DMDM hydantoin (Glydant, Lonza) 0.4
D. Citric acid qs
100.0
Procedure: Combine A. Heat to 65ºC, mixing gently until melted. Turn off heat.
Add B to A. Cool to 40ºC. Add C with mixing. Adjust pH to 6–7 with D.
276
Formula 29.2. Rinse-off Conditioner

% w/w
A. Water (aqua) 50.0
B. Hydroxyethyl cellulose (Natrosol 250 HHR, Hercules Inc.) 1.5
Cetrimonium chloride (Araquad 16-19, Akzo Nobel Chemicals, Inc.) 0.3
C. Cetearyl alcohol (Lanette Wax O, Cognis Corp.) 1.0
Glyceryl stearate (and) PEG-100 stearate (Arlacel 165, Uniqema) 1.0
D. Water (aqua) to 100.0
E. Preservative 0.2
Fragrance (parfum) 0.5
100.0
Procedure: Heat A to about 75ºC and add B, mixing until uniform. Using a water
bath, combine C and heat to 60ºC to 70ºC. Heat D to 80ºC. Add D to C while mixing
at high speed for 10 min. Add CD to AB with gentle mixing. Cool to RT with gentle
mixing. Add E.
Trained panelists evaluated pairs of hair tresses, one the control and the other
having the encapsulated fragrance treatment. The tresses were subjectively as-
sessed by combing each tress three times and evaluating the fragrance intensity.
Figure 29.4 compares the number of panelists who selected the encapsulated
sample as having greater fragrance retention to those who selected the control
that contained free oil.
Figure 29.4.
The results of this screening provide additional support to the concept of

achieving a long-lasting effect using an encapsulated fragrance in a formulation.
The initial evaluations of fragrance retention in a rinse-cycle fabric softener and a
rinse-off hair conditioner suggest a range of other potential applications in personal
care, including skin care, sun care and wipe products.
277
Performance Enhancement
Encapsulation also has demonstrated the potential for improving material
physical properties and performance benefits. During the development of a new
personal care ingredient designed to reduce the appearance of skin imperfections,
researchers at Lipo Chemicals Inc. and Lipo Technologies Inc. discovered that
encapsulation provided enhanced material function. The new material consisted of
the reaction of a fluorescent compound with a porous polymer matrix. This reacted
particle is then subsequently encapsulated with a translucent polymer coating. The
fluorescent polymer, incorporated into the polymer substrate, absorbs UV light and
then re-emits this energy in the form of diffuse visible light. This light illuminates
shadowed areas of wrinkles or other skin imperfections reducing their appearance.
Figures 29.5 and 29.6 show scanning electron microscope micrographs of the
absorbent matrix before and after encapsulation.
Figure 29.5.
Figure 29.6.
278
The resultant encapsulated fluorescent polymer improved fluorescent perfor-

mance of the polymer compared to the nonencapsulated material. This distinction
is evidenced by measuring the fluorescence intensity of the light emitted by and
refracted off the particle and comparing the result to nonencapsulated material.
Measurement of this enhanced effect was completed using both a fluorescence
spectrophotometer and UV spectrophotometer. The structure of the particle along
with the translucent coating diffuses the light from the skin surface providing a
soft-focus effect and reduces the appearance of skin imperfections. Figure 29.7
demonstrates the improvement in light intensity for the encapsulated material.
The unique optical effect of the material is due to an interaction of fluorescence,
diffusion and light scattering by the particles. The encapsulation of the particles
provides additional benefits including the protection of the fluorescent material
from formulation ingredients such as polar solvents that could possibly degrade
efficacy, and enhancing the ability to remove the particles from the skin more eas-
ily when needed.
Figure 29.7.
From a research and development perspective, the potential systems that can
be employed to produce a suitable delivery system are extensive. The appropri-
ate system of choice can generally be determined by taking into account several
basic attributes. These characteristics of the final system are the essential basis for
preparing customized encapsulation systems.
Before approaching a microcapsule producer, a formulator should assess the
following factors:
• Physical and chemical characteristics of the material to be encapsulated,
including its sensitivities and incompatibilities.
• The environment in which the microcapsules will be used, including the
nature of the base formulation and whether it will be a wash-off or leave-on
product.
• Restrictions on the origin of materials to be used in the product, including
if they are animal or nonanimal derived.
279
• The form in which the capsules must be supplied. This assessment should
include whether the required form will be dry or slurried, and if slurried,
the type of liquid.
• Requirements for the microcapsule rupture mechanism, including whether the
capsules must be soft or hard, and if sustained release is required.
• The desired capsule size, whether large and visible, or small and invisible.
• Desired color, if any.
Conclusion
Microencapsulation as a delivery system has proved useful in numerous commer-
cial applications in a variety of industries. Practical application of these technologies
can range from taste-masking drugs in pharmaceutical applications to the protec-
tion of two-part adhesive monomers in industrial fasteners. The techniques used
to produce these capsules vary from simple blend operations to complex polymeric
coating systems. The approaches described here provide a brief introduction to
the world of microencapsulation and its potential for high-performance personal
care products. Through the combined skills of creative formulators and innovative
microencapsulation experts, consumers can benefit from next-generation personal
care product forms based on stable systems of cosmetic actives and long-lasting
fragrances.
References
1. Meyer, Age 2000: Census 2000 Brief, US Department of Commerce (2001)
2. Branna, What’s New in Cosmetic R&D, Happi, 44(3) 61–66 (2007)
3. MH Gutcho, Microcapsules and Microencapsulation Techniques, 1, 8–9, 133–135,
Noyes Data Corporations (1976)
Chapter 30
What Every Formulator

Needs to Know about
Fragrance
The purpose of this chapter is to provide an overview and
checklist of the types of problems that one can expect when
fragrancing a variety of products.
key words: fragrance, stability, color compatibility, solubility, PBTs
W hat questions should any product formulator ask of their fragrance supplier?
This question is a bit like the tail wagging the dog. Since the perfumer has an
intimate knowledge of the chemical and physical properties of the materials being
used in fragrance, it would be more productive if the fragrance supplier raised the
following questions to the formulator.
1. What is the end product?

2. What are the components?
a. Are they Hydrophilic?
b. Are they Lipophilic?
3. To whom is this product going to be marketed?
a. How will they use it?
b. What is the targeted age group?
c. What geographic area?
4. How will this product be packaged?
a. Clear bottles? Glass, plastic, (What type?)
b. Opaque?
5. What color will this product be?
6. What are the pricing guidelines?
7. What is the intended percentage of use? (maximum/minimum)
8. Are there stability requirements or protocols?
9. Is the fragrance required to be all natural?
10. Is the fragrance required to be environmentally friendly?
11. What IFRA 42nd Amendment category does the product belong to? (1–11)
These basic questions, when answered correctly, can provide the necessary in-
formation for the development of an appropriate, odor and color stable product.
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282
What Every Formulator Needs to Know about Fragrance Beginning Cosmetic Chemistry
What product are you making?

This deceptively simple question is the key to understanding the type of fragrance
that will be required. It can answer the following hidden questions:
• Who will use it?
• How will it be used?
• How will the product be processed? (Time & Temperature?)
• What are the base ingredients likely to be? (pH?, Acidic?, Basic?)
• How will it be packaged? (Clear or Opaque)
• What will it look like? What color will it be? Single Phase? Clear, Pearlized?
Opaque?
• How long will it remain on the retail shelf and in the hands of the
consumer?
In order to convey effective information, the question must be answered very
specifically, not in a general category. For example, a response such as “Personal
Care Product” will not provide any information that would be sufficiently reveal-
ing or helpful. The type of answer we are seeking is “Clear Shower Gel” or “Con-
ditioning Shampoo.” These “specific” types of answers will provide a different
framework for fragrance selection in both odor and stability performance as well
as base compatibility. Additionally, each answer starts a series of questions down
a different path or branch.
All chemists know that nothing is completely stable. Only a very few things in
the universe are not changing all the time. Seemingly innocuous environments
or simple formulations like fragrance and alcohol start making changes as soon as
they are mixed together.
Aldehydes begin to be transformed to acetals within minutes and their pres-
ence can be analytically identified within hours. A classic example is hydroxy
citronellal.
We have made a solution of hydroxy citronellal and SDA alcohol 39C (a com-
monly used perfume alcohol) in our laboratory and left it in the light and in the
dark (Figure 30.1). We then analyzed the samples by gas chromatography, which
showed that both samples formed the diethyl acetal within one day and continued
at a steady pace throughout the week. The above example clearly indicates that
almost any aldehyde when mixed with ethanol will undergo rapid changes. It should
be an indication that other reactions, known or unknown will be taking place. The
experienced chemist realizes that many more unknown reactions may occur than
known ones. One has to take some time and anticipate, as best as one can, the obvi-
ous problems and be alert to the possibility that other reactions will be taking place.
No substitute exists for testing and keen observation. This process is the only way
to provide assurance that a reasonably stable system has been accomplished.
283
O
O 2C2H5OH O
HO HO
Hydroxy Citronellal Hydroxy Citronellal Diethyl Acetal
Figure 30.1 A solution of hydroxy citronellal and SDA alcohol 39C
Solubility
This issue is something that should be thought of in terms of properties or
overall properties of the base. In a wax or lipstick or petrolatum the base is lipo-
philic so the fragrance has to be completely lipophilic and should contain no glycols
or polar ingredients. In a shower gel that has a preponderance of water, the base
is hydrophilic and the fragrance should be skewed to be as polar as possible and
minimize the use of non-polar types like citrus or wood based fragrances, which
are extremely hydrophobic. The good news is that most cosmetics, shampoos and
lotions can tolerate a wide range of solubility characteristics in this area. Solubility
usually only becomes an issue when the base is extreme like mineral oil, which is
so non polar and, so it is consequently difficult to achieve clarity without testing
and using the minimum amount of almost any fragrance.
Table 30.1
Product Fragrance Color Solubility Stability Comment

Clear Orange/ X X X Oxidizes and is
Shower Gel Citrus Hydrophobic often add
Color
Shampoo Orange X X Oxidizes or affects
Citrus viscosity
Conditioner Citrus X X Adds color, oxidizes
or Fruits or hydrolysis of esters
Lotions & Balsams X X Color changes or some
Creams materials affect
viscosity
Antiperspirant Citrus X X Oxidizes or fruit or
or Fruits hydrolysis of esters
Talc Citrus X X Oxidizes or volatilizes
or Fruits away prematurely
Aerosol Vanilla/ X X X Crystal may form in
Powder actuator & clog orifice
Air VOC California Air Resource
Freshener Limits Board Restrictions
284
Each product will have its own set of problems that must be addressed and
overcome.
In the case of a “Clear Shower Gel”, compatibility with a specific regard to
solubility becomes the initial and primary concern. Often, a fragrance is selected
or requested by the type of odor desired without regard to the system or stability
requirements. A great example would be selecting a fresh lemon or citrus for clear
shower gel. Since all citrus products tend to oxidize and are naturally hydrophobic,
problems will definitely arise with stability as well as solubility. This situation will
leave the cosmetic chemist with the problem of how to solubilize to clarity. The
goal for the fragrance creator should be to prevent this type of problem from the
outset. This forethought will also minimize the occurrence of phase separation or
haziness over a range of temperatures that a product must endure over the manu-
facture, shipping, storage and shelf life.
In many cases a “Clear” product packaged in a “Clear” bottle is the recipe
for difficulty. A clear package allows the consumer to see a product completely
with all the potential pitfalls of change in clarity, color or phase separation. These
changes may be initiated or caused by temperature and/or light, both ultraviolet
as well as sunlight.
The first step is to examine the product. Usually the product is formulated with
a significant amount of water. In general, most fragrance components are lipophilic
(they do not like water at all) and in the best cases are only marginally soluble. They
are usually compatible with oil depending on the fragrance type. Within that general
guideline are degrees of solubility. Terpenes, sesquiterpenes and other aromatic,
cyclic or polycyclic materials are extremely insoluble in any type of water system.
In order to have a clear product that can be easily manufactured, tested through
several freeze/thaw cycles and survive extreme storage conditions without phase
separation can be a significant challenge. These challenges must be overcome.
This situation is where an experienced, knowledgeable perfumer with reasonable
chemistry experience is needed to accomplish this daunting task. It is in the end,
reduced to understanding the physical properties of the fragrance materials as well
as the physical properties of the preponderance of the materials used in the prod-
uct. The objective is the selection of materials with the correct physical-chemical
properties and elimination of the materials with the undesirable properties. The
odor properties must be considered separately and secondarily.
Color Changes: The nemesis of all product marketers is color change. So many
areas of instability occur in this area that many doctoral theses could be written and
in the end the problems would not go away. Color change can come from fragrance
and often does but it is not the only source. Color change can be caused by dye
instability, fragrance/fragrance interaction, fragrance/dye interaction, fragrance/
base interaction, light-induced change as well as base/package and fragrance/pack-
age interaction. I am keenly aware that I have not included all possible sources for
color change. These few are the most common causes. Further, when fragrances
are required to be all natural, color stability and change cannot be guaranteed.
Now is the time to consider any items that are prone to color change due to
UV and or sunlight radiation. (This cause is not the only source or reason for color
285
change but it is a major one.) It can often be mitigated by a UV absorber in the

product as well as in the plastic or glass packaging. Color is one of those issues that
can be quite frustrating. Often the odor change is insignificant but the visual aspect
is what the customer responds to. If it does not look good, it cannot be good.
Other factors that contribute to color change are oxidation, subsequent conden-
sation reactions and fragrance ingredient/fragrance ingredient interactions. These
reactions can be further catalyzed by trace elements of iron or other materials
negatively or positively charged particles that come from water, mixing vessels or
the components themselves. The drums in which fragrances are normally shipped
are double coated with an inert resin; however the threads of the bung openings are
not. An example that occurs frequently is that the fragrance is ordered, shipped to
the customer, who uses a portion of the drum. The material “touches” the unlined
threaded portion of the steel drum. The portion of the material drips back down
into the liquid carrying parts per million of iron from the steel drum and catalyzes
color changes over the next few weeks. The color changes and also may cause a
color drift in the finished product. This cantankerous problem can be somewhat
mollified by either using all the fragrance at one time from a single batch. However,
we know that this procedure is not always practical. Another solution may be to
incorporate a sequestering agent in both the fragrance and the product that will
scavenge any free metallic ion contamination and help maintain color stability. It
is extremely difficult to accurately predict color changes due to the many variables
and sources of contamination in the manufacture of any product.
The “Conditioning Shampoo” requires a different solution to compatibility.
Often the pH is the determining or limiting factor. If the conditioner is very basic
it can cause an equilibrium shift and hydrolyzation of esters.
Additional problems may include discoloration and phase separation, effects
due to viscosity may also be a consideration. The fragrance selected should also be
one that is resistant to large changes due to oxidation. In summary, citrus products,
which are high in unsaturated terpenes and are prone to oxidation under basic
conditions, should used minimally.
Another class of chemicals that are unstable under basic conditions is lactones.
These chemicals tend to open up to the hydroxy acid from which they were origi-
nally made.
This type of change might be a small chemical change, but would create a very
different and negative odor profile.
What is an odor profile?

Before we examine any other products, I will take a moment to explain the
nature of a fragrance.
Many people have heard about top note, middle note and ase note (often
referred to as dry down). This description gives one an overview of the type of
volatility of materials used in fragrance and is somewhat useful but not a very good
representation of reality. A better way to look at fragrance construction is to look
at it from a compositional point of view. An analogy would be to examine a piece
of music. These sections are similar to fragrance.
286
The top note would be analogous to melody, the middle note analogous to the
rhythm section and the base note would be analogous to the bass and drum sec-
tions. One can quickly see that a top, middle and base note analogy does not make
complete sense because we do not listen to music in sections but rather, we hear
all the parts, melody, rhythm and bass/percussion blended together simultaneously.
This correlation is also true of fragrance. It is really the balance and blend of all the
sections that make the fragrance what it is. When one part is adjusted the other
part looms into or out of balance with the remaining sections. This analogy gives a
more accurate portrayal than the top, middle and base note explanation.
Shampoos and liquid detergents can be viewed as similar products in terms
of stability requirements. A neutral pH or slightly alkaline is the norm for these
types of products. Still, one must be aware that oxidation and a slight equilibrium
shift due to alkalinity can compromise the stability of many esters that are normally
used in fragrances. Additional performance loss might be attributed to volatilization
through the packaging. While most shampoos and liquid detergents are fragranced
at 0.2–0.8% range, a loss of top notes or volatiles on the lower use range will be
more dramatic than on the higher ranges. The fragrance should be constructed
accordingly, utilizing more of the mid range notes.
Conditioners and high pH preparations that may contain a quaternary
agent or ammonium hydroxide may exhibit instability when unsaturated terpenes
are used. These items are common in all citrus products. Since citrus is such a
popular theme and often used in a wide variety of products, you might ask how is
this accomplished? A wide variety of citrus like products are at the disposal of the
perfumer. These “surrogate” citrus notes possess a citrus-like character without
the unsaturated terpene content that can be so problematic in functional products.
Alternate choices for citrus fragrances would be deterpinated or terpeneless prod-
ucts that are low in unsaturated molecules and are less prone to oxidation such as
straight chain or branched alcohols that posses a citrus character (Figure 30.2).
O OH
-OH
O HO
O
Epsilon Hexalactone 6 Hydroxy Hexanoic Acid
Figure 30.2 Conditioners and high pH preparations
Lotions & Creams have fewer problems than most of the above formulations.
These products experience little problem with compatibility. Color stability can be
a problem. This issue is the bane of every marketer who wants the consumer to
actually see the product they are purchasing. It can be mitigated by packaging and
the use of antioxidants as well as UV absorbers in the product and the packaging.
Problems of viscosity are generally easily solved but one should always be cognizant
that many fragrance ingredients can alter the viscosity drastically and occasionally
some alternate fragrance types or ingredients must be substituted.
287
Antiperspirants use aluminum chlorohydrate, which produces a very acidic

solution in the presence of trace metals that serve to catalyze a variety of reactions.
This type of medium requires the elimination of unsaturated aldehydes as well as
terpenes.
As can be seen, unsaturated molecules will be oxidized and or catalyzed to
the aldehydes; and subsequently acids that can have quite a negative effect on the
fragrance as well as creating additional reactive chemicals which in turn, can react
with some of the base components.
Any talc or powder formulation presents a different medium for chemical
reactions. The vast surface area of a powder provides an ideal environment for
evaporation, volatile oil loss as well as rapid oxidation. These problems must be
addressed in the earliest phase of fragrance selection. Citrus based fragrances,
which are prone to evaporation as well as oxidation, must practically be eliminated
at the outset. The utilization of deterpinated or terpeneless materials should be
a standard practice as well as using saturated molecules to replace those that are
unsaturated. In general floral or powder oriental blends fare better but an effort
to control color stability must be made.
Aerosol sprays can pose problems of compatibility with the medium used for
delivery. Will the product be hydrocarbon, alcohol or water based (Table 30.2)?
Table 30.2
Base Delivery Material Fragrance Properties

Hydrocarbon Non Polar Ingredients
Alcohol Usually all soluble but limited amount of Terpenes
Water Polar Ingredients and no terpenes or sesquiterpene
hydrocarbons
In addition to compatibility some attention must be paid to the type and amount
of materials that may crystallize in the spray orifice. They may come from naturally
crystalline materials from the fragrance. As volatile materials evaporate the concen-
tration of the crystalline material increases and forms crystals on the surface of the
valve which can eventually block the spray orifice and prevent proper spray. This
process can take place slowly and accumulate over time. Experienced formulators
know not to use too much crystalline material in this type of product.
Environmentally Friendly
Materials that are natural or naturally occurring may be preferable to the cus-
tomer. They are not always better or safer, but are generally thought to be “better”
by the consumer and public. Science does not take the same view. One of the most
potent carcinogens occurs naturally in peanuts, {aflatoxin} and is 100% natural but
not safe. An entire paper could be devoted to this subject and is beyond the scope
288
of this chapter. It is also a “hot button” topic for the promoters and detractors. The
phrase “certified organic” is something that is occuring more frequently. It refers
to the production of natural essential oils, isolates or biochemical transfer products
that do not use pesticides and have been certified by one or more agencies like the
US Department of Agriculture’s organic program.
Having said that, naturals do have a history of safe use and evidence of good
biodegradability exists. I cannot think of a single naturally occurring material
from essential oils or isolates that accumulates in the environment or causes any
ecological problems. It is more often the dosage or huge volume of materials that
present ecological problems. Nature is judicious about the amount of anything that
is biologically manufactured.
Materials of concern are described as persistent bioaccumulative toxic or
PBTs.
Some of these materials are nitro musks like musk xylol, ketone, tibetine as well
as polycyclic musks like indane musks or hexamethyl tetralin musks. As the “green
movement” gains momentum, I believe we will see more requests that address the
concern of the fate of the fragrance chemicals that go into the environment and
the ecosystem. The bulk of the effort has begun by introducing environmentally
friendly laundry detergents and cold water formulations that require less energy.
Even though fragrance is a minor portion, (less than 0.5%) it is logical to anticipate
that the fragrance portion will be viewed as an area for improving biological or
ecosystem friendly materials.
Increased regulation and control of what is being put into the environment on
a world wide basis is something that we can expect for the future.
Scale Up: This area is another one for surprises. Prototype products that are
developed in glassware or ceramic vessels in the laboratory can be markedly differ-
ent from batches prepared in a manufacturing plant environment. Stainless steel
is not an inert mixing vessel. Often times temperatures that are easily controlled
in the laboratory are impossible to regulate in a manufacturing plant. Another
variable is personnel and their training, education and ability to recognize where
a seemingly insignificant change in procedure may affect subsequent stability. An
example might be the simple change in the order of addition.
Example I.
Water 90%, Surfactant 5%, Fragrance 5% Add to tank & Mix.
If these materials are added in this order, two things happen, the fragrance will
not be evenly dispersed, in the water and the batch will foam considerably making
mixing a problem.
Example II.
Step 1. Add Water to Tank First.
Step 2. In separate vessel thoroughly mix Surfactant 5% mixed with
Fragrance 5%
Step 3. Add Surfactant / Fragrance mix to Water in Tank.
289
Example II solves many problems by having the fragrance completely envel-

oped by the surfactant, allowing proper micelle formation. This step also minimizes
foaming during mixing.
Keep in mind that order of addition and procedures can be very important for
ease of manufacture. This type of thinking can alleviate many problems.
Unpredictability!
Despite everyone’s best efforts elements of unpredictability are always with
us. We are trying to predict what will happen when we mix several hundred in-
gredients with the variables of time, temperature, light energy exposure as well
as shipping, storage and use conditions. These reactions occur at extremely low
levels often catalyzed by trace elements. It is not uncommon to go through testing
and refinement and then nearly at the 11th hour a small seemingly insignificant
base change is made. It can be as simple as a supplier change with no apparent
difference in quality.

290
INITIAL CHECK LIST Summary
What is the Specific Product? _________________________________________
Is the product Hydrophilic? __________ or Lipophilic? __________ Y/N
Is there ANY water in the product? _____ Y/N How much? _____ % by Weight
What is pH of product _________

(Note: Products without water will not have a true pH)
Is packaging clear _____ or opaque? Y/N Will the product be colored? ______
What material will the package be?
Plastic? ____________ Glass? ____________ Other? ______________________
What percent by weight of fragrance is intended to be used? ________________
Are there any VOC (volatile organic chemical) restrictions? _________________
What are the stability parameters and requirement or protocols required by the
customer? ________________________________________________________
__________________________________________________________________
Are there any price guidelines? Cost at use level?_______________________
Who will use the product? ____________________________________________
Are any materials restricted by the customer? ____________________________

Phthalates, polycyclic musks?
Are there any performance guidelines? _________________________________
What IFRA 42nd Amendment Category does the product belong? (1–11)
__________________________________________________________________
Chapter 31
Fragrance in Emulsion and

Surfactant Systems
Fragrance is a complex system of aroma chemicals whose
potential to interact with the base in formulated products is
reviewed in this chapter, with a focus on fragrance in emulsion
systems and surfactant systems.
key words: fragrance, formulation, emulsions, surfactants, solubility

parameter, water/octanol partition coefficient, phase diagrams
M uch has been written on fragrance chemistry and applications, but many
formulators remain unaware of the detailed mechanisms by which aroma
chemicals interact with bases. With the daunting complexity of fragrances, no text
will resolve all the situations that are encountered. Nevertheless, an understanding
of the underlying chemistry can notably enhance the probability of success.
Fragrance is used in most personal care products. Sometimes, its purpose is
simply to mask an undesirable base odor; more often it is a key sensory attribute.
For some products, such as shampoo and body wash, fragrance may be the most
important element in consumer appeal.
Formulators usually view fragrance as a single ingredient, a liquid in an amber
bottle, often added at the end of the development process with little regard for
its properties. The marketing department treats fragrance by its odor description,
demographic appeal and cost. In reality, fragrance often is the most chemically
complicated component of the formulation, and understanding its technical aspects
is essential for the creation of an acceptable product.
Fragrance Materials
In constructing a fragrance, volatility is a key factor. The materials that are most
volatile, and last the shortest time during use, are called top notes. Materials of
intermediate volatility comprise the middle notes. The least volatile, longest-lasting
components make the bottom notes. A pleasing blend of a few materials is called
an accord. A fragrance, in its most basic form, can be constructed from a bottom
accord, a middle accord and a top accord. More than 40 years ago, Jean Carles1
provided a classic summary of fragrance construction that is still valid. (See Sidebar
31.1. The Creation of a Fragrance)
291
292
Fragrance in Emulsion and Surfactant Systems Beginning Cosmetic Chemistry
Sidebar 31.1. The Creation of a Fragrance

The classic tale of accidental perfume creation concerned the earliest
successful fragrance, Eau de Cologne. Allegedly, a perfumer in Cologne
fell down some stairs while carrying a tray of various flower extracts. The
resultant mixture seemed not only pleasant, but noticeably stronger than
any of the individual ingredients. The effect of the whole being found to be
greater than the parts, modern perfumery was born.54
Many fragrances are created first as hydro-alcoholics, for which the term perfume
usually is used. If the fragrance is successful, line extensions are made into skin,
hair and bath products. The materials that can be employed—and the balancing
of the components—must be modified for aesthetic, economic and technical con-
siderations.2 It is easy to understand the economics. While functional fragrances
frequently derive from fine fragrances, the fine fragrances have much higher price
points. Expensive nuances in the fragrance usually will not be used in personal
care. The aesthetic and technical aspects of translating fragrance into successful
applications will occupy the remainder of this chapter.
Perfumers, even if they are blissfully unaware of chemistry, learn to solve many
common problems through training and experience. When modifying fragrance for
a specific base, some materials must be removed because of their negative impact
on stability. Materials must be added to the fragrance or subtracted from it to com-
pensate for the physical or olfactory qualities of the base. Raw material studies can
identify problematic ingredients. Databases give the stability of aroma chemicals over
a wide pH range or in common applications. Compendiums from aroma chemical
suppliers frequently include indications of appropriate applications.
Although it is possible to solve problems without a theoretical foundation, the
curious formulator will still desire a deeper understanding of why fragrances behave
as they do. Fragrances embrace a widely diverse range of chemical types. Some
characteristic examples of those types are shown in Figure 31.1. Aroma chemicals
often contain more than one functional group, and they each contribute to the
properties of the material. The literature includes numerous books3–8 that treat the
chemistry, synthesis and properties of aroma chemicals in detail.
Fragrance in Emulsion Systems

Since the 1940s, application chemists have studied the effects of fragrances in
emulsion systems.9–11 With emulsions, the obvious consequences of undesirable fra-
grance interactions were the thinning and breaking of emulsions, and discoloration.
Odor changes taking place over time include the loss of strength and character,
and the development of sour or rancid notes. An acidic note also may be detected.
Surfactant systems experienced viscosity changes, solubility issues in clear systems,
color changes and interactions with certified colors. Exposure to heat and UV light
often exaggerated these problems.
293
Figure 31.1.
294
Early investigators published many specific examples of the interaction of

aroma chemicals with cosmetic bases. Pickthall12 noticed the destabilizing effects
of fragrance materials such as alcohols, phenols, acids and some esters. Hydroxy-
citronellal and α-terpineol are two prominent examples. Hydroxycitronellal contains
two polar groups: hydroxyl and aldehydic. Its polarity enables it to compete for
space on the surface of the micelle, leading to either a decrease in viscosity or a
breaking of the emulsion. The α-terpineol has one hydroxyl group on a relatively
rigid molecule, less disruptive than hydroxycitronellal but still capable of destroying
the balance of the emulsion. It also is possible for perfume ingredients to produce
closer packing of the hydrophobes on the micelle surface, in which case emulsion
stability will improve.
Karas13 studied TEA-stearate lotions. He observed immediate separation with
phenylethyl alcohol and hydroxycitronellal, breaking after five days with linalool,
amylcinnamic aldehyde, terpineol and methyl ionone. Methyl anthranilate showed
discoloration and slight creaming.
Wellenkamp14 used acetals rather than the corresponding aldehydes to aid
emulsion stability. He considered the acetals of phenyl acetaldehyde, phenyl pro-
pylaldehyde, cyclamen aldehyde, amyl cinnamic aldehyde, hydroxycitronellal and
hydratropic aldehyde. The acetals were found to be longer-lasting, less harsh and
more delicate than the aldehydes. Significantly, the acetals did not discolor soaps
and creams.
In a 1980 paper,15 Bonadeo proposed Kd to explain the effect of fragrance on
emulsions. The Kd is the water/dioxane partition coefficient. The aromatic material
is considered part of the oil phase, and an HLBr is assigned, corresponding to the
required HLB commonly used as a guide for nonionic emulsification. Bonadeo
proposed one additional concept: the critical limit of the water phase (CLWP),
which quantifies the water that can be tolerated by the emulsifier system.
Bonadeo concluded that the olfactory properties of a fragrance in a w/o or
o/w emulsion are the same if the system is properly balanced; otherwise, a mixed
system is formed, upsetting the fragrance distribution. He firmly places the fra-
grance in the oil phase, becoming a determinant in calculating the total HLB, and
he concluded that the CLWP of each perfume component contributes to the limit
of water that can be tolerated.
A useful method for adjusting the perfume to compensate for the effect of the
substrate was presented by Saunders.16 The smell of a fragrance out of a bottle is
different from the smell after it is applied to a substrate or put in a base. What is
being smelled corresponds to the headspace composition. Saunders compared the
headspace proportion of each component out of the bottle and in the air over the
base, deriving a ratio for each material for use as a correction factor. The perfumer’s
formula then is adjusted by these correction factors, resulting in a new formula. The
new formula’s headspace analysis in the base should be the same as the headspace
of the neat oil made from the original formula. This is illustrated in Table 31.1.
295
Table 31.1. Analysis of headspace composition when a fragrance mixture is

placed in a base (From Reference 16)
a b c d e
Headspace
Headspace over Original Adjusted
Fragrance of fragranced fragrance fragrance
component fragrance base a/b formula formula
Limonene 31.9 15.9 2.0 2.0 4.0
Linalool 13.2 12.9 1.0 2.0 2.0
Linalyl acetate 12.3 7.7 1.6 2.0 3.3
PEA 6.2 22.6 0.3 3.5 1.1
Benzyl acetate 11.6 18.7 0.6 2.1 1.3
Polarity
It is clear that, with the obvious exception of the interaction of functional groups,
the key to understanding the behavior of aroma chemicals in diverse media is polarity.
The simplest division of materials is into two groups, polar or nonpolar, but either
solubility parameters (SP) or the water/octanol partition coefficient (P) is much
more informative. P usually is expressed as its calculated logarithm, clogP.
Solubility parameters: Vaughan has covered the personal care applications of
SP in a valuable series of articles.17–21 The SP is a measure of all the cohesive forces in
a molecule. Its consequence can easily be seen in the size of a drop. Using a uniform
pipette, the weight of a drop of water, mineral oil or ethyl alcohol will be different,
and the difference can be correlated directly to the SP of the materials.
In a simplified way, where aroma chemicals might partition in an emulsion system
can be seen using the solubility parameter. Table 31.2 shows the solubility param-
eter of selected fragrance materials and some common emulsion ingredients.
The most common type of emulsion is o/w, with anionic or nonionic emulsifiers.
The emulsion has an oil phase of small droplets covered by emulsifier molecules,
an external phase and liquid crystal structures. These different phases must be kept
in mind when examining the fate of fragrance in the system.
A simplified view of the location of aroma
chemicals in an emulsion is shown in Figure 31.2.
Once the fragrance mixes into the emulsion, the
individual components of the fragrance partition
in varying degrees into the different structures of
the product. Pinene, with an SP under 9 and no
oxygen groups, will migrate into the internal oil
phase. Hydroxycitronellal, with its surface activity,
can concentrate on the micelle surface; there it
can displace some emulsifier, lower the viscosity Figure 31.2.
or break the emulsion. Phenylethyl alcohol and
296
vanillin, with SP greater than 11, can have substantial presence in the external
aqueous phase. The amyl alcohol, with a fatty chain and hydroxyl group, can parti-
tion into the liquid crystal structure. The partitioning takes time, accounting for
the aging necessary before one can accurately evaluate the effect of the base on
the fragrance’s olfactory performance.
Table 31.2. Solubility parameters (SP) of selected fragrance materials and

some common emulsion ingredients
Ingredient SP
White mineral oil 7.09
Stearic acid 7.75
-Pinene 8.03
Amyl acetate 8.44
Citronellal 8.83
Stearyl alcohol 8.90
Citral 9.34
Linalool 9.62
Amyl alcohol 10.84
Benzaldehyde 11.00
Eugenol 11.12
Dipropylene glycol 11.78
Phenylethyl alcohol 11.79
Benzyl alcohol 12.31
Vanillin 12.34
Propylene glycol 14.00
Water 23.40
Water/octanol partition coefficient: The water/octanol partition coefficient

was conceived as a wet chemistry process, but the “calculated” coefficient in clogP
refers to the fact that it now is more commonly determined by an algorithm of
functional groups in a computer program. Because most chemical structures can-
not be typed on a keyboard for computer entry, they first must be converted using
programs such as the Simplified Molecular Input Line Entry System (SMILES).
In SMILES, case is important: aliphatic regions are upper case and aromatics are
lower case. Hydrogen is not notated. Logically enough, a single bond is C-C and a
double bond is C=C, but a triple bond requires special treatment, and is C#C. Rings
are denoted by a number at the start and end: c1ccccc1Br is bromobenzene.
A more recent tool is the Graphical Input of SMILES, or GRINS. It allows
some ring structure to be inserted in a process similar to using a chemical drawing
program. Figure 31.3 shows the SMILES notation and Table 31.3 shows a detailed
analysis of the clogP for vanillin acquired from a Web-based calculator.22
297
Table 31.3. ClogP analysis for vanillin, calculated at

www.daylight.com/daycgi/clogp
Class Type Log P Value

Fragment #1 Ether –0.610
Fragment #2 Aldehyde –0.420
Fragment #3 Alcohol or hydroxy –0.440
Carbon 1 aliphatic isolating carbon 0.195
Carbon 6 aromatic isolating carbons 0.780
ExFragment Hydrog 6 hydrogens on isolating carbons 1.362
ExFragment Bonds 1 chain and 0 alicyclic (net) –0.120
Electronic SigRho 4 potential interactions; 1.95 used 0.787
Ortho Ring 1 1 normal ortho interaction –0.250
Result 4/22+ All fragments measured 1.284
The clogP of fragrances preferred

in specific applications are specified in
many patents. A notable example is the
Procter & Gamble patent23 protecting the
Febrezea cleaners. Although the inventors
claim cyclodextrin as the principal odor
control agent, they devote more space
to specifying the preferred fragrance
composition. The ideal fragrance will
consist of a preponderance of hydrophilic
Figure 31.3.
materials, especially those with clogP of 3
or less. These aroma chemicals are most
compatible with aqueous systems.
Fragrance in Surfactant Systems

The study of fragrance in surfactant systems has a long history. Munden24 pub-
lished a study on the effect of fragrances on viscosity. He used a perfume consisting
mainly of phenylethyl alcohol, lillial, citronellol, hexylcinnamic aldehyde, methyl
dihydrojasmonate and methyl cedryl ketone. The surfactant system consisted of
10% sodium lauryl ether sulfate, some minor additives and sodium chloride to adjust
viscosity. It was noted that fragrances usually decrease viscosity, but occasionally
increase it. Blakeway’s25 study concluded that the odor of a solubilized perfume
in the aqueous phase, not the fraction contained in the micelle, determined the
odor impact. The greater the number of micelles, the less the odor intensity, and at
higher surfactant concentrations the micelles must burst, releasing aroma chemicals
into the solution.
298
Behan and Perring26 used headspace analysis to examine the vapor phase con-
centration over a shampoo system. Sodium dodecyl sulfate (SDS) was used at a
range of 5–20%, but with 10% as the standard level. Aroma chemicals from 0.5–3%
were used, with 1% the standard. The aroma chemicals studied were octan-2-one,
benzyl acetate, anethole, limonene and heptan-1-ol. Several solvents/solubilizers
also were considered. It was found that the solvent could profoundly influence the
headspace composition of the volatile components. The perfume partitions in the
SDS/water system, and increasing the surfactant concentration reduces the quantity
of aroma chemicals in the headspace.
It is known that different perfume components could concentrate in differ-
ent areas of the micelle. Additionally, some polar materials can be present in the
external phase. Materials with some water solubility, such as phenylethyl alcohol
or vanillin, become less soluble if the polarity of the external phase is increased by
the addition of salt. Systems that overly rely on salt to build viscosity may be hard
to fragrance for two reasons: the low level of surfactant and the excessive polarity
of the external phase.
The partitioning of aroma chemicals
in a surfactant system is shown in Figure
31.4. Some materials will migrate into the
core of the micelle, some will align in the
hydrophobic tails, some will be near the
micelle surface and a small amount will
be in the external aqueous phase. The
viscosity is determined by the number, size
and geometry of the micelles, in addition
to any thickening that has been created in
the external phase. The fragrance materials
can change any of these parameters, and
make the viscosity increase or decrease. Figure 31.4.
The viscosity changes can be extreme and
difficult to correct.
Knowledge of the structure of bases and the chemical nature of aroma chemi-
cals allows intelligent conclusions to be drawn concerning the fate of fragrance
materials in finished products, but it is not conclusive scientific proof. Research
by a number of workers under the general guidance of Friberg27–42 confirmed the
nature of the interaction of fragrance chemicals with larger environments with the
a priori observations of many formulators
It is impossible to examine every aspect of complex systems in a thorough
way: the sheer number of variables make the calculations impractical. Three- or
four-component systems of clearly defined composition must be used to provide
manageable data. The methods used by Friberg involve titration combined with
visual and polarized microscopic examination, and low angle X-ray diffraction. The
X-ray diffraction measures the spacing of liquid crystal structures (Figure 31.5).
The titrations yield phase diagrams that map the different structures present in
the mixtures.
299
Figure 31.5. Figure 31.6.
Changing the initial blend a number of times allows a complete analysis of the
system (Figure 31.6). The line from A to B has no water content. Point A is 100%
oil; B is 75% oil, 25% surfactant; C is 50% oil, 50% surfactant; D is 25% oil, 75%
surfactant; and E is 100% surfactant. Water is titrated into the system, providing
data along the lines AG, BG, CG, DG, EG, where the point G is 100% water.
To add a fourth vari-
able, a blend of two in-
gredients is fixed and the
titration performed as in
the three-phase system.
Figure 31.7 has a 50:50
mixture of geraniol and
olive oil in a system with
steareth-10 and water.
Areas of lamellar liquid
crystals and microemul-
sions are formed.
The microemulsion Figure 31.7.
regions occur where the
mixture becomes clear.
Liquid crystals can be observed by a cross pattern in the micelles viewed in a polar-
izing microscope. The spacing between lamellar liquid crystals can be measured
by low-angle X-ray diffraction, revealing quantitatively the impact of the fragrance
molecules on the geometry of the system.
The cumulative work of Friberg’s group showed conclusively that different
fragrance molecules occupy different areas in the surfactant or emulsion system,
which certainly will affect the viscosity and stability of the system. The location
of the fragrance in the surfactant structures and the interaction of the surfactant
with the fragrance materials will affect the vapor pressure of the aroma chemicals
in the base. Thus the odor impact will be affected also.
300
Summary
This chapter has only considered a few aspects of the importance of fragrance
chemistry in personal care. Interactions with packaging; safety and regulatory is-
sues; color interactions; problems at extreme pHs; incompatibilities with active
ingredients mean that the subject is endless. Some additional articles43–50 and Web
sites51–53 are included in the references to help guide interested readers, but many
more exist.
The challenge to perfumers and application chemists arises from the complexity
of fragrance chemistry, the varied interactions of aroma chemicals with the envi-
ronment of emulsion and surfactant systems, and the added influence of external
factors such as heat and light. Practical experience helps as a guide, and the brute
force approach of raw material studies can produce effective fragranced products.
True understanding comes with the realization that fragrances are chemicals, that
bases create an environment of varied character, and that the core of fragrance
chemistry is chemistry.
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Chichester, UK: (1975)
4. RR Calkin and JS Jellinek, Perfumery: Practice and Principles, Wiley Interscience,
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16. HC Saunders, An approach to fitting a perfume to the polarity of its substrate, Cosmet
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17. CD Vaughan, Using solubility parameters in cosmetic formulation, J Soc Cos Chem
16(5) 319–333 (1985)
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22. www.daylight.com/daycgi/clogp
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103(11) 65 (1988)
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solutions, Int J Cosmet Sci 9 261–268 (1987)
27. SE Friberg et al, “The location of vanillin in a food emulsion system.” In SL Holt, ed,
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Washington, DC: (1982)
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dodecylsulfate and pentanol, Soap Cosmet Chem Spec 32–40 (Aug 1994)
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polyoxyethylene-4 lauryl ether (Brij30), Progr Colloid Polym Sci 101 18–22 (1996)
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43–56 (1996)
31. SE Friberg et al, Vapour pressure of a fragrance ingredient during evaporation in a
simple emulsion, Int J Cosmet Sci 19(6) 259 (1997)
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microemulsion formulations, Int J Cosmet Sci 19 75–86 (1997)
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polyoxyethylene-4 lauryl ether, J Molecular Liquids 72 31–53 (1997)
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solution, Colloids Surf A 127 233–239 (1997)
35. SA Vona Jr et al, Location of fragrance molecules within lamellar liquid crystals,
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Polym Sci 109 93–100 (1998)
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water and laureth 4, Int J Cosmet Sci 20(6) 355 (1998)
38. SE Friberg, Fragrance compounds and amphiphilic association structures, Adv
Colloid Interface Sci 75 181–214 (1998)
39. SE Friberg et al, Stability factors and vapor pressures in a model fragrance emulsion
system, J Cosmet Sci 50 203–219 (1999)
40. SE Friberg et al, Vapor pressures and amphiphilic association structures, Colloids &
Surfaces 159 17–30 (1999)
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systems, Int J Cosmet Sci 22(2) 105–119 (2000)
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(2000)
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44. SJ Herman, Fragrance chemistry, Chem Tech (Aug 1992)
45. SJ Herman, Fragrancing emulsions, Cosmet Toil 109(8) 71–75 (1994)
46. A Baydar et al, Behavior of fragrance on skin, Cosmet Toil 111(2) 49–57 (1996)
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47. R Schueller and P Romanowski, Common “scents”: Fragrance in personal care

products, Cosmet Toil 111(2) 59–66 (1996)
48. BD Mookherjee et al, A novel technology to study the emission of fragrance from the
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Cosmet Toil 118(6) 47–63 (2003)
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53. www.leffingwell.com (Accessed Feb 8, 2006)
Chapter 32
Fundamentals of
Formulating Hair Care
Products
An overview of formulating a variety of hair care products, the
chemistry behind them and why they are effective.
key words: relaxers, hair dyes, shampoo, conditioner, substantive,

surfactants
F ormulating hair care products requires a combination of science and art. The
science involves treating the physical needs of consumers’ hair; the art is in
giving consumers products that are pleasing to use and enhance their appearance
and, therefore, their self-esteem. Cosmetic scientists must keep these goals in mind
when formulating hair care products.
How products enhance hair: Hair care products physically enhance hair in
four basic ways. First, these products cleanse hair and leave it looking and feeling
better. Second, conditioning products overcome damage that has been done to the
surface of hair and enhance its feel and appearance. Third, styling products are
designed to enhance the configuration of hair and give the consumer better control
over their appearance. Finally, reactive products, those that chemically interact
with hair’s structure, can change both the color and the physical shape of the hair.
This chapter discusses some of the fundamental considerations of formulating
these hair care products.
Cleansing Products—Shampoos
Hair becomes soiled through a variety of mechanisms including natural secretion
of sebum (from oil glands beneath the scalp), sweat (and the salt it produces), styl-
ing residue (from hair sprays and other hair holding products), and environmental
pollution (such as dirt and dust). Shampoos are specially designed to remove all
of these materials. But they must do so without stripping hair of the natural oils
that give it sheen and manageability. Therefore, shampoos are formulated with
detergents (also known as surfactants) and other materials that are relatively mild
to biological surfaces.
303
304
Fundamentals of Formulating Hair Care Products Beginning Cosmetic Chemistry
Surfactants
Surfactants are a class of chemicals used in shampoos to cleanse hair. They are
compounds which are both hydrophilic (“water loving”) and lipophilic (“oil lov-
ing”). The water soluble portion of the molecule is typically a polar group which
ionizes in solution to yield charged species. Water solubility may also be imported
through the polar moieties such as hydroxyl groups (OH-) which can hydrogen
bond with water to increase the solubility of the molecule. The oil soluble part of
the molecule is typically a long chain hydrocarbon, which can be either branched
or straight chain. According to the chemical principle of “like dissolves like,” the
lipophilic portion associates itself with oily materials, while the polar portion of the
molecule is attracted to water. The surfactants reduce the surface tension of the
solution, thus allowing them to disperse oil in water. In addition, these surfactants
create foam, which is a signal to the consumer that the product is working.
Choosing surfactants: The surfactants used in shampoo formulations are
selected on the basis of their cleansing and foaming properties. The primary types
include anionics, nonionics and amphoterics. The most commonly used anionics are
alkyl sulfates that are made up of long chain hydrocarbon backbone with a sulfate
group on one end. Examples include ammonium and sodium lauryl sulfates. A variety
of related surfactants can be created by altering the nature of the polar head group
and the carbon chain. For example, alkyl ether sulfates, alkyl phosphates, dialkyl
sulfosuccinates and alkanolamide sulfates are all examples of anionics.
Amphoteric surfactants such as beta aminopropionates (e.g., sodium laurimino-
dipropionate) are good detergents as well. Amphoterics are zwitterionic meaning
that they acquire a positive charge in acidic environments and a negative charge
in alkaline solutions. These materials are generally less irritating than anionics but
they also provide less foam. They are commonly used in mild formulations such
as baby shampoos.
Nonionic surfactants have no net charge and are good degreasing agents but
they provide little foam. They are frequently used to solubilize fragrances and other
oily materials. Examples include polysorbate compounds and fatty alcohol ethers
such as PPG-10 cetyl ether.
Conditioning Agents
Besides surfactants, shampoos also contain conditioning ingredients that smooth
the cuticle and improve the hair surface. These ingredients, which include silicones,
polymers, and other emollients, are discussed in detail in the next section.
Other Ingredients
In addition to surfactants and conditioning ingredients, other ingredients used
in shampoo formulations include thickeners, viscosity modifiers, preservatives,
colorants, and fragrances. It is the job of the formulator to combine these ingredi-
ents in the proper ratios to produce a product that will cleanse the hair and leave
it with a pleasant feel.
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Improving the Condition of Hair: Rinse-out and Leave-in Conditioners

Hair can be damaged in a variety of processes. Chemical processes such as
coloring and permanent waving can weaken the hair’s structure and render it
more susceptible to breakage. Even simple combing and brushing can disturb
the surface of hair. These effects make hair weaker, causing it to appear dull and
lifeless. Conditioners are used to combat the effects of this damage by improving
the surface characteristics of hair. This improvement may be achieved through a
variety of mechanisms, and therefore through a variety of chemical ingredients.
Two primary types of conditioners are available: rinse-off and leave-on. Both types
of conditioners employ a variety of different types of ingredients including cationic
surfactants, polymers, emollients, and humectants.
Cationic Surfactants
Cationic hair care ingredients are important for two reasons. First, since they
have a positive charge, they tend to be more substantive to hair, which has a net
negative charge. In other words, they tend to remain on the hair through the rins-
ing process. For this reason, cationics are important in rinse-out formulations.
Furthermore, the charge on the molecule lets it dissipate static charge and keep
hair from becoming flyaway. Cationics are most commonly found in the form of
fatty quaternary ammonium compounds, or quats, and cationic polymers. Cationic
surfactants, in the form of quaternary ammonium salts, or quats, are widely used
to condition hair. Quats can be thought of as ammonium salts with the hydrogen
molecules replaced by alkyl groups. At least one group is a hydrophobic molecule
with a long hydrocarbon chain (typically 12–22 carbons). Methyl groups can oc-
cupy the remaining sites. The anion is usually chloride, but it can also be bromide
or methyl sulfate.
Improving hair manageability: A quat’s ability to condition comes from the
hydrophobic nature of the long hydrocarbon tail and the cationic charge of the polar
head group. In aqueous cosmetic formulations, quats dissociate into their ionic
components. The cation attached to the hydrocarbon chain is attracted to anionic
charges present in hair’s protein structures. This electrostatic interaction, coupled
with the fatty nature of a molecule’s hydrocarbon portion, inhibits rinse-off.
With the fatty portion of the quat deposited on the surface, many benefits become
apparent. The hair cuticle is smoothed, resulting in a more lubricious, softer feel
with easier combing ability. Also, quat conductivity reduces static electrical build
up. This reaction reduces flyaway and improves manageability.
Quat drawbacks: Potentials for formulation compatibility problems and irrita-
tion are some drawbacks of quats. For example, combining cleansing and condi-
tioning systems in products such as 2-in-1 shampoos can lead to stability problems
because quats and anionic surfactants may be incompatible. Another drawback is
the relatively high potential for skin and eye irritation.
A wide variety of quats exist, including ethoxylated and mono-, di- and tri-
substituted forms. If the degree of substitution increases, more fatty material is
deposited, and quats normally will exhibit better conditioning. However, this increase
306
also reduces the material’s water solubility, making formulation more difficult. In
a process known as “ethoxylation,” formulators can overcome this insolubility by
increasing the number of molecular hydrophilic groups. The drawback, in this case,
is that a higher water solubility reduces quat substantivity.
Cationic Polymers
Cationic polymers are another type of substantive raw material commonly used
in hair-conditioning formulations. They are made by attaching quaternized fatty
alkyl groups to modified natural or synthetic polymers. While structurally similar to
quats, they have many more cationic sites per molecule and much higher molecular
weights. Cationic polymers must be substantive to effectively condition. As with
quats, a polymer’s cationic nature allows substantivity via coulombic attraction to
anionic surfaces. Cationic polymers are also used in anionic surfactant-containing
formulas, such as shampoos, where they are solubilized and expected to wash
away during use. However, that does not happen because of a unique solubility
mechanism.
Anionic surfactant systems containing cationic polymers can be designed so
that polymers are soluble in the product but become insoluble during rinsing and
depositing on the hair. This result occurs because of an association between the
cationic polymer and the anionic surfactant in cosmetic formulations like sham-
poos. With excess surfactant, the polymer is solubilized, creating a clear solution.
However, during rinsing, the surfactant concentration falls below the critical level
required for solubilization, and the polymer/surfactant complex deposits on the hair.
Once deposited, cationic polymers provide hair with slip, manageability, and good
combability. They increase body in damaged hair, have good spreading properties,
and can improve split ends. Their relatively high activity allows low-use levels.
Emollients
Emollients are materials that provide lubricity and slickness to the hair. These
materials include long-chain hydrocarbon esters, silicones, and other oily materials.
Silicones, specifically dimethicone, are highly effective in smoothing hair. These
materials work by forming thin, uniform films on the surface of hair. A siloxane
backbone makes dimethicone very hydrophobic and capable of waterproofing the
hair to protect it from environmental damage.
Humectants
Humectants are a class of conditioning agents that work by an entirely different
mechanism. They are “hygroscopic,” meaning they absorb water from the environ-
ment and promote water retention. This mechanism is helpful in controlling certain
physical properties of hair, such as brittleness. A variety of humectants are common
throughout the industry in both hair and skin care products.
Most humectants are “polyols,” meaning they contain multiple hydroxyl groups
that attract and bind water. Glycerin and sorbitol are two common examples often
used in hair care products to help retain moisture in the hair and to prevent the
307
product from drying out. Polyols are typically used at relatively low concentrations
ranging from 1–5%.
Emulsifiers
Since many of the fatty materials used to condition the hair are not very water
soluble, other types of surfactants, known as emulsifiers must be used to allow
the water and oil soluble ingredients to form a homogeneous mixture. Common
emulsifiers include fatty alcohols such as cetyl and stearyl alcohol, and ethoxylated
chemicals such as steareth-21.
Other Ingredients
Other ingredients used in conditioners include auxiliary emulsifiers, thickeners,
preservatives, colorants, fragrances and preservatives as described above.
Styling Products—Gels, Hair Sprays and Mousses

The cleansing and conditioning processes naturally leave hair in a disheveled
state. Since this condition is generally considered unfashionable, people modify
their appearance by using styling tools like combs, brushes and blow dryers. This
process is aided by the use of styling products like hair sprays, mousses and gels
that can hold hair in place. The primary compounds that allow people to achieve
the styles they desire are setting polymers.
Styling Polymers
While polymers are used for various reasons in cosmetic formulations, perhaps
the most extensive is in hair styling products like hair sprays, gels and mousses.
These products use polymers to make the hair sufficiently rigid so it stays in place
throughout the day. Typically, styling polymers are referred to as resins because
the first materials used for this purpose were natural resins, such as shellac. The
key property of polymers that make them useful in styling hair is their tendency to
form films when they dry. After a styling product is applied to hair, the individual
hair strands are coated with the polymer. As it dries, an invisible film is formed,
which bonds hair strands together at points of contact.
The ideal styling resin: For a polymer to make a good styling resin, it should
have certain characteristics. The ideal styling resin would have the following char-
acteristics. It creates a substantive film on the hair that can be easily washed out.
The film holds hair, but is flexible enough to allow some movement without break-
ing. It is transparent so it does not reduce the hair’s natural gloss. It does not flake
when it is brushed out. Finally, it does not absorb moisture from the atmosphere
and become sticky.
Two of the polymer’s properties, namely molecular weight and glass transition
temperature, have a significant impact on its performance as a styling resin. In
general, the higher the molecular weight of a resin, the greater the holding power.
However, a higher molecular weight can result in higher viscosity that can nega-
tively affect the spray pattern of the hair spray. The glass transition temperature
308
(Tg) also affects how a polymer behaves on hair. Above the Tg, the film is flexible.
Below this temperature, the film is harder and more brittle. These factors must be
considered when using a styling polymer.
Shellac and PVP: The first hair sprays used shellac—a resinous material
derived from insects. Unfortunately, while this material held the hair in place, it
produced a water insoluble film when it hardened that was difficult to wash out.
This problem was overcome by the incorporation of synthetic polymers into hair
styling products. Initially, polyvinylpyrrolidone (PVP) was used. PVP is produced by
the polymerization reaction of 1-vinyl-2-pyrrolidone. It is a water soluble material
that is substantive to hair and produces a clear, flexible film. This development was
a significant improvement over shellac but it did have its problems. PVP’s primary
disadvantage is that it is hygroscopic which means it tends to absorb moisture
from the air and makes hair sticky. This problem led to the development of the
copolymer resins.
Many different copolymer resins are now available for use in styling products.
Polyvinylpyrrolidone vinyl acetate (PVP-VA) copolymers provide a clear film with
good hair holding abilities. The incorporation of the vinyl acetate makes the material
less susceptible to atmospheric moisture. However, this addition also makes it harder
to remove through shampooing, so the proper ratio must be found. Carboxylated
resins such as vinyl acetate\crotonic acid copolymer are said to provide the excellent
flexibility in formulating. Because they yield a film whose characteristics such as
hardness, solubility, and moisture susceptibility, they are controlled by the degree
of neutralization of the free carboxylic acid groups.
Solvents
In addition to the styling polymer, a solvent is used in styling products. Perhaps
the most common solvent is ethanol. It is particularly effective in hair sprays because
of its high compatibility with many propellants and styling polymers. Water is also
used as a solvent because it has a low cost and does not add to the volatile organic
compound (VOC) content of the product. With the advent of current regulations
about VOCs a significant amount of work is going on to develop new hair styling
polymers that are more compatible with formulas that contain water. This change
represents a significant challenge to polymer manufacturers as well as cosmetic
formulators.
Other Ingredients
To modify the effects of the polymers, various other types of materials are added.
For example, plasticizers like isopropyl myristate are used to make the film more
flexible and less brittle. Neutralizing agents are also used. These materials, such as
aminomethyl propanol (AMP), help control the hardness of the film as well as the
solubility. Various emollients and conditioning agents that help make hair easier
to comb may also be included in styling preparations.
309
Styling Product Forms

A common delivery system for styling products is aerosol hair spray. These
products consist of a pressurized can that contains a concentrate formulated with
a solvent, the styling polymer, a plasticizing agent and other ancillary ingredients.
The hair is first combed and styled, then the button on the hair spray is pressed to
dispense product on the hair. When applied, the product helps to hold the hair in
place. Similarly, nonaerosol hairsprays are also available. These products have no
propellant and require the user to depress a pump to expel the product.
Mousse and Gels: Some styling products are applied prior to combing and
drying. These products help the consumer shape the hair as desired and then hold
it in place. Additionally, the products can improve the condition of hair. A popular
aerosol product of this type is a mousse. These water based formulations contain
styling polymers as well as conditioning agents. Another common example of this
type of product is a gel. A gel is a semi-liquid product usually dispensed from a
squeezable package. A numerous types are available including sculpting gels, spray
gels, freezing gels, post-foaming gels, ringing gels and aerosol gels. Gels typically
include a thickening agent such as acrylic polymers in addition to the styling poly-
mers. These materials give the gel its desirable rheology. The INCI (International
Nomenclature for Cosmetic Ingredients) name for one of the most commonly used
synthetic polymers is “carbomer.”
Reactive Hair Care Products—Colors, Permanent Waves and Relaxers

While styling hair can improve the appearance on a daily basis, more long-term
solutions are also desirable. Over the years, cosmetic chemists have developed
products that can actually change the chemical makeup of hair. These include
products such as permanent waves that make hair curlier, relaxers to straighten
hair, and dyes to change the color of hair.
Perms
Permanent waving products are designed to change the configuration of hair
to make it permanently curlier. During the early 1900s waving was accomplished
by heating hair with various electrical devices. These physical methods have been
largely replaced by chemical methods developed during the last 50 years. In these
products the primary reactive chemicals are thioglycolates and bisulfites. To un-
derstand the basics of permanent waving, it must be known that hair is composed
of helical proteins that are crosslinked by sulfur-sulfur bonds. These bonds give
the hair structure that can be modified by changing these bonds. (An experienced
chemist will note that this descripition is a simplified explanation of what is a
complex process.)
A 3-step process: The perming process can be broken down into three steps.
First, hair is physically rearranged with curlers or rollers. Before rolling, the hair is
protected with thin sheets of tissue which cover the ends. Next, the perming solu-
tion is applied and worked into the hair. During this stage, the bonds crosslinking
310
the hair proteins are broken. Finally, the hair is rinsed with water and treated with
a neutralizing agent to reform the bonds in a new configuration.
In general, perms contain several different types of ingredients including reduc-
ing agents, wetting agents, buffering agents, conditioning agents, oxidizing agents,
stabilizers and ancillary agents. These ingredients are formulated into three general
types of perms, alkaline, acid and bisulfite. Alkaline perms, called cold waves, use
thioglycolic acid. :”Alkaline” may seem like a misnomer, but the name is derived
from the final pH of the product. Alkaline perms typically have a pH greater than
9. Acid perms are customarily made with glyceryl monothioglycolate, a derivative
of thiglycolic acid that is effective at a lower pH of 7–8. Even though the pH is
neutral to alkaline, these products have historically been referred to as “acid perms”
in comparison to their higher pH cousins. The name also has some marketing equity
since acid perms are perceived to be less damaging. Bisulfite perms were designed
for mildness; they are based on hydrogen bisulfite rather than thio derivatives.
Relaxers
Hair relaxing is a process used to straighten excessively curly hair. It is typically
done on African-American hair which has a unique, elliptical structure that makes
hair extremely twisted or kinked. Straightening can be done mechanically by press-
ing the hair with hot implements or chemically by breaking the bonds in the hair
with reactive products. The latter method is the topic of this discussion.
Relaxers work in a manner similar to permanent waves. Basically, they rely on
reactive chemicals to break amino acid-based sulfur bonds that allow the structure
of hair to be rearranged. The process of hair straightening is also known as lanthion-
ization, which refers to the conversion of the amino acid cystine to the amino acid
lanthionine. Relaxers are commonly based on metal hydroxides such as ammonium
hydroxide, sodium hydroxide, lithium hydroxide or guanidine hydroxide. These
agents react more aggressively with the hair than perming solutions.
Relaxer application: The procedure for relaxing hair begins with dividing
hair into sections to simplify application. Next a thin layer of protective process-
ing cream is applied to the hairline to protect the ears and the ends of the hair.
Cream relaxer is brushed on section-by-section and the hair is smoothed with the
back of the comb until the desired straightness is achieved. The relaxer cream is
then rinsed off after 20 minutes with warm water to remove the reactive agents.
Commonly, a neutralizing shampoo is used to remove any excess relaxer cream and
to neutralize excess alkalinity. The result is hair that is locked into a straightened
configuration.
Relaxer formulations contain three key components, an oil phase, a water phase
and an alkaline agent. The oil phase is made up of materials like petrolatum or
mineral oil to help protect the scalp. Fatty alcohols are also included to thicken the
product and alkali-stable emulsifiers help stabilize the formulation. Lye relaxers
contain between 1.85–2.4% sodium hydroxide, depending on the strength required.
No lye relaxers are formulated with guanidine hydroxide and are significantly less
irritating than the sodium type. Relaxers can also be formulated with different
specialty ingredients such as conditioner agents.
311
Coloring
Changing hair color has been done for centuries. Cosmetic chemists developed
several ways to alter hair color, some of which involve reactions with the natural
pigments of the hair. This reactive technique is known as oxidative, or permanent,
hair coloring. To understand this process, the chemist should be familiar with
the chemistry of hair pigmentation. Primarily two melanin-based pigments affect
natural hair color: eumelanin, which produces blond, grey, brown and black shades;
and pheomelanin which produces reds and yellows. Oxidative coloring addresses
problems associated with natural hair pigmentation by producing lasting changes
in hair color. In this process, color is produced inside the hair shaft from aromatic
amines and phenols reacting with hydrogen peroxide resulting in hair color that is
locked inside the hair shaft. As new hair grows, the dyeing process must be repeated,
approximately every 30–45 days.
Simultaneous reactions: Permanent dye formulations consist of two compo-
nents that are separate until the product is ready to be applied. The first component
contains the oxidative dye precursors that are typically Thearomatic p-diamines or
p-aminophenols, such as p-pheylene diamine. These colorless precursors react to
form dye intermediates that in turn react with dye couplers to produce color. The
dye couplers include such materials as resorcinol, 1-napthol, and hydroquinone. To
produce different colors, formulations may contain five or more dye precursors or
couplers, so many reactions are occurring at the same time. An alkali is used as part
of the dye base to swell the hair and enhance penetration of the dye precursors. In
addition, this portion of the formula may include solvents, surfactants, thickeners
and metal chelating agents. The second formula component contains hydrogen
peroxide and stabilizing agents.
Oxidative hair coloring involves several steps. First, the two components are
mixed together to initiate the reactions that will form the permanents dyes. The
hair is then partitioned and the tint is applied from the scalp to the porous ends.
The hair is left for 10–20 minutes while the reaction proceeds. During the last 5
or 10 minutes, the solution is spread toward the ends to even the color. The hair is
then rinsed and shampooed to remove excess color and halt the reaction.
Summary
This chapter has discussed a few of the prime considerations for formulating hair
care products. We have not attempted to cover other important areas of product
development issues such as stability testing, performance evaluation, safety testing,
claims support, and packaging.
For Further Reading

MM Reiger, ed., Harry’s Cosmeticology, 8th edition, CHS Press Inc., NY
(2000)
McCutcheon’s Detergents & Emulsifiers, North American Edition, MC Publish-
ing Co., McCutcheon Division, Glen Rock NJ (1994)
312
RY Lochhead, The History of Polymers in Hair Care 1940–Present, Cosm &

Toil 103 36-49 (1988)
WH Schmidt and C Williams (Eds.), Chemisty and Technology of the Cosmetics
and Toiletries Industry, Springer, London (1996)
ET Borish, Hair Waving, Hair and Hair Care, Marcel Dekker Inc., NY
(1997)
CR Robbins, Chemical and Physical Behavior of Human Hair 4th edition,
Springer-Verlag (2001)
Milady’s Standard Textbook of Cosmetology, Cengage Learning, Albany, NY
(2008)
AN Syed, et al, African-American Hair, Cosm & Toil 110 (10) 39 (1995)
KC Brown, Hair Coloring Hair and Hair Care, Marcel Dekker Inc., NY
(1997)
M Paye, A Barel, and H Maibach (Eds.), Handbook of Cosmetic Science and
Technology, 2nd edition, Taylor & Francis Group (2006)
P Becher, Principles of Emulsion Technology, Reinhold Publishing Corp., NY
(1955)
Chapter 33
Introduction to Shampoo
Thickening
Obtaining the desired viscosity of a shampoo product is critical
to determining the product’s process and manufacturing costs,
performance, application and sensory profile.
key words: viscosity, rheology, thickener, Newtonian flow

behaviors, surfactants, electrolytes, micelles, salt curve
C osmetic chemists are constantly searching for methods to control the various
physical and chemical characteristics of their formulations. Controlling these
characteristics is important because these factors, more than anything, determine
whether a consumer will like a formulation. Some of the most important char-
acteristics that we attempt to control include viscosity in addition to odor, color,
appearance, and feel.
The term viscosity generally relates to the thickness of a cosmetic formula-
tion. Typically, products with an optimized viscosity are easier to use, have better
efficacy, and are more aesthetically pleasing. Since most cosmetic products are
water and surfactant based, researchers have had to develop numerous methods
for controlling viscosity.
This chapter provides an introduction to a variety of thickening ingredients
used by cosmetic chemists. While it focuses on shampoos, much of the information
is applicable to other systems such as skin creams and hair conditioners. It also
provides information about basic rheology that will be particularly helpful to the
beginning cosmetic chemist.
Shampoos are Complex Systems

Shampoos are based on complex systems of surfactants and function primarily
to cleanse the hair. Because these products tend to be used daily, it is not surpris-
ing that the shampoo market comprises approximately 12%1 of the personal care
industry. However, shampoos do more than just solubilize sebum and remove soil
from the hair.2,3 Various performance additives are used in the formulation to im-
prove hair conditioning and product aesthetics. A typical shampoo consists of water
(~80%), surfactants (~10%), viscosity modifiers (<5%), preservatives, fragrance
and color (~2%), and performance additives (<3%)3 (Figure 33.1). Among the
surfactants, the mixtures of Sodium Lauryl/Laureth Sulfate and Cocamidopropyl
Betaine are widely used for shampoos. These mixtures are not only superior to the
313
314
Introduction to Shampoo Thickening Beginning Cosmetic Chemistry
single surfactants with respect to cleansing, foaming and mildness but also provide
an ideal basis for further rheology adjustment.
Figure 33.1. Shampoo Ingredients
Shampoo action: Within these parameters, a shampoo is expected to be easy

to use, function to both clean and condition the hair, and meet sensory criteria that
will appeal to the consumer. The thickness and flow characteristics of a shampoo
are described by the term “viscosity”. Viscosity affects both the cleansing efficiency
and consumer perception of a product. In a simplified term, the viscosity of a fluid
may be defined as the value of shear stress (τ) divided by shear rate (D). On the
other hand, the rheology of a fluid is more complex, which deals with the change
in form and flow of matter, comprising elasticity, viscosity and plasticity. The rhe-
ology or viscosity characteristics of a shampoo also affect the foaming properties,
production/filling, packaging, storage and stability of the product.4
Many different rheology additives are available to the cosmetic chemist. The
choice of a cosmetic thickener depends on both the desired rheology of the fin-
ished product and the compatibility of the thickener with the other components
in the shampoo. Rheological behavior can be described as Newtonian or non-
Newtonian.
Newtonian or non-Newtonian: Newtonian flow is represented by a linear
relationship between the shear stress and the shear rate (flow). This type of flow
means the apparent viscosity of the product remains constant (the slope of the line)
and is independent of the shear rate (Figure 33.2). Non-Newtonian flow means that
the viscosity is no longer constant when shear rate is varied, i.e ,, a system appears
to either thicken or thin at a non-linear rate with an increasing shear rate. Dilatant
behavior refers to the “shear-thickening” and pseudoplasticity refers to the “shear-
thinning” (Figure 33.2). Some fluids can further exhibit a change of viscosity with
315
time under constant shear rate. A thixotropic fluid displays a decrease in viscosity
with time under constant shearing, while a rheopectic fluid shows an increase in
viscosity with time under constant shearing. These effects may or may not be re-
versible. For a reversible thixotropic fluid, the initial viscosity can be regained over
a period of time, after the shear stress is removed and left undisturbed.
Figure 33.2. Flow Behaviors
Shear-thinning products can be stored upside down or in a hanging package.

These products thin for dispensing when the package is squeezed. An example of
a finished good displaying this viscosity behavior is the hand soap found in public
rest rooms.
Choosing a thickener: Other components within a shampoo system can also
be a consideration when choosing a thickener. The percentage of solids in the for-
mulation can affect what viscosity range can be attained in the finished product.
The choice of a thickener also depends on how much thickening is required to
achieve the desired viscosity. Typically, higher percent solids give a higher viscosity
system. However, some thickeners may require larger amounts of water and low
surfactant solids to allow for thickening by polymer swelling.
Price is another important formulation parameter. If a formulation is not af-
fordable to either the consumer or manufacturer, then the product can not be
profitably made or sold. It is important to balance the effectiveness and the cost of
performance additives in such formulations.
Certain performance additives such as silicones, esters, glycols and alcohols can
change the viscosity of a system and will influence the efficiency of the formulator’s
chosen thickener. The following section describes the commonly used cosmetic
thickeners in shampoo systems. This information is also applicable to facial and
body washes.
316
Salts
Electrolytes, although not usually referred to as thickeners, can be used to affect
the rheology of a shampoo system. Primarily, chloride salts of sodium, potassium and
magnesium can be added to anionic-amphoteric combination systems to provide
a thickening effect. These materials tend to be used between 1–2% as a solid or as
an aqueous solution and provide Newtonian rheology. Electrolytes are the most
commonly used rheology modifier and are often used in conjunction with other
salt responsive thickeners.
Micelle function: Shampoo systems consist mainly of water and surfactants,
which will form micelles. Surfactant molecules contain both water-loving (hydro-
philic) and oil-loving (hydrophobic) portions. In aqueous solutions, surfactant
molecules align themselves into micelles where the “like-loving” portions orient
themselves together. Micelle formation is a dynamic process where these portions
are constantly orienting and reorienting themselves. These orientations can take
many shapes and function in cleansing.
The primary surfactants of the shampoo tend to be anionic and the electrolyte
that is used to thicken should be compatible with the metal portion of the surfactants.
Micelles function in hair cleansing as the mechanism for soil and sebum removal.
When salts are added to these systems, the surfactant micelles swell and that affects
the overall ionic charge of the system. This swelling results in a resistance to move-
ment, thus increasing the system’s viscosity. The extent to which this mechanism
works depends on the type of surfactant, ratio of shampoo components, pH, ionic
strength of the electrolyte and the amount of electrolyte used.
The salt curve: The amount of salt added to the surfactant system versus the
viscosity achieved can be graphed as the “salt curve.” This relationship is rarely
linear and typically the product has a maximum viscosity value where the addition
of more salt will decrease the viscosity of the system (Figure 33.3). Typically, the
salt is added in 0.1% weight increments to the formula and the viscosity is measured
after each addition. Salt can be added as an aqueous solution so that the viscos-
ity can be immediately measured. Additions may be made to the same sample or
increasing increments of salt can be added to a series of samples of the base. The
salt curve is then graphed from this data. Viscosity data is collected typically until
at least two points past the maximum viscosity point are determined.
Avoiding “salting out”: After the maximum viscosity has been achieved and
more electrolyte is added, the electrolyte level interferes with the micelle structure,
lowers the resistance to movement, and thins the shampoo system. This event is
referred to as “salting out”. Salts can also be formed from incompatibilities within
the system. A formulator needs to be aware of separating charged species, such as
anionic surfactants from cationic conditioning aids. This occurrence is commonly
addressed by the order of addition and the inclusion of a betaine or by diluting
the anionic surfactant in one part of the water phase; then diluting the cationic
surfactant in another part of the water phase. When these solutions are combined,
it is referred to as the “dilution of species.”
317
Figure 33.3. Salt Curve
Alkanolamides
Alkanolamides are low molecule weight hydrophobic thickeners, which consist
of a mixture of ethanolamides that are derived typically from a coconut source. His-
torically, these products have provided an easy and cost effective means to modify
the rheology of shampoo systems. Both mono- and dialkanolamides are available,
however the dialkanolamides tend to be more effective for any given carbon chain
length (R group) (Figure 33.4).
Figure 33.4. Alkanolamide Structure
Non-Newtonian rheology: The thickening mechanism of alkanolamides

functions by interacting with the anionic surfactant micelle and produces a non-
Newtonian rheology. Alkanolamides are salt responsive and can be combined with
electrolytes to maximize the efficiency of thickening as well as the maximum viscosity
achieved. The viscosity of a formula thickened by this type of low molecule weight
hydrophobic thickener is in general less affected by temperature variations.
In addition to building viscosity, alkanolamides also function to enhance the
foaming properties. These products increase the amount of foam, form tighter
bubble structures and promote longer-lasting foam. The most commonly used
alkanolamide is cocamide DEA. This material is easy to incorporate into shampoo
systems and is a cost-effective way to enhance foam and thicken the system.
Possibly carcinogenic: It has been recently reported that alkanolamides have
the potential to form toxic (or cancer causing) nitrosamines when incorporated
318
into a cosmetic product.5 Free amine is an impurity found in alkanolamides and

is potentially nitrosating agent. The possibility of forming nitrosamine is much
greater for secondary amine such as diethanolamine than the primary and tertiary
amine. The personal care industry does not have an official opinion on whether
alkanolamides should be formulated out of consumer products; however consumer
perception has driven a reformulation effort. Manufacturers are looking at replacing
diethanolamines with monoethanolamides to deliver product performance without
impacting cost.5 Other alternatives based on monoisopropanolamine (MIPA) such
as isostearamide MIPA are also available for controlling rheology or foam.
Polyethylene Glycol Modified

The most commonly used class of nonionic thickeners is the polyethylene gly-
col (PEG) modified materials. These compounds are represented by the general
structure in Figure 33.5.
Figure 33.5. PEG Structure
The R group denotes the fatty moiety and “n” represents the average number of
repeating units of polyethylene glycol. This R group can be a fatty alcohol, glyceryl
ester or propylene glycol ester. Laureth-3 (Figure 33.6) is an example where the
R group is a fatty alcohol.
Figure 33.6. Laureth-3
The “laureth” corresponds to the carbon chain length distribution and “3” cor-
responds to an average of three moles of PEG modification. This material produces
a shear-thinning rheology. PEG-18 glyceryl oleate/cocoate (Figure 33.7) is an
example where the “R” group is a glyceryl ester.
Figure 33.7. PEG-18 Glyceryl Oleate/Cocoate
The “R” is the “oleate/cocoate.” This designation denotes the carbon chain
length distribution, which is a blend of coconut and oleic fatty acids, and the “18”
is the average number (x+y+z) of moles of ethylene oxide. This material produces a
Newtonian rheology. PEG-55 propylene glycol oleate (Figure 33.8) is an example
where the R group is a propylene glycol ester.
319
Figure 33.8. PEG-55 propylene glycol oleate
The “oleate” denotes the carbon chain distribution and “55” represents the
average number of moles of ethylene oxide. This material provides a Newtonian
rheology. The chart in Figure 33.9 summarizes the thickening properties of these
types of materials in different surfactant systems.
Figure 33.9. Effect of Shear on Flow Behavior
The flow properties of a fluid can be characterized by the ratio of two fluid
viscosities, one measured at higher shear rate to the other one at lower shear rate.
A ratio of 1 indicates a Newtonian flow. For pseudoplastic (shear thinning) flow,
the ratio will be less than 1 and decreases as the degree of pseudoplastic behavior
increases. On the contrary, for dilatant (shear thickening) fluids, the ratio will be
greater than 1 and becomes bigger as the degree of dilatant behavior increases.
As demonstrated in Figure 33.9, the length of each bar represents the ratio
between the viscosity measured at a highest shear rate (spin speed 100 rpm) and
the viscosity measured at the lowest shear rate (spin speed 5 rpm) using Brookfield
Viscometer with same spindle. The longer the bar the more the solution follows
a Newtonian flow and as the bar length decreases the pseudoplastic properties
increases.
A fundamental difference between high molecule weight hydrophilic polymeric
thickeners and low molecular hydrophobic thickeners is evident from Figure 33.9.
A shampoo system thickened with polymeric thickeners such as PEG-55 propylene
glycol oleate and PEG-18 glyceryl oleate/cocoate shows its flow behavior more like
Newtonian (only weak shear thinning properties), while a system thickened with
the low molecular weight hydrophobic thickener such as laureth-3 shows a strong
pseudoplastic behavior (reduction of viscosity with increasing shear rate).
320
Because of their highly hydrophilic nature, highly PEG-modified materials

(30–200 ethylene oxide moles per molecule)3 are less irritating to the stratum cor-
neum and may mitigate irritation in the overall system. The thickening effect comes
from the dissolution of high molecular weight polymer chains into the surfactant
system. This mechanism is driven by the high molecular weight of the material and
is independent of the surfactant system itself. These thickeners are less susceptible
to hydrolysis and offer better viscosity stability under a broad range of pH. Of this
class, the best known material is PEG-150 distearate (Figure 33.10).
Figure 33.10. PEG-150 Distearate
Highly ethoxylated PEG thickeners have been developed and work along the
same principles as the other high molecular weight polymers. They were developed
to offer the formulator creative ways to thicken surfactant systems, to moisturize
the skin and hair, and to mitigate irritation from the primary surfactants. Both solid
and predispersed forms are available. The thickening efficacy of these high mol-
ecule weight hydrophilic thickeners is more sensitive to temperature variations. A
formulation thickened with this type of thickener will have lower viscosity at higher
temperature and will become more viscous at room temperature. This feature may
facilitate the bottle filling process during manufacturing at higher temperature
before the formula finally settled down at room temperature.
Cellulose
Cellulose derivatives are effective thickeners in water-based systems. Cellulosic-
derived thickeners, primarily cellulose ethers, are one of the most widely used
thickeners in all types of cosmetic products. Cellulosic thickeners vary based on the
method of modification, cost and viscosity characteristics provided. These materials
are water-soluble polymers that are compatible with most shampoo ingredients. The
most common of these cellulosics used to thicken shampoos are methylcellulose,
hydroxypropyl methylcellulose and hydroxyethylcellulose. As shown in Figure
33.11, these materials are based on cellulose structures.
Figure 33.11. Cellulose Structure

321
Cellulose is a natural carbohydrate that contains repeating units of anhydro-

glucose, which are linked through beta-glycosidic bonds. Each of these units has
three hydroxyl groups that may be reacted to form a variety of cellulose derivatives.
To be effective, cellulosic thickeners are restricted to aqueous systems with a high
water content (>90%).5 This restriction allows for only a small amount (typically
10%) for the surfactant solids. These types of materials are compatible with a wide
variety of cosmetic materials including anionic and cationic surfactants, electrolytes
and nonionic materials. In shampoo systems, they provide increased foaming with
a tight bubble structure and are pH stable over a wide range.
Pseudoplastic behavior: Cellulosic derivatives build viscosity because of their
high molecular weight. In this type of matrix, cellulosic thickeners show substantial
shear-thinning or pseudoplastic behavior.6 The powdered materials are hydrophilic
in nature and readily swell in the presence of water. These materials are typically
used at a 1% level.
Acid-Based Acrylics
High molecular weight crosslinked carbomer
resins are polymers of acrylic acid 7 (Figure
33.12).
The higher the molecular weight of the polymer
used results in a higher viscosity achieved. These
products are offered in a variety of molecular weights.
The carbomer does not function as a thickener
Figure 33.12.
until it is neutralized and formulators commonly Acid-based acrylics
use triethanolamine or sodium hydroxide. This
neutralization forms an acid salt, which results in
ionization of the polymer accompanied by rapid swelling of the polymer network.
The many swollen “arms” of this polymer trap water in “pockets” which results in
thickening. For efficiency, nonneutralized stock solutions of concentrated disper-
sions can be made. These stock solutions can then be diluted and used as required
by the formula.
Viscosity enhancement using carbomer systems can be effectively seen between
pH 6–8. However, carbomers are incompatible with cationic surfactants and do
not work well in the presence of electrolytes. Hydrophobically modified polyacrylic
acid polymers and polyacrylic acid/hydrophobically modified acrylate copolymers
(acrylate/alkyl acrylate copolymer) show benefits on improvement on electrolyte
tolerance and wider pH range for viscosity. Surfactant systems incorporating carbom-
ers show a non-Newtonian behavior. Many varieties of acrylic resins are available
to meet the formulator’s requirements. Examples include easy to disperse, clear
formulation compatibility, and rheology specific varieties.
Natural Gums and Clays

Commercially, many types of natural gums and clays are available for use
in shampoo systems. Three of the more popular viscosity building gums include
xanthan gum, magnesium aluminum silicate and bentonite. These materials are
322
naturally occurring and exhibit non-Newtonian behavior. Typically, these materi-

als are added first to the water phase and incorporated using vigorous agitation.
These rheological aids are also commonly used under 0.5% to stabilize colloidal
systems (pearl stabilizer).
Xanthan gum is a polysaccharide (Figure 33.13) that is cold water soluble and
can be used in a wide pH range.
Figure 33.13. Xanthan Gum
Xanthan gum solutions exhibit a pseudoplastic behavior. Magnesium aluminum

silicate is a naturally occurring clay supplied in a flaked form. Although insoluble,
magnesium aluminum silicate swells in the presence of water, forming a hazy viscous
matrix, which exhibits a reversible thixotropic behavior. (The loss of viscosity due to
shear over time is regained over a period of time after shear without disturbance.)
This material is used in opaque or pearled surfactant systems. Bentonite is hydro-
philic and can be dispersed into water. This gum forms a lattice structure, and when
wetted, swells to produce a gel that is thixotropic. Thickening can be enhanced
with small amounts of electrolytes. Other examples of this type of thickener include
carrageenan, gum arabic and locust bean gum.
Conclusion
Thickeners function by many mechanisms including hydrogen bonding, poly-
mer swelling, chain entanglement of the polymer backbone, surfactant micelle
323
interaction and various other intermolecular interactions.8 A formulator’s goal is

to obtain a desired viscosity in a finished product with the lowest concentration
of a chosen thickener. The rheology of a shampoo product affects the product’s
processing, application and sensory profile. Although the thickener typically makes
up less than 5% of a shampoo formula, it greatly influences the sensory profile of
the finished product. Chemistry may determine the effectiveness of a thickener,
however cost, cosmetic attributes, and rheology will determine the performance
and consumer acceptance of a shampoo product.
Originally Published in 2000 Cometics and Toiletries magazine.
References
1. Drug Chain Review, Vol 22, No 2 ,15, 16, 18, 21, 22, 24, 26 (January 17, 2000)
2. HI Leidreiter, U Maczkiewitz, Utilizing Synergistic Effects in Surfactant Mixtures, Th.
Goldschmidt AG, Essen, Germany (1996)
3. JB Wilkinson, RJ Moore, Ed, Harry’s Cosmeticology: Shampoos, 7th Edition (1982)
4. HI Leidreiter, K Jenni, U Maczkiewitz, Rheology of Toiletry Product—Physical
Properties and Sensory Assessment, Th Goldschmidt AG, D-45116 Essen, Germany
(1995)
5. T Schoenberg, Formulating Alkanolamide-free Products, McIntyre Group, Happi, Vol
36, No 7 ( July 1999)
6. H Plate, “Hydroxyethyl Ethylcellulose: A New Surface Active Hydrocolloid for Use in
Personal Care Products, Cosmetics and Toiletries Manufacture Worldwide, 10th Ed
208 (2000)
7. RY Lochhead, WJ Hemker, D Casta–eda, D Garlen, Novel Cosmetic Emulsions, Cosm
& Toil., Vol 101, No 11, p 125 (1986)
8. J P Pavlichko, Cold Process Viscosity Enhancement of Surfactant Systems with a
New Naturally Derived Methyl Glucoside Triester, Amerchol Corporation.” Cosmetics
and Toiletries Manufacture Worldwide 10th Ed. 107 (2000)
Chapter 34
Innovations in Hair Styling

Technology
The regulatory climate for cosmetic products is becoming
more difficult for formulators. Here, the authors describe how
new rules have inspired cosmetic chemists to use a variety of
strategies and partner with raw material suppliers and packaging
houses in order to provide consumers with what they want.
key words: VOCs, aerosol hair spray, pomades, hair dressing,

packaging, solvents, polymers
I n previous pieces we reviewed the basic technologies behind the primary styling
product forms including aerosols, pumps and gels.1 This chapter reviews how
changes in technology and regulatory pressures have “inspired” innovation. In order
to understand how and why chemists are innovating to accommodate regulations
presently, we need to start by looking at where it all began.
A History of Styling Technology

For almost as long as there have been cosmetic chemists, regulatory agencies have
existed to control their work. The incursion of regulatory requirements has forced
changes in hair styling products more than in any other type of hair product.
Since their introduction in the 1940s, hair sprays led the popularization of
modern styling products. The first sprays were pump-type systems, but public
demand for a better product prompted the development of the aerosol hair spray.
The aerosol spray was based on Goodhue and Sullivan’s patent of low-pressure
propellants (fluorocarbon 12) and Abplanalp’s patented valve design.
The first aerosol hair spray was introduced to the public in 1949 in Chicago by
the Global Liqinet Corporation, and created a multi-million dollar business. These
early formulas used shellac as the fixative polymer but shellac exhibited several major
drawbacks—such as being difficult to wash out of hair—that led to the development
of synthetic polymers with properties that could be better controlled.
For the next 20 years business boomed but by the late 1960s environmental
and safety concerns began to threaten the industry. While styling formulations gave
good fixative properties, many contained environmentally sensitive solvents and
propellants. Chlorofluorocarbons (CFCs) were the first to gain notoriety because
they depleted the ozone layer, prompting fears that an unhealthy amount of UV
radiation could reach the Earth’s surface.
325
326
Innovations in Hair Styling Technology Beginning Cosmetic Chemistry
In 1979, regulatory agencies banned CFC propellants from aerosol formulations

in most industrialized nations. (Despite what anyone may tell you, CFCs are no
longer used in hair care aerosols today.) Shortly thereafter, the popular co-solvent
methylene chloride came under scrutiny after it was discovered to be a potential
carcinogen.
Fortunately the cosmetic chemists of the day found innovative solutions to these
regulatory realities. Ethyl alcohol and alcohol/water systems became increasingly
popular substitutes as solvents and dimethyl ether/hydrocarbon mixtures replaced
CFCs as the primary propellant system. All was right in the world of cosmetic
science—at least for a short while.
By the early 1980s this new breed of “eco-friendlier” formulations was coming
under scrutiny because of concern for air pollution. These formulations relied heav-
ily on ethanol and other hydrocarbons which belong to a class of chemicals known
as volatile organic compounds (VOCs). Researchers found that when exposed to
sunlight, VOCs were capable of combining with nitrogen oxides (NOx) to form
ground level ozone, or smog. Ironically, the industry had swapped one material that
destroyed ozone for another that created it. But this ozone stays near the Earth’s
surface and has negative health effects.
Concerns about smog led to VOC reductions in 1983, just after CFCs were
banned. Originally, the South Coast Air District in California wanted to ban aerosols
but industry activists succeeded in obtaining amendments to the law to preempt
California Districts from doing just that. The result was the establishment of legal
safeguards for development of regulations by the California Air Resources Board
(CARB). These rules were developed through intense negotiations that occurred
in the early 1990s. They ultimately limited the amount of VOCs that could be used
in any cosmetic aerosol product.
Sidebar 34.1.
History of Consumer Product VOC Regulations in the USA
• 1978: CFC Ban
• 1983: South Coast AQMD (Los Angeles)
• 1988: California Clean Air Act
• 1989–1992: California Rules
• 1990: Federal Clean Air Act Revisions
• 1990–1995: Other State Rules
• 1996: EPA National Rule
• 1997-1999: More California Rules
• 2000: Reactivity-Based Aerosol Paint Rule in California Rule in
California
• 2000-2004 Northeastern State Rules 2004
• 2003: New California Rule
• 2005–2010: More California Rules
327
Federal laws soon followed that supplemented an ever-growing number of state

rules, but California remained the most stringent. California proposed still more rules
during the late 1990s and the trend continued through the new millennium.
In 2000–2004 the Northeastern State Rules were first proposed and they were
followed by still more California rules in 2003. As of 2005, California remains the
state with the most stringent requirements. Texas, New York, Massachusetts, New
Jersey, Delaware, Pennsylvania, Maryland and Virginia are somewhat less stringent
than California, but more stringent than the National Rule. Arizona and Georgia
have local rules that affect products other than aerosols. All states are subject to
the EPA National Rule.
As of 2005, the rules state that hair mousse may contain no more than 6%
VOCs, hair shine and hair holding sprays no more than 55% and gels no more than
6%. And according to industry experts, we can expect to see even more rulings in
California through 2010.
Strategies to Create Low VOC Formulas
What do all these rules mean to the formulator? Well, to begin with, we can
no longer use ethyl alcohol as the major solvent in styling products. This limitation
is a huge impediment because ethanol is really an ideal ingredient. It solubilizes
holding polymers, has excellent spray properties, is easy to use, dries quickly, smells
nice, and has no serious toxicologic issues. Instead of ethanol, many manufacturers
have resorted to adding water to their products. However, an increase in the water
concentration can adversely affect the performance of a hair spray by accelerating
the initial curl droop and/or increasing the dry time on the hair. Other styling prod-
ucts have similar issues related to drying time and application properties. Cosmetic
formulators must rise to the challenge to do more with less, to create formulations
that satisfy consumers despite rigorous regulatory constraints.
To achieve these goals, various strategic approaches have been suggested. Doug-
las Fratz, of the Consumer Specialty Products Association (CSPA), listed several
approaches for creating VOC-compliant products by using the following: exempt
compounds, low vapor pressure compounds, water-based formulations, increased
amounts of inorganic compounds and solids, innovative product exemptions, al-
ternative compliance plans and product use instruction labeling.2
To achieve these goals, various strategic approaches have been suggested. At the
24th International Aerosol Congress in September, 2003, the Consumer Specialty
Products Association’s Douglas Fratz discussed creating VOC-compliant products
and suggested the seven approaches described next.2
Exempt compounds: This strategy involves formulating with compounds that
the authorities consider exempt from VOC consideration. For example, hydro-
flourocarbons (HFCs) are exempt propellants and acetone is an exempt solvent.
Certain types of silicones can be used in some products but they are very expensive.
Chemicals with negligible photochemical reactivity (e.g., compounds that have less
ozone formation potential than ethane) are also exempt. Also exempt are materials
with vapor pressures less than 0.1 mm Hg at 20°C. Similarly, fragrances are exempt.
328
It is best to check with the Cosmetic, Toiletry and Fragrance Association (CTFA)
or the CSPA to find a list of exempt compounds.
Low vapor pressure compounds: Materials with low vapor pressure such as
glycol ethers and propylene glycol can be used without affecting VOC content. This
strategy is useful for products such as gels but less useful for hair sprays.
Water-based formulations: By using water-based formulas the amount of
VOCs is easily reduced. Unfortunately, adding water usually requires surfactants or
emulsifiers to be added to the formula. These compounds will have various effects
on the product performance, many of which are not desirable. Water itself also
has negative impacts on the finished products such as increasing drying time and
decreasing hold. To date, most hair spray manufacturers have used this formulation
strategy even though it results in an arguably inferior product.
Increased amounts of inorganic compounds and solids: Compressed gas
propellants like carbon dioxide and nitrogen are not considered VOCs so they
could be used as substitutes. However, their use is limited due to technological
challenges. The major hurdle yet to be solved is the loss of pressure that products
using compressed gas experience. A consumer using such a product will notice a
weaker spray over time until eventually nothing gets dispensed. If product remains
in the container but cannot be removed, the consumer will be turned off and likely
never purchase the product again.
This strategy is more effective for products like antiperspirants, where VOC
levels can be decreased by adding non-volatile organic solids, such as surfactants
and polymers.
Innovative product exemptions: CARB allows an exemption for certain in-
novative formulations. To use this strategy, the chemist has to be able to provide
“ëclear and convincing evidence’ that, owing to some characteristic of the product
formulation, design, delivery systems or other factors, the use of the product will result
in less VOC emissions…”3 than a product with a comparable amount of VOCs. For
example, a concentrated hair spray can be produced to have more active ingredients
but be dispensed with less solvent.
Alternative compliance plans: California allows the VOC emissions of some
products to be averaged, or grouped together. This approach allows mixing products
that can be over-reduced with others than cannot be reduced much at all. To use
this strategy, cosmetic manufacturers have to submit an application to show the
VOC content of the products in the plan, a sales verification method, and other
emission tracking information.
Product use instruction labeling: Another way to reduce VOC emissions is
to educate consumers on an alternative method for using a product. This approach
attempts to change consumer behavior to increase use efficiency and deter exces-
sive VOC emissions. For example, instructing consumers to use less hair spray at
a given time will make the product last longer and reduce emissions over a given
time. While this method is not currently applied to hair care products, it could be
in the future.
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Styling Technology Today

All of the strategies have been attempted (with various degrees of success) to
face the challenges of ever-increasing regulations of hair care products and more
specifically, styling products. Let’s take a closer look at some of the specific innova-
tions that have been employed by formulators in today’s styling products.
A quick review of some recent patents shows how formulators have compensated
for VOC regulations in all types of styling categories including hair sprays, gels,
and mousses. We’ll begin with aerosol hair sprays because they are arguably the
most complex, dynamic systems of all personal care products, and have also been
subject to the most difficult regulations.
Aerosol hair spray: Aerosols face all the “standard” formulation problems imag-
inable such as phase separation, sedimentation, malodor generation, discoloration,
pH drift, and so on. But additionally, they have a set of potential problems unique
to their delivery system, including can corrosion, poor spray-ability, dry time, film
formation, Department of Transportation pressure issues, can cause evacuation,
dip-tube elongation, and so forth.
The two most successful methods for creating new VOC-compliant aerosol
products are as follows.
First, the formulator can try to modify the solvent/propellant mix to optimize
its properties. This approach typically involves finding substitutes for ethanol as a
solvent or replacing hydrocarbon propellants. In the latter case, a choice between
using either HFC-152a propellant (a non-VOC classified material which allows
for anhydrous systems) or dimethyl ether (DME) with hydrocarbon combinations
(which allow water-compatible systems) is the norm.
Second, the formulator may choose to alter the holding resins in the formula
to improve the way the product functions. The technical literature indicates for-
mulators have had some degree of success with both approaches. Optimizing the
solvent/propellant mix is the most common solution to the VOC issue. While using
HFC-152a propellant in an aerosol formulation is a straightforward replacement,
it usually results in a product that is of significantly higher cost. DME formula-
tions can be made less costly but have required innovative solutions to deal with
the presence of water. Ethanol replacements have been harder to develop, but
progress has been made. Consider the following three patents which deal with
optimized solvent systems.
• US Patent No. 6,752,983 discloses the replacement of ethanol and isopro-
panol by alkyl acetates, particularly methyl acetate and t-butyl acetate.4
These solvents can be problematic because they hydrolyze in the presence
of water to form harmful acids. They may also have pungent chemical odors
and may stain clothing. This patent discloses a way to mix alkyl acetates with
lower levels of alcohols to over come these difficulties while lowering VOC
content.
• US Patent No. 6,464,960 involves the use of acetone as a solvent.5 Acetone is
not widely used in hair sprays because it has an unacceptable odor, it evaporates
too quickly, and it is a poor solvent for some polymers. This patent discloses
330
the use of a hair-setting polymer in a solvent/propellant system containing a

1- to 4-carbon alcohol, water, a cosolvent such as acetone, and a propellant
mixture consisting of dimethyl ether and a fluorocarbon. According to the
patent, this invention allows for water containing, reduced VOC hair spray
that approximates the performance properties of conventional water-free
hair sprays.
• In a similar vein, US Patent No. 6,432,390 uses a concentrate blend of alcohol
and methyl acetate along with dimethyl ether propellant.6 The composition
consists of 50–90 weight percent concentrate and 10–50 weight percent
propellant and it provides competitive styling properties with minimal VOC
emissions. Recent examples of formulators changing styling polymer proper-
ties can also be found.
• US Patent No. 6,638,992 discloses a styling product that involves the
incorporation of latex chemistry in the formula.7 It uses a spray-dried
hybrid-graft copolymer of a sulfopolyester and an acid-functional polymer
segment. Purportedly, such compositions exhibit superior curl retention
even at high humidity and they may be prepared over a wide range of VOC
concentrations.
• US Patent No. 6,562,325 relates to a non-aerosol hair spray based on poly-
acrylic acid and nonionically derivatized starches.8 The starches are hydrolyzed
and modified by cationic substitution to give a clear solution with a stable
viscosity. Furthermore, this formula provides a clear film which is not tacky,
that has good stiffness and improved humidity resistance and is substantive
to hair.
Gels and mousses: Hair sprays are not the only product category of interest.
Other styling product categories such as gels and mousses have their own unique
formulation challenges as well.
While not necessarily focused on low VOC content, US Patent No. 6,663,855
does reveal a clever approach to formulating a mousse.9 It uses graft copolymers
which allow physical and chemical attributes like glass transition temperature
and solubility to be varied independently. The result is a novel class of polymers
that can be tailored to the particular application, particularly related to providing
longer-lasting hold and/or improved feel.
Hairdressings and pomades: Finally, no discussion of styling products would
be complete without a reference to hairdressings and pomades. US Patent 6,649,154
discloses a method to make conventional hairdressings less sticky and oily-feeling.10
This outcome is accomplished by incorporating a polysaccharide such as beta-1,3-
glucan. Formulas based on this type of polymer provide an excellent hairdressing
effect and hair-setting power when applied with heat at reduced VOC levels.
US Patent No. 6,579,517 reveals a way to make a dual component system using
at least one cross-linked, water-soluble or water-dispersible polyurethane combined
with at least one polymer having isocyanate-reactive groups.11 This method is a new
way to achieve benefits of these polymers from a low VOC system.
331
The Role of Packaging

As you can see from even this brief review, VOC regulations have prompted
a tremendous innovation effort for new hair styling formulations—but the story
does not end there. Packaging companies have been busily innovating to help aid
formulators in the development of lower VOC products.
Typically, changes in formulation technology help drive packaging development
and the recent low VOC formulas are no different. Consider these recent attempts
by packaging suppliers to develop new, more functional packaging and dispensers.
For example, TricorBraun has a new line of special fine mist sprayers designed for
lower VOC hair sprays and spray gels. Similarly, SeaquistPerfect Dispensing now
offers actuators for new high viscosity styling products.
Companies have developed new anti-clog pumps that do not clog even with
high resin content products. Some of these dispensers are also available in a 360°
spray version that can be used upside down. Emsar offers a directional spray pump
that provides precise application that is ideal for concentrated products such as
root volumizers. Similarly, Saint-Gobain Calmar markets the Mark VI fine mist
sprayer with a spray extender. It is a pressure build-up type of sprayer that delivers
performance for 55% VOC formulations.
Finally, Airspray International has introduced the first foam pump on the market,
the Finger Pump Foamer. It is a mechanical foamer and therefore does not require
gas propellant to create thick foam. The dispenser is suitable for simple water-based
(non-VOC) formulations such as mousses.
Packaging companies have also aided formulators in dealing with low VOC is-
sues by creating options for different kinds of styling products. While hair spray is
still the biggest part of the styling category sub-segment, waxes and gels are rapidly
growing in popularity. A recent trend in styling products is the use of putties and
pastes which tend to have fewer VOC issues. This shift in product choice is attrib-
uted to the consumer’s desire for a messy, matte look, but could also be a reaction
to the lower performing, VOC-compliant products now being produced.
Pastes and putties are typically sold in tubes and jars and these containers dictate
a certain formula texture and viscosity which chemists must take into consideration
when formulating. The trend toward hair that is grungy, unkempt and wild has
led to products which support that look. These include products that can create a
tousled or stringy look like D:fi Beach Bum, Estée Lauder’s Bumble and Bumble
Surf Spray, Redken’s In the Loop, and Sebastian’s Bondage.
Packaging technology allows these products to match the look that the consum-
ers want. For example, they give the packaging a matte look with special resins
such as Velva-soft. Or they can use bi-injection molding to give the package a dif-
ferent, softer feel. In addition to making them VOC-compliant, formulators are
also using newer types of styling polymers to help meet consumer expectations
for these products.
Conclusion
The regulatory climate for cosmetic products is arguably becoming more and
more difficult for formulators. Different states have different regulations that are
332
constantly changing. This outlook does not even take into consideration regulations
proposed around the world. And these new rules have been particularly hard on
cosmetic chemists who are responsible for developing styling products.
Fortunately, innovation is alive and well in the styling field of cosmetic chemis-
try. By using a variety of strategies and partnering with raw material suppliers and
packaging houses, formulators have found ways to reduce the VOCs released and
still provide the consumers with what they want. Future regulations will likely make
the formulating job even more difficult, but they will also spark true innovation—
and that can’t be all bad, right?
References
1. P Romanowski and R Schueller, Aerosols for apprentices, Cosm Toil 111(5) 35–40
(1996)
2. D Fratz, USA VOC Regulations and Compliance Alternatives for Aerosol Products,
presented at the 24th International Aerosol Congress, Consumer Specialty Products
Association (September 2003) Available at: http://www.aerosols-info.org/nic02/
t_cspa.pdf
3. California Air Resources Board (CARB) regulations 94511, Innovative Products, Div. 3,
Ch. 1, Sub 8.5, Consumer Prod. Art. 2 (2004)
4. US Pat 6,752,983, Hair spray and consumer sprays with reduced volatile organic
compounds (2004)
5. US Pat 6,464,960, Water containing aerosol hair spray with a reduced content of
volatile organic compounds (2002)
6. US Pat 6,432,390, Low VOC methyl acetate hair sprays (2002)
7. US Pat 6,638,992, Hair care compositions (2003)
8. US Pat 6,562,325, Use of stabilized starches in low VOC, polyacrylic acid-containing
hair cosmetic compositions (2003)
9. US Pat 6,663,855, Cosmetic and personal care compositions (2003)
10. US Pat 6,649,154, Hairdressing cosmetic preparation and hairdressing method using
the same (2003)
11. US Pat 6,579,517, Cosmetic product (2003)
For Further Reading

On the Web: For more on package design, visit http://www.
cosmeticpackaginganddesign.com/features/featureFall011.htm
Publications:
M Sangiovanni, Sprays under pressure: EPA announces consumer products
rule, Spray Technology & Marketing, Vol 6, no 5. 8–16 (May 1996)
M Johnsan, The analysis of aerosol hair sprays, Spray Technology & Marketing,
Vol 4, no 2. pp 19-24 (Feb 1994)
Scientific basis for VOC reactivity issues raised by Section 183(e) of the Clean Air
Act Amendments of 1990, J Air & Waste Management Assn 46 (Oct 1996)
E Walls and HK Krummel, Low VOC Hair sprays: Formulation challenges for
a changing industry, Cosmet Toil 108(3) 111-117 (1993)
Chapter 35
Understanding “Mild”
Cosmetic Products
Mildness for personal care products is defined and strategies to
achieve mild products discussed. The industry standard tests for
ascertaining mildness are also briefly described.
key words: allergic contact irritation, surfactant, preservative,

fragrance, sunscreen
A s cosmetic science has advanced, so have consumer expectations for cosmetic

products. While consumers were once content with products that simply per-
formed their primary function, now it is taken for granted that products will have
a high degree of performance. In addition, products are expected to be estheti-
cally pleasing and safe to use. One aspect of safety that concerns consumers can
be described as “mildness,” which is the product’s ability to perform its intended
function without irritating skin or eyes. This article defines mildness in the context
of cosmetic products, provides tips on how to formulate them, and describes some
techniques used to measure product mildness.
What is “Mildness?”
The term “mildness” means different things to different people. A consumer
generally understands the term as describing a product that will not cause irritation.
The second edition of the “American Heritage Dictionary” defines mild as follows:
“gentle or kind in disposition, manners, or behavior; moderate in type, degree, effect,
or force; and not very severe, not extreme.” In the context of cosmetic products,
consumers generally believe that mild cosmetic products will not cause extreme
or severe side effects. Even though the term does not have a specific meaning for
consumers, it does set up certain expectations that the formulator must address.
A specific technical definition is no easier to come by: A literature search was
unable to come up with a standard definition of mildness. So, for the purposes of
this article, we define it as follows: “Mildness is the ability of a product to perform
its primary function without causing an unacceptable level of negative side effects
such as irritation, allergic reaction, or sensitization of the skin or eyes.” A key term
in this definition is “unacceptable level.” For some products, a certain level of side
effects may be acceptable. For example, products designed to enhance skin exfo-
liation that contain alpha hydroxy acids (AHAs) or retinoic acid may cause some
minor burning and redness. Such reactions are generally considered acceptable
333
334
Understanding “Mild” Cosmetic Products Beginning Cosmetic Chemistry
because of how such a product works and the benefits it provides. However, a
similar level of irritation from a foundation makeup or skin cleanser would be
completely unacceptable.
What “Mildness” is not: Irritation

To understand mildness, it is important to understand its opposite. Products
that are harsh can cause irritation, allergenicity, and sensitization. Irritation, or
more accurately irritant contact dermatitis (ICD), is the most common adverse
reaction to skin-care products. Symptoms include erythema (redness), burning,
itching, and flaking. The defining characteristic of this type of irritation is that the
damage to the stratum corneum (SC) does not involve associated immunological
reaction. This damage may be caused by chemicals with an excessively high or low
pH, or by solvents or surfactants that dissolve and disrupt the natural barrier lipids
of the skin. Irritation can also be caused by purely physical effects, like the rubbing
used to apply some products, or by abrasive particles used in scrub products.1 In
general; development of irritation depends on the wholeness of the SC barrier. If
the outer layer is intact, irritants are less likely to penetrate and irritation is less
likely to occur.
Allergic Reactions
Allergic contact dermatitis (ACD) presents symptoms similar to ICD but differs
in cause. ACD is an immunologic phenomenon in which invasive chemicals are
viewed as antigens, or potentially infectious agents, by the body. The presence of
these antigens triggers the body to produce antibodies: proteins that are capable of
interacting with the offending chemicals. Specifically, contact allergens are materials
that cause a response in T lymphocytes. This process can occur even with intact
skin as contact allergens are almost always small molecules that can penetrate the
skin and interact with the living tissue.1 Similar reactions can stem from exposure
to another class of materials known as haptens. Haptens are small molecules that
can not elicit an immune response by themselves but can prompt a reaction when
they are attached to a larger carrier molecule such as a protein. For both allergens
and haptens, the factors that cause a chemical to be sensitizing are related to its
molecular weight, charge, electrophilic potential, and to some degree its structure.
Because this cellular response can take time, initial exposure to allergen or haptens
may not cause symptoms. But after the antibodies have been developed, subsequent
exposures can rapidly cause the problem. How the allergy is expressed depends
on a combination of genetic factors, concentration of exposure, duration of skin
contact and the allergenic potential of the material.2
Sensitization
Once an individual has this immune response, that person is said to be sensi-
tized to the material. Subsequent exposure is more likely to result in appearance of
symptoms. A special type of sensitization is photoallergic dermatitis, which occurs
when the allergens are activated by certain wavelengths of light. When the offending
material is present on areas of skin that are exposed to sunlight, an allergic response
335
is triggered. For both irritation and allergic reaction, the end result is similar: the
consumer may experience, redness, itching, and burning sensations
Harsh Ingredients
A variety of ingredients used in cosmetics and over-the-counter drugs are
known to cause allergic reactions. To name a few, sensitizers include: fragrances,
preservatives, hair dye (p-Phenylenediamine), lanolin, glyceryl thioglycolate (used
in permanent wave formulations), propylene glycol, toluenesulfonamide/formal-
dehyde resin (used nail polishes), and sunscreens.1
Interestingly, researchers have demonstrated that product mildness can be af-
fected by extraneous factors such as water hardness. Surfactant exposure is widely
recognized to cause contact dermatitis, which is a general term used to describe
nonspecific skin irritation. This irritation is due, at least in part, to the water loss
that occurs when the intercellular lipids are disrupted. Surprisingly, research by
Raphael Warren and Keith Ertel has shown that calcium ions present in wash water
can increase this damaging effect.
Using a forearm controlled-application technique, they evaluated the irritancy
of surfactant solutions with different levels of water hardness. Their results showed
that even water hardness levels found in homes with water softeners (0–11 grams)
caused increased skin damage. They surmised that this effect has a dual cause:
One is the direct effect of calcium on the skin and the other is related to the indi-
rect effect of calcium with surfactants. This correlates well with studies showing
that calcium can interfere with the skin’s ability to repair its moisture barrier after
exposure to surfactants. Therefore, harder water—with its higher level of calcium
can increase the damage caused to skin by certain surfactants.3
Harsh products
As one might imagine, a wide range of products can cause ACD, the North
American Contact Dermatitis Group reports the main causes in Table 35.1.
Table 35.1. Major causes of allergic contact dermatitis according to the

NACDG (survey done in 1987)2
Skin-care products 28%

Hair-care products 24%
Facial cosmetics 11%
Nail cosmetics 8%
Fragrance products 7%
This list would be expanded if causes of irritation were surveyed as well. De-
tergent materials which degrease the skin and affect its barrier function are prime
problems in this case. These products include skin cleansers, bar soaps, facial
washes and shampoos.
336
Hypoallergenicity
Another important term associated with mildness is hypoallergenicity. Here,
too, no definition is universally accepted. Hypoallergenicity means that a product
is less likely to cause an allergenic reaction, such as redness, rashes, itching and
burning sensations. In 1974, the US Food and Drug Administration (FDA) stepped
in and proposed a standard definition for the term: that hypoallergenic products
cause significantly fewer adverse reactions. However, this regulation never took
effect because it was challenged in court by two cosmetic companies. Ultimately,
the courts did not uphold the FDA’s definition. A 1978 consumer survey seems to
corroborate that this is not a good definition.4 In this survey, panelists who were
familiar with the term hypoallergenic were asked to define it in their own words.
Next, they were asked to choose the most suitable definition from a multiple choice
list which included the FDA’s proposed definition. Finally, the panelists were asked
if hypoallergenic is considered to refer to all types of negative reactions or only
those involving an allergic reaction.
The responses to the first question indicated that about one third of the people
thought that hypoallergenic simply refers to products that are advantageous for,
or that are designed for, people with allergies or sensitive skin. Many respondents,
about 20%, thought that the term means that these products are nonallergenic,
meaning they do not cause any allergic reaction whatsoever. Other responses con-
sidered hypoallergenic products to be “milder” than comparable products. In the
multiple-choice questions, only a small number of panelists, about 9%, agreed with
the FDA’s proposed definition. Foremost, they considered the term to mean simply
that the products cause fewer allergic reactions. While Eiermann indicated that these
panel results represented good reason to not accept the FDA’s proposed definition,
he also noted that few consumers have the medical background to distinguish the
difference between irritation and sensitization. He also observed that a fairly large
number of respondents, about 37%, believe that hypoallergenic products cause
no adverse reactions whatsoever. This belief is somewhat alarming; it means that
consumers may have a falsely high sense of product safety.4 It might be interesting
to run a similar study again, as this panel was conducted in 1974. Nonetheless, it
indicates the need for careful consideration of truthful cosmetic labeling.
Formulating Mild Products

While every formula should be designed with safety in mind, mild products re-
quire special considerations. Perhaps the simplest way to formulate a mild cosmetic
product is to reduce or eliminate the level of an irritating ingredient. In general,
a reduced amount of an irritating ingredient leads to a reduction in irritation. The
drawback to this method is that, by reducing that ingredient, you may theoretically
be reducing the efficacy of the formula. A balance must be struck between the op-
timum performance level and the optimum mildness level. Formulators should also
consider how ingredients are delivered in the formula. While some ingredients are
irritating when they are incorporated directly into a formula, their sensitizing effect
can be reduced by using an appropriate delivery system. Delivery systems that can
reduce the irritancy of an ingredient include specialized emulsions, liposomes, and
337
nanosomes. These systems help minimize exposure, thereby improving mildness.

Unfortunately, even after optimizing ingredient concentration and the delivery
system it is likely that your formula will still contain functional ingredients such as
surfactants, fragrances, preservatives, and solvents that are potential irritants.
Surfactants and quats: Surfactants are used in nearly all cosmetic products for
myriad reasons. They provide cleansing, emulsification, foaming, and thickening.
However, they are also some of the most irritating types of cosmetic compounds,
affecting many people’s skin and eyes. For example, in a shampoo, ingredients
like sodium lauryl sulfate and ammonium lauryl sulfate can cause eye stinging.
Quaternized surfactants, which are the primary ingredient in hair conditioners, also
exhibit an irritation potential. Because these ingredients are highly functional and
inexpensive, it is a challenge to formulate effective, mild products with them.
One method for reducing the irritancy of surfactant-based products is to use
amphoteric surfactants or succinic ester sulfonates. These are zwitterionic sur-
factants that become protonated in an acidic environment or deprotonated in an
alkaline one. In the United States, the most commonly used amphoterics include
disodium cocoamphodiacetate, sodium lauroamphoacetate, and disodium lauro-
amphodiacetate. Other mild surfactants include sodium cocoyl isethionate, decyl
polyglucoside and disodium cocoamido methyl ethyl amine (MEA) sulfosuccinate.
However, these latter substitutes have been reported as being slightly more irritating
than the amphoterics. When formulating with these less-irritating surfactants, the
amphoterics are typically incorporated in blends that balance reduction in irritancy
with the desired performance characteristics.5 The irritancy of surfactants may
also be reduced by increasing ethoxylation. For example, an anionic material like
sodium lauryl sulfate (SLS) is more irritating than its related ethoxylated product
sodium laureth sulfate (SLES). Surfactant irritation can also be reduced by adding
refatting agents or large, hydrophobic polymers to the formula.
Preservatives: Preservatives constitute another type of raw material that can
display harsh reactions with certain consumers. The currently available crop of
preservatives can cause both contact sensitization and skin and eye irritation. Ide-
ally, you would want to avoid using preservatives that cause sensitization, but this
scenario is not possible in most formulations. Even the so-called “preservative free”
formulations found in the cosmetics industry rarely have no preservation system at
all. Instead, such products are more likely to use self-preserving systems. To address
the desire of formulators to have more mild products, preservative suppliers have
tried developing less irritating preservative systems.
You can employ a variety of strategies to reduce the irritancy of a preservative
system. One way is to use multi-functional ingredients, materials that have other
functions in addition to preserving the product. For example, phenoxyethanol is
both a natural preservative and a fragrant material. Other aroma chemicals—such
as alcohols, esters, aldehydes and terpenes—also show antimicrobial activity. Some
botanicals and herbals can be used: tea tree oil is known to have a natural fungicidal
effect. Certain surfactants have a preservative effect. The overall irritation potential
of a formula using multifunctional ingredients can be reduced because a single
ingredient replaces multiple, more irritating ingredients.
338
Another way to mildly preserve a product is by adjusting the pH of the system.

Microorganisms only grow within defined pH parameters. High-acid products
tend to be more unfavorable for microbial growth. Highly alkaline pHs tend to
prevent microbial growth also. While adjusting the pH may lead to some sensi-
tivity in certain individuals, it is less likely to be a problem than using sensitizing
preservative compounds.
Other ways to reduce the amount of preservative, thus increasing mildness,
include using packaging that is more protective, including synergistic ingredients
or using the latest in preservative technology. For instance, chelating agents are
added to a system to work synergistically with the main preservative. This allows
the total concentration of preservative to be reduced.
The latest technology in the preservative field covers the so-called enzymatic
systems. Enzymatic microbial-control systems involve using biochemical reactions
to preserve a product. For example, glucose oxidase in conjunction with glucose
uses up the oxygen in a closed system, thereby preventing microbial growth.6
Fragrances: Nearly as important as the “active” ingredients in a formulation is
the fragrance. It imparts a pleasant odor that masks undesired raw material odors
and body odors. Unfortunately, many of the ingredients used for creating fragrances
are irritants and can cause contact dermatitis. Potentially irritant or sensitizing fra-
grances are so prevalent that they are the most common cause of cosmetic-related
allergies. Some fragrance ingredients that cause reactions include methyl octin
carbonate, methyl heptin carbonate, and benzylidene acetone.1
One way that cosmetic chemists have produced mild products has been to
remove fragrances from consumer products. These products are often labeled
“fragrance free” or “unscented.” In other cases, the odor of the base raw materials
remains too objectionable for consumers, so manufacturers must put fragrances
in products to cover the smell of these materials. The fragrances chosen for “mild”
products are much less complex and include fewer ingredients than typical product
fragrances.
Other ingredients: Some specialty ingredients have been shown to cause ir-
ritation. Certain sunscreen ingredients are known to cause allergic reactions. PABA
has been reported to be a sensitizer at relatively low levels (5%). Cinnamates are
also sensitizers. To a lesser extent, ingredients like benzophenones, salicylates and
anthranilates can all be sensitizers. Physical sun-blocking chemicals like titanium
dioxide are not sensitizing.
Botanical additives which have alcohol-containing solvent systems can be drying
to certain people’s skin. Colorants can be sensitizing. For example, coal tar is thought
to cause dermatitis. Some D&C red dyes are reported to be comedogenic.
Certain product types are sensitizing by their nature. These include AHA skin
creams, depilatories, hair relaxers, hair colors and bleaches.1
Mildness Testing
Developing a mild formulation requires testing to ensure that the new product
is milder than standard products. A variety of tests have been developed for this
purpose.
339
Human testing: Patch testing assesses the effect of an ingredient or formulation

on skin. It is used to determine whether a product can cause irritation or sensitiza-
tion or not. For patch testing, products are applied on a human volunteer’s back
or forearm as either neat or dilute solutions in sterile water. The area is covered
with either an occlusive or semi-occlusive patch and left there for two days. Then
the patch is removed and the site is examined after 15 min, 24 h and 48 h. Using a
standard scoring system, the level of irritation can be determined.
The Repeat Insult Patch Test resembles a standard patch test, but the same
area of the body is tested multiple times. Ten patches are applied to the same site
at 48 h intervals for three to four weeks. The skin is allowed to rest two weeks and
then product, is again applied to the area for another 48 h. Readings are taken
to determine if a material is a sensitizer or low-level irritant. Another patch test,
called the 21-day cumulative irritancy test, may also be done to measure a product’s
irritancy potential. This test is designed to maximize irritant reactions. A newer
14-day test is now available that is gaining popularity as a predictive test. When
the photosensitivity of a product is in question, a photopatch test can be run. This
method involves irradiation of the site and evaluation after 24–48 h.7
The soap chamber test is designed to work for soaps, lotions and cream products.
It is similar to a patch test. However, it employs aluminum chambers to deliver the
test product to the human volunteer’s forearm. These chambers are taped on. The
product is applied daily to the same spot and worn for 24 h. It is repeated each day
for one week. At the end of the test, the test chamber is reapplied for a few hours.
The subjects are then evaluated for levels of erythema, scaling, and fissuring.1
For further details on specific patch test methodology, visit the web site listed
in reference 8.
Animal testing: In the United States, cosmetics and skin-care products can be
evaluated using the Draize tests. In this test, six albino rabbits are exposed to a test
substance for 24 h. The skin is examined and an irritancy score can be assessed.
Intradermal safety testing is also done with rabbits. Rabbits are injected with
a test product solution and then an Evans blue solution. The diameter of the zone
of bluing gives an indication of irritation potential.9
Other animal tests may also be performed to ensure a product’s mildness. The
guinea pig maximization test measures the sensitizing potential of ingredients. The
albino rabbit eye irritancy test evaluates whether a product will be an eye irritant
or not.
Alternatives to animal testing: Because animal testing has been seen as a
potential public relations problem, companies have developed some alternative
in vitro testing methods. Two methods are the LDH leakage assay and the MTT
reduction test. These procedures test for cytotoxicity in human fibroblast cultures.
Cytotoxicity testing can also be done in skin/eye tissue equivalents like Epi Derm
and Epi Ocular. In addition, cytokine testing is another viable option.
The LDH test takes advantage of the fact that lactate dehydrogenase leaks from
cells when they are damaged by surfactants. The amount of the LDH that leaks is
an indication of the amount of cellular damage. This has been shown to correlate
with skin irritation.
340
The MTT test allows you to evaluate the mitochondrial dehydrogenase activ-
ity. It demonstrates toxic effects on cell metabolism by the rate of color change of
the MTT compound from yellow to blue. It tests mitochondrial integrity and cell
viability. These values have been shown to relate to surfactant irritation.10
The authors would like to thank Catherine Lazaro, Senior Regulatory Affairs Specialist at Alberto Culver
for her help in preparing this article.
Summary
Table 35.2 summarizes some of the principles of formulation to avoid irritancy
as explained in this article. Application of these principles should result in a milder
product than if they are ignored. However, a formulation must be properly tested
before mildness can be claimed; even applying all the principles may still not give
a totally nonirritating product, especially if the product type is inherently irritating,
such as an AHA renewal cream, or a permanent-wave solution.
References
1. Z Draelos, Cosmetics in Dermatology, 2nd ed, Churchill Livingstone, NY (1995)
2. R Rietshel and J Fowler Jr, Fisher’s Contact Dermatitis, 4th ed, Williams and Wilkins,
Baltimore (1995)
3. R Warren and K Ertel, Hard water: its impact on the mildness of personal care
products, Cosm Toil 112(11) 67–74 (1997)
4. H Eiermann, Consumers perceptions of hypoallergenic cosmetics, Cosm Toil 110(7)
33–7 (1995)
5. T Schoenberg, Formulating with non-traditional amphoterics, Cosm Toil 111(10)
99–103 (1996)
6. J Kabara and D Orth, (Eds.), Principles for Product Preservation in Preservative Free
and Self Preserving Cosmetics and Drugs Principles and Practice, Marcel Dekker NY
(1996)
7. R Bronaugh and H Maibach, Cosmetic Safety in a Primer for Cosmetic Scientists,
J Whittam (Ed.), Marcel Dekker NY,24 (1987)
8. http://www.dermatest.com.au/dermatest/protocolso.htm#patch
9. EM Jackson, Eye Irritation, Cosmetic Safety in a Primer for Cosmetic Scientists,
William Waggoner (Ed.), Marcel Dekker. NY 199(1987)
341
Table 35.2. Checklist of mildness problems and suggested fixes
Problem Factor(s) to try changing Possible drawbacks

Surfactants • Substitute amphoteric surfactants High cost,
and quats or succinic ester sulfonates, such Potential for
as disodium cocoamphodiacetate, reduced efficacy
sodium lauroamphoacetate, and
surfactants disodium
lauroamphodiacetate for some or
all anionic surfactants.
• Other mild surfactants include sodium High cost,
cocoyl isethionate, decyl polyglucoside Potential for
and disodium cocoamido MEA reduced efficacy
sulfosuccinate.
• Increase ethoxylation. Potential for
reduced efficacy
Preservatives
• Use multi-functional ingredients like Potential for
phenoxyethanol (natural preservative, reduced efficacy
fragrant); aromatic alcohols, esters,
aldehydes, terpenes (antimicrobial);
botanicals, herbals (antimicrobial,
fungicidal); surfactants to replace
multiple, more irritating ingredients.
• Adjust the system pH to prevent Limitations on
microbial growth. product pH
• Use more protective packaging High cost
Desired package type
may not be possible
• Include synergistic ingredients like Higher cost
chelating agents
• Use the latest in preservative High cost
technology, such as the so-called
enzymatic systems.
Fragrances • Avoid methyl octin or heptin carbonates Limits fragrance
and benzylidene acetone.2 choices
• Remove fragrance for a “fragrance free” Off odor from
or “unscented” product. ingredients
• Choose a much less complex fragrance Limits fragrance
with fewer ingredients than typically choices
used.
Sunscreens
• Delivery systems to minimize Higher cost
exposure, thereby reducing other irritancy: specialized
irritating materials emulsions, liposomes,
and nanosomes.
Sensitizers • Avoid known sensitizers: coal tars, Limits color,
some colors, some sunscreens, etc. active choices
Chapter 36
Formulating for Efficacy

Via the introduction of the Relative Polarity Index, the authors
show that the choice of emollients in cosmetic formulations
determines the total amount of skin penetration of active
ingredients whereas the choice of the emulsifier determines its
distribution within the skin.
key words: active ingredients, emollient selection, formulation

design, octanol/water partition coefficient, Relative Polarity Index,
skin distribution profiles
A ctive ingredients have been popular for more than a decade, and new actives
are continuously being identified, studied and promoted. Many of these actives
are supported by good in vitro efficacy data, and we have an increasing number of
ingredients for which also good in vivo efficacy evidence is available.
Based on this evidence, one would expect to find many active cosmetic products
in the marketplace, but unfortunately that is not the case. Assuming that the efficacy
data provided is robust (i.e., the active ingredient has indeed its claimed cosmetic
activity); questions arise about the formulation development process that should
assure that the efficacy of an active ingredient is transformed to an efficacious
cosmetic product. Cosmetic formulators should therefore select their ingredients
and manufacturing procedures in such a way that cosmetic efficacy is obtained. In
other words, they should formulate for efficacy. In many cases, however, it does
not happen.
Many companies have a number of standard formulations to which the latest
new active ingredient is simply added. Following stability testing and elimination of
those failing the stability tests, small clinical trials are performed with the remain-
ing formulations to assess whether the claimed efficacy of the active ingredient is
maintained in the standard formulation. In most cases, no efficacy is seen and after
some additional work, the active ingredient is discarded. Whereas the reasons for
using standard formulations are very understandable, this strategy does not lead to
the best possible product because it completely ignores the principles that underpin
the skin delivery of the active ingredient.
This chapter describes the selection criteria for ingredients in cosmetic formu-
lations that help to optimize the delivery of the active ingredient into the skin. As
formulations can be very complicated, many factors must be taken into account.
To date only a few have been systematically studied. The guidelines described in
this chapter are, therefore, only guidelines but the guideline recipe will be much
343
344
Formulating for Efficacy Beginning Cosmetic Chemistry
closer to an efficacious cosmetic formulation than a random choice from a selection

of standard formulations. As further results from new work become available, the
system will be further refined.
Theoretical Considerations for the Skin Delivery of Cosmetics

As illustrated in Figure 36.1, Barry described the skin penetration process as
a series of consecutive steps, each of which can potentially be rate limiting.1 First,
the chemical must diffuse within the formulation to the skin surface. There it parti-
tions into the skin, diffuses through the stratum corneum, partitions into the viable
epidermis and diffuses through the viable epidermis. It then partitions into and
diffuses through the dermis before partitioning into the fat deposits or it partitions
into the blood capillaries just beneath the viable epidermis/dermis interface.
Figure 36.1.
From this process, it can be concluded that both partition and diffusion are
very important in determining skin penetration. They are normally combined in
the permeability coefficient according to the formula:
(Eq. 36.1)
345
in which kp is the permeability coefficient, Koct/water the octanol/water partition

coefficient, D the diffusion coefficient and L the length of the pathway of diffu-
sion of the penetrating molecule. The unit of the permeability coefficient, cm/s,
indicates that this parameter basically reflects the speed with which a chemical
diffuses through the stratum corneum. However, in order to obtain efficacy a suf-
ficiently high concentration of the active ingredient must be reached at the site
of action and maintained for a sufficiently long period of time. Absolute amounts
are therefore also important but here some conflicting evidence is obtained from
skin penetration theory.
The most logical way to increase the degree of skin penetration is to increase
the concentration of the active ingredient in the formulation, according to the
well-known formula:
(Eq. 36.2)
in which Δ is the concentration difference of the penetrating molecule over the

stratum corneum (i.e., the difference in concentrations between the formulation
and the deepest layers of the stratum corneum). The larger this concentration dif-
ference, the greater the flux through the stratum corneum. At the same time, the
more soluble an active ingredient is in the formulation, the more active ingredient
can be contained in the formulation and the more can therefore penetrate into
the stratum corneum.
But difficulties arise when increasing the solubility of the active ingredient in
the formulation. According to the definition of the partition coefficient, the Ksc/form
of the penetrating molecule, the solubility of the active ingredient in the stratum
corneum is related to its solubility in the formulation as expressed in Equation
36.3:
(Eq. 36.3)
in which Cpenetrant represents the solubility of the penetrating molecule in either

the stratum corneum or the formulation. Because this K is the same as those in
Equations 36.1 and 36.2, the quantity of penetrating molecules into the stratum
corneum can be increased by increasing the solubility of the penetrating mol-
ecule in the stratum corneum or by reducing its solubility in the formulation. One
therefore must increase the solubility of the active ingredient in the formulation in
Equation 36.2 to achieve sufficiently high quantities to obtain efficacy in the skin,
but one must reduce the same solubility in order to force the material to leave the
formulation and partition into the stratum corneum.
The remainder of this chapter will describe how one can increase and reduce
the solubility of the active ingredient in the formulation at the same time via for-
mulation design using the Relative Polarity Index (RPI).
346
The Influence of Formulation Characteristics on Skin Delivery

The theoretical discussion above clearly indicates that the formulation deter-
mines the following parameters:
• The total amount dissolved in the formulation that is available for skin
penetration; the higher this amount, the more will penetrate until a satura-
tion concentration is reached in the skin, therefore a high solubility in the
formulation is required.
• The polarity of the formulation relative to that of the stratum corneum; if a
penetrant dissolves better in the stratum corneum than in the formulation,
then the partition of the active ingredient will favor the stratum corneum,
therefore a low solubility in the formulation is required.
Both requirements cannot be fully met at the same time but the problem can
still be solved using the novel concept of a RPI. In this systematic approach, it
is essential to consider the stratum corneum as yet another solvent with its own
polarity.
It appears that the stratum corneum behaves very similar to butanol, but in a
somewhat more polar fashion than butanol with respect to its solubilizing ability
for penetrants.2 The experimentally determined log Koctanol/water of 1-butanol is 0.88.3
For the purpose of this work, the polarity of the stratum corneum as expressed by
its octanol/water partition coefficient is set at 100.8, which is 6.3.
Partition Coefficient Determination or Calculation

For the following, it is essential to know what an octanol/water partition coefficient
is. The octanol/water partition coefficient is calculated according to the formula:
(Eq. 36.4)
n-Octanol and water do not mix and the octanol/water partition coefficient is a
measure of the polarity of a chemical. If the chemical is lipophilic, larger amounts
will dissolve in the lipophilic n-octanol than the polar water. For a hydrophilic
chemical, this process will be reversed.
This coefficient can be experimentally determined by assessing the maximum
solubility of a chemical in n-octanol and in water, respectively, or by assessing the
ratio of the concentrations of the chemical when dissolved in both phases at levels
below the maximum solubility. Alternatively, the partition coefficient can be esti-
mated from the chemical structure, although care should be taken which method
of calculation is being used.4 One should realize that the partition coefficient is
often expressed by its logarithmic value; in this chapter the RPI value of a chemi-
cal, stratum corneum or formulation is the 10log of the corresponding octanol/water
partition coefficient.
347
The Relative Polarity Index

The RPI is a way to compare the polarity of an active ingredient with that of
the skin and emollient components of cosmetic formulations. It is visualized as a
vertical line with a high polarity at the top and a high lipophilicity at the bottom. The
polarity is expressed by the octanol/water coefficient. In order to use the concept
of the RPI, three numbers (on log10 scale) are required, namely:
• The polarity of the stratum corneum, here set at 0.8 (but in reality this value
will change with the hydration state of the stratum corneum that is deter-
mined by factors such as the external relative humidity);5
• The polarity of the penetrating molecule;
• The polarity of the formulation. For multiphase (i.e., multi-polarity) systems
like emulsions, this is the phase in which the active ingredient is dissolved.
The polarities of these three entities can be placed on the RPI by simply mark-
ing their position on the vertical line.
Case I: Penetrants with a polarity equal to the stratum corneum: Imagine
the example of an active ingredient with a log Koct/water equal to that of the stratum
corneum (0.8). If the formulation now also has the same polarity, the solubility of
the penetrant in the stratum corneum and the formulation would be the same.
After equilibrium is reached, the concentration of active ingredient over the two
phases (formulation and stratum corneum) would be the same although the absolute
amount in both layers will depend on their respective volumes.
Based on the physicochemical characteristics of the system, no drive exists for
the active ingredient to leave the formulation and enter the skin, apart from the fact
that the stratum corneum does initially not contain any penetrant (i.e., a dilution ef-
fect). Such a situation is very unlikely because in reality almost all active ingredients
have polarities that differ from that of the stratum corneum. The second and third
cases are therefore much more common and deserve separate discussion.
Case II: Penetrants more polar than the stratum corneum: In order to
illustrate the use of the RPI with a penetrant that is more polar than the stratum
corneum, it is assumed that the active ingredient is the skin whitener arbutin
with a calculated log Koctanol/water of 0.01. First, the polarity difference between the
stratum corneum and the penetrant is calculated by subtracting the polarity of the
penetrant from that of the stratum corneum; in this case 0.8 – 0.01 = 0.79. See
Figure 36.2.
Figure 36.2.
348
In the second step, the polarity of the formulation is calculated. The polarity of
the phase of the formulation in which the active ingredient is dissolved should be
0.79 more or less than that of the active ingredient itself; that means either greater
than 0.8 (0.01 + 0.79) or smaller than –0.78 (0.01 – 0.79).
For formulations that are more lipophilic than the stratum corneum, the arbutin
will be more soluble in the stratum corneum than in the formulation and would
therefore prefer to be located in the stratum corneum, creating a driving force for
partitioning into the stratum corneum. The more extreme the difference in polarity
between the formulation and the active ingredient, the greater this driving force for
partition into the stratum corneum. This event is illustrated on the left in Figure
36.3 by the width of the red blocks (arrows).
However, at the same time, the solubility of the penetrant in the formulation
will reduce if the polarity difference between formulation and active ingredient
is enlarged. This phenomenon is illustrated by the green blocks on the right in
Figure 36.3.
Figure 36.3.
In the case of arbutin, a formulation with a polarity of 4 has a greater driving force
for partitioning arbutin into the stratum corneum than a formulation with a polarity
of 1 because 3.99 (4 – 0.01) is greater than 0.99 (1 – 0.01). Likewise, a formulation
with a polarity of –3 has a greater driving force for partitioning arbutin into the
stratum corneum than a formulation with a polarity of –1 because 3.01 (–3 – 0.01)
is greater than 1.01 (–1 – 0.01). Only the absolute difference counts. Practically, of
course, it is much more difficult to dissolve arbutin in an aqueous solvent with a
polarity of –3 than –1 or a lipophilic solvent with a polarity of 4 than 1.
Case III: Penetrants more lipophilic than the stratum corneum: A much
more common situation is that in which the penetrants are more lipophilic than the
stratum corneum. This time, it is assumed that the active ingredient is octadecene-
dioic acid (referred to hereafter as dioic acid), a much more lipophilic skin whitener6
with a theoretical log Koctanol/water of 5.84 and an experimentally determined log Koctanol/
water
of 5.74 ± 0.29. For simplicity, the value of 5.8 has been used in the calculations.
Again, the polarity difference between the stratum corneum and the active ingredi-
ent must be calculated first, which is 5 (5.8 – 0.8). See Figure 36.4.
349
Figure 36.4.
In the next step, the polarity of the formulation should be calculated. The
polarity of the phase of the formulation in which the active ingredient is dissolved
should be more than 5 away from that of the active ingredient itself; that is, either
above 10.8 (5.8 + 5) or below 0.8 (5.8 – 5).
For formulations that are less lipophilic than the stratum corneum, the dioic
acid is more soluble in the stratum corneum than in the formulation and would
therefore “prefer” to be located in the stratum corneum rather than in the formula-
tion, creating a driving force for partition into the stratum corneum. As before, the
more extreme the difference in polarity between the formulation and the active
ingredient, the greater the driving force for partition into the stratum corneum.
This is illustrated on the left in Figure 36.5.
At the same time, the solubility of the penetrant in the formulation will reduce
if the polarity difference between formulation and active ingredient is enlarged.
This phenomenon is illustrated on the right in Figure 36.5.
Figure 36.5.
In the case of dioic acid, a formulation with a polarity of 10 has a greater driv-
ing force for partitioning dioic acid into the stratum corneum than a formulation
with a polarity of 7 because 4.2 (10 – 5.8) is greater than 1.2 (7 – 5.8). Likewise, a
formulation with a polarity of –3 has a greater driving force for partitioning dioic
acid into the stratum corneum than a formulation with a polarity of –1 because
350
8.8 (–3 – 5.8) is greater than 6.8 (–1 – 5.8). Again, only the absolute difference
counts. Practically, of course, it is much more difficult to dissolve dioic acid in an
aqueous solvent with a polarity of –3 than –1 or a lipophilic solvent with a polarity
of 10 than 7.
Using the Relative Polarity Index in Practice

From the theory discussed above, it can be concluded that the polarity of the
formulation must be as far away as possible from the polarity of the active ingredi-
ent in order to increase the driving force of the active ingredient into the skin, but
at the same time as close as possible to that of the active ingredient to ensure that
high concentrations can be reached to ensure that enough material penetrates.
Because these two opposing requirements cannot be met at the same time, it is
necessary to describe how to find the optimum polarity of the formulation from
the point of view of skin delivery.
Step 1: Optimizing the solubility by selecting the primary emollient or
solvent: After having calculated the polarity difference between penetrant and
stratum corneum and hence the acceptable polarity ranges of the formulation, the
formulator should have an idea whether the phase containing the active ingredient
will be hydrophilic or lipophilic in nature. In other words, will the formulation be
at the top or at the bottom of the RPI as indicated by the arrows in Figures 36.3
and 36.5? It is important to note that if a lipophilic penetrant is dosed in an o/w
emulsion and dissolved in the internal oil phase, the phase containing the penetrant
is lipophilic in nature whereas the formulation may be hydrophilic in nature.
As a first step, an emollient (for lipophilic active ingredients) or a water-miscible
solvent (for hydrophilic active ingredients) in which the active ingredient dissolves
well should be identified. This primary emollient or solvent is chosen in the direc-
tion of the required RPI. In other words, choose an emollient with a RPI value not
too far away from that of the active ingredient, for instance 7 or 8 in case of dioic
acid if the polarity of the final formulation will be lipophilic or 3 or 4, if the final
formulation will be hydrophilic. Table 36.1 provides RPI values of some typical
emollients and hydrophilic solvents that span a wide range. These RPI values can
be used to select a suitable solvent or emollient.
Step 2: Optimizing the driving force by selecting the secondary emollient
or solvent: Once a suitable primary emollient or solvent has been selected, the
driving force for penetration into skin must be increased by reducing the solubility
in that solvent. This reduction is typically done by incorporating another solvent,
the secondary emollient or solvent, in which the active ingredient is far less soluble
but still miscible with the originally chosen solvent or emollient.
When adding increasing amounts of the secondary emollient or solvent, the
solubility of the active ingredient is gradually reduced and, as a consequence, the
total amount of active ingredient dissolved relative to what could be dissolved in-
creases. Sufficient secondary emollient or solvent has been added when this fraction
of maximum solubility has reached a value of about 90% in that solvent mixture.
351
Table 1. Relative Polarity Index values for some hydrophilic solvents and
lipophilic emollients typically used in cosmetic formulations
Calculated
log P
INCI name Trade name, supplier value
Glycerin Pricerine 9091, Uniqema –1.76
Dipropyleneglycol DPG LO+, Dow Chemical USA –1.20
Propylene glycol 1,2-Propylene Glycol Care, BASF –0.92
Ethanol Pharconix BPS PF, Ichimaru Pharcos. –0.32
Triethylhexanoin Estol 3609, Uniqema 2.70
Glyceryl isostearate Prisorine 2040, Uniqema 4.76
Isopropyl myristate Estol 1512, Uniqema 5.41
Propylene glycol isostearate Prisorine 2034, Uniqema 6.08
Isopropyl isostearate Prisorine 2021, Uniqema 7.40
Ethylhexyl palmitate Estol 1543, Uniqema 9.12
Ethylhexyl isostearate Prisorine 2036, Uniqema 10.05
Vegetable squalane Pripure 3759, Uniqema 14.93
Triisostearin Prisorine 2041, Uniqema 18.60
Trimethylolpropane
triisostearate Prisorine 3630, Uniqema 20.27
Pentaerythrityl
tetraisostearate Prisorine 3631, Uniqema 25.34
Isostearyl isostearate Prisorine 2039, Uniqema 26.98
Skin Delivery Experiments Demonstrating Use of RPI

An example of the use of RPI is the formulation of dioic acid for which RPI
values of more than 10.8 and less than 0.8 would be acceptable.
Propylene glycol isostearate with an RPI of 6.08 was chosen as the solvent for
this particular penetrant and the solubility assessed to be 17% w/w. This solubility
was too high to guarantee a good driving force for diffusion; therefore, increasing
amounts of triethyl-hex--anoin were added to reduce the solubility to just above
2% in the total formulation (10% in the oil phase). In this way, the composition
shown in Formula 36.1 was created. Formula 36.2 was made simply based on
physical stability of the emulsion system. Formulas 36.1 and 36.2 were used to
demonstrate the influence of the emollients on skin delivery. Formula 36.3, which
differed from Formula 36.1 principally in the choice of surfactants, was used to
investigate the influence of the emulsifier on skin delivery.
The influence of the emollients: Formulas 36.1 and 36.2 were tested sepa-
rately for skin delivery.
352
Formula 1. Dioic acid-containing o/w formulation designed according to

the Relative Polarity Index principles, i.e. skin delivery optimized
Propylene glycol isostearate (Prisorine 2034, Uniqema) 15.0% w/w
Triethylhexanoin (Estol 3609, Uniqema) 3.0
Octadecenedioic acid (Arlatone Dioic DCA, Uniqema) 2.0
Steareth-21 (Brij 721, Uniqema) 5.0
Glycerin (Pricerine 9091, Uniqema) 4.0
Xanthan gum (Keltrol, Kelco) 0.2
Phenoxyethanol (and) methylparaben (and) propylparaben (and) 0.7
2-bromo-2-nitropropane-1,3-diol (Nipaguard BPX, Nipa)
Aqua (water) qs 100.0
Formula 2. Dioic acid-containing o/w formulation designed solely on

physicochemical stability and not optimized for skin delivery
Caprylic/Capric triglyceride (Estol 3603, Uniqema) 10.0%w/w
Glyceryl stearate SE (Estol 1461, Uniqema) 3.0
Cetyl alcohol (Lanol C, Seppic) 2.0
Benzoic acid (Unisept BZA, Universal Preserv-A-Chem Inc.) 0.2
2-Amino-2-methyl-1-propanol (AMP, Angus Chemie GmbH), to pH 5.5 qs
Aqua, distilled qs 100.0
Formula 3. Dioic acid-containing o/w formulation designed according to

the Relative Polarity Index principles using a different emulsifier system
than Formula 1
Propylene glycol isostearate (Prisorine 2034, Uniqema) 15.0%w/w
Triethylhexanoin (Estol 3609, Uniqema) 3.0
Sorbitan stearate (and) sucrose cocoate (Arlatone 2121, Uniqema) 5.5
Xanthan gum (Keltrol, Kelco) 0.2
Phenoxyethanol (and) methylparaben (and) propylparaben (and)
2-bromo-2-nitropropane-1,3-diol (Nipaguard BPX, Nipa) 0.7
Aqua (water) qs 100.0
For the delivery-optimized formulation (Formula 36.1), full-thickness pigskin

dermatomed to 400 µm was used in vitro in a Franz-diffusion cell dosed at a rate
of 10 µL/cm2. Cells were left in place for 24 hours after which the formulation was
removed; the skin was tape-stripped 21 times; strips, remainder of skin and recep-
tor fluid were analyzed to assess skin penetration.
353
For the formulation that was not optimized for skin delivery (Formula 36.2),
full-thickness pigskin (500 µm) was used in vitro in a Bronaugh flow-through dif-
fusion cell dosed at a rate of 66 µL/cm2. Cells were left in place for 20 hours after
which the formulation was removed; the skin was tape-stripped five times; strips,
remainder of skin and receptor fluid were analyzed to assess skin penetration.
Results of these experiments are given in Figure 36.6.
As can be seen from Figure 36.6, the total delivery (i.e., the sum of the amounts
recovered in the tapes, the skin and transdermal delivery) is far greater from the
formulation that was optimized for skin delivery, therefore illustrating the validity
of the use of RPI values for selecting emollients to enhance skin delivery.
Figure 36.6.
The differences in skin penetration methodologies between the two experiments

were only minor; although the delivery-optimized formulation had a six-fold lower
dosing rate than the formulation not optimized for skin delivery (favoring the skin
penetration from the latter), both were performed under infinite dosing conditions.
Dermal delivery after 22 hours may be considered to be constant after steady-state
transdermal fluxes have been achieved (data not shown). In other words, we believe
the observed difference in skin penetration to be due to differences in formulation
design rather than to differences in skin penetration methodology.
Because dioic acid must be delivered to the melanocytes where it reduces the
quantity and/or half-life of the tyrosinase enzyme (the enzyme involved in skin
color formation),7 the delivery to the skin layer should be as high as possible. Due
to the use of the RPI concept, the skin delivery has increased 3.5-fold, from 4.3
to 14.0 µg/cm2, without an increase in the concentration of the active ingredient
in the formulation.
Concentrations of above 2% dioic acid in the formulation that was not opti-
mized for skin delivery were previously tested for skin delivery8 and demonstrated
that a four-fold increase in dioic acid concentration in the formulation (from 2
to 8%) resulted in only a two-fold increase of skin delivery (from 4.3 to 8.0 µg/
cm2). It may therefore be advisable to change a standard formulation by selecting
354
emollients according to the RPI concept rather than change the active ingredient
or its concentration.
The influence of the emulsifier: So far, the tested formulations only differed
in terms of their emollients, which showed that the choice of the emollients greatly
influences the total quantity of active ingredient absorbed into the skin. But the
effect of the emulsifier on skin delivery of active ingredients is also of interest.
Emulsifiers often act as skin penetration enhancers, in particular the cationic, fol-
lowed by the anionic and finally the nonionic. Whereas the nonionic surfactants
penetrate better into skin, their interaction with skin lipids and therefore skin
penetration enhancement is less extensive.9
In order to investigate the effect of the emulsifier on the skin penetration of
dioic acid, Formula 36.3 was prepared using the same concentrations of dioic acid,
propylene glycol isostearate and triethylhexanoin as in the skin delivery-optimized
formulation, but a different surfactant was selected. Because this emollient combina-
tion was selected on the RPI concept, it is also a skin delivery optimized formulation.
The only difference from the Formula 1 is the emulsifier system.
Skin delivery results are depicted in Figure 36.7 and show that while the total
amount delivered is high in both cases (due to the choice of primary and secondary
emollient via the RPI concept) a completely different skin distribution pattern is
obtained. Because it has been observed a few times for different emulsifiers, both
o/w and w/o, it is suggested that the emulsifier influences the distribution of the
active ingredient within the skin. No explanation can be given for this phenomenon
at the present time.
Figure 36.7.
Conclusions
Most cosmetic companies will formulate their active ingredients into a few
standard formulations prior to efficacy testing, almost exclusively based on physical
and chemical stability and sometimes on sensory properties. Subsequent efficacy
tests often reveal the cosmetic product to be without cosmetic activity.
355
Based on theoretical considerations, it was predicted that the polarity of the

phase in which the active ingredient of a cosmetic formulation is located would have
a profound influence on the flux of the active ingredient into the skin. Examples
for a hydrophilic and a lipophilic penetrant clearly demonstrate that the efficacy of
formulations can be improved by selecting the right emollient (system) using the
Relative Polarity Index. This involves dissolving an active ingredient at the highest
possible concentration in a primary emollient and then reducing its solubility to
an acceptable level using a secondary emollient.
Initial skin penetration experiments showed that formulations designed accord-
ing to this concept deliver significantly more active ingredient into the skin than
formulations that have “only” been optimized for physical stability.
Further research into the other components of cosmetic formulations revealed
that the choice of emulsifier is also important, because it seems to determine the
distribution profile of the active ingredient within the skin. Whereas the reasons
for the choice of the emollient are clearly understood from a theoretical point of
view, the rationale for selecting the right emulsifier remains unclear and further
research will be necessary to elucidate the exact influence of the emulsifier on
skin delivery.
Published March 2004 Cosmetics & Toiletries magazine.
References
1. BW Barry, Dermatological Formulations, Marcel Dekker, New York 128 (1983)
2. RJ Scheuplein and IH Blank, Mechanism of percutaneous absorption. IV. Penetration
of non-electrolytes (alcohols) from aqueous solutions and from pure liquids, J Invest
Dermatol 60 286–296 (1973)
3. C Hansch and A Leo, Substituent Constants for Correlation Analysis in Chemistry and
Biology, J Wiley & Sons, New York (1979)
4. R Mannhold, RF Rekker, C Sonntag, AM ter Laak, K Dross and EE Polymeropoulos,
Comparative evaluation of the predictive power of calculation procedures for
molecular lipophilicity, J Pharm Sci 84 1410–1419 (1995)
5. JA Bouwstra, A De Graaff, GS Gooris, J Nijsse, JW Wiechers and AC Van Aelst, Water
distribution and related morphology in human stratum corneum at different hydration
levels, J Invest Dermatol 120 750–758 (2003)
6. JW Wiechers, FJ Groenhof, VAL Wortel, NA Hindle and RM Miller, Efficacy studies
using octadecenedioic acid, a new nature-derived ingredient to even Asian skin tone,
SÖFW 128 2–8 (Sep 2002)
7. JW Wiechers, Melanosomes, melanocytes and dioic acid, Proceedings of the 37th
Annual Conference of the Australian Society of Cosmetic Chemists, “Cosmetics on a
New Horizon”, Hamilton Island, Queensland, Australia (13–16 March 2003)
8. JW Wiechers, FJ Groenhof, VAL Wortel, RM Miller, NA Hindle and A Drewitt-Barlow,
Octadecenedioic acid for a more even skin tone, Cosmet Toil 117(7) 55–68 (2002)
9. SB Ruddy, “Surfactants.” In EW Smith and HI Maibach (Eds), Percutaneous
Penetration Enhancers, CRC Press, Boca Raton 245–257 (1995)
Chapter 37
Formulating for
Sensitive Skin
Controversies, preliminary research and the complexity of the
numerous dermatological reaction patterns that encompass
sensitive skin.
key words: skin sensitivity, stratum corneum desquamation,

heightened neurosensory input, enhanced immune responsiveness,
defective barrier function, anatomic cutaneous changes
T he concept of sensitive skin is intriguing to the cosmetic chemist and the

dermatologist. Approximately 40% of the population considers themselves to
possess the characteristics of sensitive skin, creating a sizeable market for products
designed to minimize skin sensitivity.1 Consumers with sensitive skin develop sting-
ing, burning, pruritus, erythema, and/or desquamation with topical formulations
that seem innocuous to the majority of the population.
At first glance, the issue of sensitive skin seems simplistic. Closer evaluation,
however, reveals great complexity. What exactly is sensitive skin? Is the tendency
toward sensitive skin inherited? Are there gender, age, and race differences in
skin sensitivity? What criteria should be used in the formulation of sensitive skin
products? What type of testing should be performed to substantiate the sensitive
skin claim? Which ingredients should be eliminated or included in sensitive skin
products?
Unfortunately, few guidelines are in place regarding sensitive skin issues. This
chapter explores current understandings, controversies and preliminary research
regarding sensitive skin.
Definition
Sensitive skin can be defined in both subjective and objective terms. Subjec-
tive perceptions of sensitive skin are derived from patient observations regarding
stinging, burning, pruritus, and tightness following various environmental stimuli.
These symptoms may be noticed immediately following product application or
delayed by minutes, hours or days. Furthermore, the symptoms may only result
following cumulative product application or in combination with concomitant
products. Approximately 50% of patients with sensitive skin demonstrate these
uncomfortable symptoms without accompanying visible signs of inflammation.2
357
358
Formulating for Sensitive Skin Beginning Cosmetic Chemistry
Cosmetics manufacturers note that one to 10% of facial cosmetic users experience
these subjective perceptions.3
Objective perceptions of sensitive skin are based on dermatologic evaluation.
These observations may include skin responses of erythema, stratum corneum
desquamation, papules, pustules, wheals, vesicles (small blisters), bullae (large
blisters) and erosions. In short, the entire repertoire of cutaneous reaction may be
included in the sensitivity spectrum. Sometimes the reaction pattern can be classi-
fied under a dermatological diagnostic heading such as: allergic contact dermatitis,
irritant contact dermatitis, contact urticaria (immunologic and nonimmunologic),
seborrheic dermatitis, perioral dermatitis, atopic dermatitis, eczematous dermatitis,
psoriasis, rosacea, comedogenic acne, and papular/pustular acne. Other labels for
skin sensitivity to cosmetics and toiletries include cosmetic intolerance syndrome
and status cosmeticus.4 Thus, the term sensitive skin is all encompassing, ill defined,
vague and somewhat bewildering as it is presently used in medical literature and
consumer advertising.
Physiology
The concept of sensitive skin remains useful, however and must be addressed in
a more organized fashion from a physiological standpoint. There is something unique
about the sensitive skin consumer. The dermatologist is familiar with the histology
and physiological findings in the traditional dermatoses previously discussed that
may contribute to sensitive skin., but not all patients with underlying dermatological
disease demonstrate the subjective complaints of stinging, burning, pruritus, etc.
in the absence of visible cutaneous disease. More puzzling are those patients who
have no objective findings and only subjective symptoms. It appears that individuals
with sensitive skin may possess one or more of the following anatomic cutaneous
changes: heightened neurosensory input, enhanced immune responsiveness and/
or diminished barrier function. Examination of each of these factors is helpful in
understanding the varied presentations of sensitive skin.
Heightened Neurosensory Input

Heightened neurosensory input represents an augmented response to otherwise
minor cutaneous stimulation. Sensitive skin consumers may have altered nerve
endings, more neurotransmitter release, unique central information processing,
chronic nerve ending trauma, or slower neurotransmitter removal to account for
this reaction.
Dermatologists frequently encounter patients with altered cutaneous percep-
tions, in particular atopic patients who prefer the cutaneous stimulation of scratching
to rubbing in contrast to non-atopic individuals for whom scratching is considered a
noxious stimulus. The effect of increased neurosensory input can also be extended
to the vascular reactivity such as the flushing induced in rosacea patients with
certain ingested foods, temperature extremes and physical or emotional stress.
Thus heightened neurosensory input allows the evaporation of volatile vehicles or
the presence of minor cutaneous irritants in cosmetics and skin care products to
induce dramatic symptoms.
359
Enhanced Immune Responsiveness

Enhanced immune responsiveness is a second contributing component of
sensitive skin consisting of heightened antibody response to antigen presentation.
This condition may be manifested in several different manners such as immuno-
logic contact urticaria 5 and allergic contact dermatitis or atopic dermatitis. Such
patients demonstrate increased positive reactions to patch and prick testing with
the height of immune responsiveness occurring around age 30 and progressively
decreasing thereafter.6
Defective Barrier Function

Lastly, defective barrier function is an important component of sensitive skin.
Lack of an intact barrier can result in heightened neurosensory input by inad-
equately protecting nerve endings. It can also contribute to enhanced immune
responsiveness through altered percutaneous absorption. This condition facilitates
increased antigen access to the dermal vasculature and antigen-presenting cells.
The permeability barrier resides in the stratum corneum of the epidermis and
requires the presence of intercellular lipids, such as cholesterol, ceramides and
free fatty acids, acting as liquid crystals.7–9 Perturbed barrier function is manifested
by many measurable physiological changes including altered calcium levels in the
stratum granulosum, increased cytokines, elevated levels of interleukin1-α and
growth factor production.10 Thus, a well organized multilayered lipid structure
between the corneocytes is essential to barrier function. Alterations in this basic
structure that cause patients with preexisting clinical or subclinical dermatologic
disease (seborrheic dermatitis, perioral dermatitis, atopic dermatitis, eczematous
dermatitis, psoriasis) to present with sensitive skin. Similarly, patients with chronic
ulceration may also present with heightened skin response.11
Testing Methodologies
One of the themes emerging from this sensitive skin discussion is the tremen-
dous variability in sensitive skin manifestation, considerably complicating cosmetic
and skin care product development. Premarketing testing is essential to insure that
products developed for this population perform up to expectations.12 This neces-
sity has resulted in development of a variety of testing protocols designed to select
panels of sensitive skin patients for assessment purposes, as well as to quantify
nonvisual responses and reinforce observer data. In addition, in vitro testing may
be necessary to assess irritancy prior to in vivo evaluation. The number of subjects
required for such testing is somewhat controversial. In general, given the power
of the data generated by human clinical testing, a minimum of 40 subjects must
undergo evaluation to achieve data that has a chance of showing statistical signifi-
cance. If the change induced by a given cosmetic or skin product is small, then
the numbers of subjects must increase. For example, when testing is undertaken
to determine if an ingredient new to the marketplace is appropriate in sensitive
skin populations, approximately 200 subjects must be tested to support the claim
of hypoallergenic.
360
The tests for assembling sensitive skin panels, bioengineering analysis of sensi-
tive skin and in vivo and in vitro tests for irritancy are summarized in Table 37.1
along with article citation. This table represents but a few of the proposed tests to
evaluate sensitive skin and irritation selected for discussion on the basis of their
current popularity.
Table 37.1. Testing methodologies for the investigation of sensitive skin
1. Tests for the development of sensitive skin panels

lactic acid facial sting test 82
chloroform:methanol (20:80) test 83
dimethyl sulfoxide (DMSO) test 84
erythema following sodium lauryl sulfate occlusion test
nicotinate test
2. Bioengineering tests to measure skin response

evaporimetry 86
polysulfide rubber replicas 87
squametry 88
chromametry 89
laser Doppler flowmetry 90
A-scan ultrasound
3. In vivo testing on sensitive skin populations

patch testing
modified soap chamber test92
forearm controlled application technique (FCAT) 93
4. In vitro tests to demonstrate irritancy

collagen swelling test 94
pH rise test 95
zein test 96
Since it is financially impossible to perform all the tests listed in Table 37.1 for
all products, test should be selected based on the product function. For example,
facial products designed for a sensitive skin population should undergo the lactic
acid facial sting test. Products designed to enhance barrier function should be tested
using the dimethyl sulfoxide (DMSO) test. Moisturizers should be evaluated using
evaporimetry. Cleansers should be assessed using the modified soap chamber test
or the forearm controlled application technique (FCAT). In summary, the test
should elucidate any adverse reaction that may be encountered when the product
is released for use by the general population.
361
Test for the Development of Sensitive Skin Panels

Assembling a testing panel requires well defined, reproducible parameters among
panelists for study. This has led to the development of cutaneous tests designed
to investigate the invisible heightened neurosensory aspects of sensitive skin. The
most popular test is the facial lactic acid sting test. This test may be performed
utilizing two methods.13
Application of a 10% aqueous solution of lactic acid at room temperature to the
nasolabial fold and cheek using brisk rubbing strokes of a cotton-tipped applicator
dipped in the lactic acid solution.
Conditioning the patient to a state of profuse sweating in an environmental
chamber at 110°F and 80% relative humidity or exposure to a facial sauna for a
period of 15 minutes, followed by a brisk application of 5% aqueous lactic acid to
the nasolabial fold and cheek.
The stinging experience is rated by the patient at 21⁄2 and 5 minutes after appli-
cation on an ordinal 4 point scale (0 = no stinging, 1 = slight stinging, 2 = moderate
stinging, 3 = severe stinging) with a cumulative stinging score (sum of the 21⁄2 and
5-minute evaluation) of 3 or higher classifying the patient as a “stinger” implying
sensitive skin. Even though this test is quite artificial it appears to correlate well
with those individuals who experience heightened neurosensory input during actual
cosmetic and skin care product use,14,15 but this remains controversial.16
Reproducibility of data from one testing population at a given point in time to
another remains a problem. Christensen and Klingman have recently proposed
dividing “stingers” into mild, moderate and severe based on application of 10%
racemic D-L lactic acid in a 1.7 cm Hilltop chamber to the malar eminence for 10
minutes.17 The time to initial stinging is noted along with the peak stinging inten-
sity. The testing revision may improve reproducibility due to its utilization of more
sensitive facial skin with a larger area of lactic acid application.
Interestingly enough, there is seasonal variability in stinging scores assigned to
sensitive skin patients with more intense responses during the winter than sum-
mer.18 This observation suggests that the increased cutaneous stinging noted must
be due to the cumulative effect of a heightened neurosensory input combined
with defective barrier function possibly associated with the xerosis of winter.
Furthermore, increased stinging is found in light-complexioned persons of Celtic
ancestry who sunburn easily19 and in persons with a history of sensitivity to soaps,
cosmetics and drugs.20
Sometimes it is advisable to test sensitive skin products on populations that
display heightened responses to burning and itching, as well as stinging. The
lactic acid sting test may be combined with the chloroform/methanol (20:80) test
designed to elicit burning and/or the application of histamine to induce itching.21,22
Sorbic and benzoic acid have also been used.23 Mills and Berger have suggested
selecting sensitive skin panelists based on the flushing response to red wine, history
of severe sunburn or allergic contact dermatitis, demonstration of a low minimal
erythemal dose (MED), a high density of facial Demodex folliculorum mites, or
heightened erythema due to friction following polyethylene-film occlusion to the
chin overnight.24
362
Another sensitive skin screening test is the application of 90% or 100% dimeth-
ylsulfoxide (DMSO) at room temperature to the forearm for five minutes. DMSO
produces a strong burning reaction in sensitive skin patients but also results in
erythema and urtica formation, not found with lactic acid.25 Other cutaneous ef-
fects include significant increases in transepidermal water loss (TEWL), hydration
of the superficial dermis, and increased blood flow and skin thickness indicating
an inflammatory response.26
A different approach to identifying sensitive skin patients relies on vasodilata-
tion of the skin as opposed to cutaneous stinging. Many investigators prefer this
approach since objective changes can be visually and biomedically assessed. These
two tests are the nicotinate test27 and erythema assessment following sodium lauryl
sulfate exposure.28 In the first test methyl nicotinate, a potent vasodilator, is ap-
plied to the upper third of the ventral forearm in concentrations varying between
1.4% and 13.7% for a period of 15 seconds. Observing the erythema and employed
laser Doppler velocimetry assesses the vasodilatory effect. Similar analysis can be
performed following application of various concentrations of sodium lauryl sulfate
to the forearm.
Bioengineering Tests to Measure Skin Response

Developing sensitive skin panels for subjective assessment of ingredient and
finished product response is both expensive and fraught with irreprodicibility.29 This
has led to great interest in the development of noninvasive mechanistic skin assess-
ment allowing presumably more accurate evaluation of small cutaneous changes.
Ideally, bioengineering tests should be able to measure preclinical disease without
altering the underlying skin condition.
One of the most popular noninvasive tests is transepidermal water loss (TEWL)
measurement, also known as evaporimetry.30 Evaporimetry can be used to assess bar-
rier dysfunction and recovery following ingredient or finished product application.31
It can also measure skin porosity indirectly predicting the rate of loss of topically
applied substances from the skin surface.32 Further information can be obtained by
analyzing changes in surface texture through profilometry or squametry. Profilometry
involves obtaining a silicone rubber cast of the skin surface, transforming the cast
into a plastic positive and obtaining a computerized contour tracing of the surface
from which two- or three-dimensional topograms can be created. Unfortunately,
this method can be inaccurate since the silicone application to the skin surface
tends to flatten and disturb the desquamating skin scale.33 This problem does not
occur with squametry where the outermost, loosely adherent skin is harvested by
pressing a sticky tape against the skin. The tape provides a specimen that retains
the topographical relationships of the skin surface and the pattern of desquamation,
which is then analyzed through computerized image processing.34
Bioengineering methods can also be used to assess color changes in the skin, a
technique known as chromametry,35,36 blood flow alterations, a technique known as
laser Doppler flowmetry37,38 and alterations in skin thickness, a technique known
as A-scan ultrasound.39 These techniques are used to add further information to
subjective patient assessments and visual assessments by a trained observer. It is
363
hoped that physiologic changes indicative of sensitive skin can be detected at low
levels prior to clinical disease presentation. An excellent review of bioengineering
of the skin edited by Andreassi can be found in the July/August 1995 Clinics in
Dermatology (Elsevier).
In Vivo Testing on Sensitive Skin Populations

In vivo testing on sensitive skin populations is valuable in product development
to determine the likelihood of adverse consumer reports following product release.
These studies include: patch testing,40 repeat insult patch testing (RIPT),41 cumula-
tive irritancy testing,42 the chamber scarification test,43 the modified soap chamber
test,44 and the forearm controlled application technique (FCAT)45,46 to name a few
of the more popular methodologies.
Patch testing can be performed with either raw ingredients or finished prod-
ucts to identify any substance or formulation likely to induce allergic or irritant
contact dermatitis. The response can be heightened through the use of repeat
insult patch testing in which 10 patches are applied to the same site at 48–72 h
intervals for a three- to four-week period. After a two-week rest, the test site is
then rechallenged and graded. Light exposure can be added to this technique to
also assess phototoxicity and photoallergy. More information regarding product
irritancy under exaggerated condition can be obtained through use of the cumula-
tive irritancy test in which a patch is applied to the same site for 10–21 days and
evaluated for irritant reactions or the chamber scarification test in which the volar
surface of the forearm is scratched to the level of the papillary dermis and the test
product applied under a Finn chamber repeatedly for three days and evaluated up
to one week after patch removal. These exaggerated use patch testing techniques
damage the cutaneous barrier, perhaps mimicking the physiologic changes seen
in some sensitive skin populations. Care must be taken however not to induce a
state of hyporeactivity.47
The class of chemicals most likely to be troublesome for sensitive skin popula-
tion is surfactants, which form the basis of most cleansing products. The original
evaluation method to predict the irritancy of soaps, detergents and cleansers was
the modified soap chamber test48, which has largely been replaced in the industry
by the forearm controlled application technique. Both trained observer evaluations
and bioengineering techniques are used to determine the effect of the product on
the skin surface. Products that produce the least skin alteration are felt to be the
mildest and the most appropriate for sensitive skin patients. Some researchers have
even suggested that individuals with sensitive skin can be selected by observing
skin changes following soaking the hands in a dilute surfactant solution for thirty
minutes.49
In Vitro Tests to Determine Irritancy

In vitro testing assumes paramount importance when developing products with
irritant potential for sensitive skin patients. The largest and most commonly used
class of irritants is surfactants found in products to cleanse the skin, hair and hands,
but also dishes, clothing, household sinks, etc. Three common in vitro screening
364
tests to evaluate the irritant potential of soaps are: collagen swelling test,50 pH rise
test,51 and zein test.52 Many more tests are available, but these three have been
chosen for discussion since they represent different methodologies of evaluating
premarket, finished products. 53,54
The collagen swelling test employs a one square centimeter collagen sheet,
which is incubated for 24 h at 500 C with a solution of the finished cleanser product
at 1% of the dry extract at its own pH. The collagen is weighed before and after
exposure to determine the amount of swelling (more swelling indicating increased
product irritation). Another approach to irritation assessment is to examine pH rise
by incubating equal volumes of a 2% solution of bovine serum albumin at a pH of
5.6 with a 2% solution of the finished product at room temperature for one hour.
The pH of the solution is measured with greater pH rises indicating increased
product irritation. The last method is the zein test which utilizes a protein that is
insoluble in aqueous solution until denatured by irritation surfactant products. The
more protein that is solubilized, the more irritating the product.
Variability
Sensitive skin has also been studied from the standpoint of gender, skin type and
prior dermatological history to attempt to identify populations at risk for sensitive
skin. Previously, it was thought that women reacted more intensely to irritants than
men.55 This number was thought to be due to a higher female skin pH with less
buffering capacity.56 However, this thinking was refuted by Bjornberg who dem-
onstrated no difference in susceptibility to irritancy between men and women by
evaluating the cutaneous effects of an anionic detergent, cationic detergent, soap,
acid, alkali, other common skin irritants.57 Lack of gender difference was confirmed
by Lammintausta,et al. who examined transepidermal water loss (TEWL) and di-
electric water content (DEWC) following sodium lauryl sulfate application.58 Work
by Reed et al. demonstrated that skin type, but neither race nor gender influence
the epidermal permeability barrier function through tape stripping alaysis.59
Although barrier permeability is key to identifying sensitive skin populations,
the effects of skin type and race on cutaneous sensitivity also appear to be very
important in predicting sensitive skin populations. Studies to determine differences
have focused on barrier permeability, barrier recovery, epidermal lipid composi-
tion, dermal vasodilatation, transepidermal water loss, and stratum corneum thick-
ness and cohesiveness. It appears that fair skin, especially skin type I, is the most
reactive to all types of irritancy,60–61 is the most resistant.. While no difference is
apparent in the thickness of white and black skin, however, black skin, whichh has
a greater number of cell layers, as assessed by tape stripping techniques, due to
greater intercellular cohesion and thus furnishing superior protection.62,63 Additional
protection is afforded to black skin by increased epidermal lipids.64 Interestingly
enough, tape stripped white and black skin demonstrate equal irritancy.65 Table
37.2 contains a compilation of racial and age related cutaneous difference reported
in the dermatologic and cosmetic industry literature.
365
Table 37.2. Racial and age-related cutaneous differences
Evaluated White Hispanic Asian Black Aged

parameter skin skin skin skin skin
SC Thickness 7.2 microns 6.5 microns Epidermis
becomes
more
compact
with age
SC layers 17 22
TEWL Higher than Higher Lower in
Following SLS white than white healthy
exposure following following aged skin
2% SLS preoccluded
skin, .5% SLS
TEWL Higher Higher
following than than white
tape stripping white
Corticosteroid Higher Lower
penetration permeation permeation
than black than white
Vessel Highest Same as Less No age-
reactivity white skin related
difference
Stinging Greatest
susceptibility Possibly less Possibly less
Response to Erythema Erythema hyper- Possibly less
irritation and Hyper- pigmentation
pigmentation

Sweat glands Fewer More
apocrine- apocrine-
eccrine eccrine
glands glands
Ceramide Intermediate Intermediate Highest Lowest Decreased
levels with age
Skin type differences in vasodilatation are somewhat ambigous.66 Application

of methyl nicotinate followed by observing erythema and employing laser Doppler
velocimetry yielded varying results depending on the assessment technique.67 It is
felt, however that black skin demonstrates a different vascular reactivity than fair
skin, when exposed to potent topical corticosteroids.68
Race differences can also be demonstrated in response to comedogens, such as
topical coal tar.69 White skin tends to develop inflammatory papules and pustules
366
two to three weeks following exposure while black skin develops open comedones
14 days after application. Thus irritants of this sort tend to induce follicular dis-
integration in fair skin types and hyperkeratosis in dark skin with production and
retention of the horny cells.
The most reliable predictor of sensitive skin appears to be prior history of
dermatological diseases, especially eczematous dermatoses. These patients exhibit
increased transepidermal water loss, possibly due to alterations in epidermal lipids
from surfactant effects.70
Formulation Considerations
The preceding discussions lead to the conclusion that formulation challenges
for sensitive skin populations are indeed complex. Package labeling of currently
marketed sensitive skin products includes phrases such as hypoallergenic, safe for
sensitive skin, allergy tested, dermatologist tested, clinically tested, non-irritating,
nonsensitizing, fragrance free, preservative free, all natural, etc. 71 These must be
largely regarded as marketing claims however, since no standard testing methodolo-
gies exist for claim substantiation. One proposed approach for testing and evaluating
sensitive skin products is presented in Table 37.3.72
Table 37.3. Approach for formulating sensitive skin products
Review of ingredients to minimize irritants and sensitizers.

Elimination of unnecessary ingredients.
Stability evaluation of ingredients as formulated.
Utilization of in vitro methods to predict final formulation skin and eye irritation.
Utilization of in vivo methods to predict final formulation skin and eye irritation.
Utilization of sensitive skin panels to confirm results of in vitro and in vivo testing.
Pre-market monitored consumer large scale testing.
Post-market monitoring of consumer responses and adverse reaction reporting.
It is important to first determine that no commonly recognized irritants or sensi-

tizers are present in the formulation. This task can be accomplished by performing
an ingredient and/or literature search on those substances which are unfamiliar to
the chemist. Ingredients that are questionable and unnecessary should be eliminated
to avoid problems. Testing must then be performed to include stability assessment,
in vitro and in vivo tests as required, and finally clinical evaluation in a sensitive skin
population for tolerability. Finally, post-marketing surveillance should be performed
to determine if the formulation goal has been achieved.
Formulations appropriate for sensitive skin must avoid inducing both visible
and invisible manifestations of skin sensitivity.73 This means objective findings such
as erythema, xerosis, edema, vesiculation must be avoided along with subjective
symptoms such as tightness, itching, stinging and burning. Furthermore, the skin
367
must not undergo physiological changes such as dehydration, barrier damage,

lipid alterations, decreased corneocyte adhesion, protein denaturation, stratum
corneum swelling, removal or denaturation of water-soluble constituents, enzyme
denaturation and cytokine or mediator release.
Any sensitive skin product must meet certain goals in order to be valuable in
this unique population. These goals are:
Common allergens and irritants must be eliminated from the formulation, or
if that is not possible, reduced in concentration.
High quality, pure materials without contaminants should be selected. If it is
impossible to eliminate highly allergenic contaminants, a suitable binding agent
should be added. For example, nickel contamination can be minimized through
the use of a sequestering agent, such as ethylenediamine triacetate.74
Autoxidation products, which may be responsible for hypersensitivity reactions,
should be prevented through the use of suitable antioxidants, such as alpha-tocopherol
butylhydroxyanisole (BHA) or butylhydroxytoluene (BHT).75,76
Volatile vehicles and substances producing cutaneous stimulation (menthol)
should be eliminated or reduced.
Solvents that promote skin penetration (propylene glycol, ethanol) should be
avoided. If necessary, higher glycols (polyethylene glycols) that do not penetrate
the stratum corneum, and may form hydrogen bonds with penetrants, should be
selected.
Surfactants, either used for cleaning purposes or as an emulsifier, should be
carefully selected. Anionic surfactants (sodium lauryl sulfate) are strong irritants due
to their ability to penetrate the stratum corneum, bind to the skin proteins, induce
stratum corneum swelling and enhance penetration of other substances (antimi-
crobials).77 Cationic surfactants are intermediate in their penetration and nonionic
surfactants penetrate the skin least.78 However, nonionic surfactants can change the
biosynthetic rate, composition and content of epidermal phospholipids.79
Preservatives with low sensitizing potential (parabens) should be selected
over those with a higher sensitizing potential (formaldehyde and formaldehyde
releasers).80,81
Certainly, the recommended approach to testing sensitive skin products (Table
37.3) and the formulation goals present a challenge for the cosmetic chemist. It
would be convenient, however, to have one simply stated test criteria that allowed
products to be classified as appropriate for sensitive skin. For example, a dem-
onstrated ability of the product to reduce 10% lactic acid malar eminence facial
stinging following six days of application.
Summary
This discussion demonstrates the complexity of the numerous dermatologic
reaction patterns that fall under the heading of sensitive skin. Subjective symptoms
of sensitive skin include stinging, burning, pruritus and tightness following various
environmental stimuli, while objective findings include allergic contact dermatitis,
irritant contact dermatitis, contact urticaria (immunologic and nonimmunologic),
368
seborrheic dermatitis, perioral dermatitis, atopic dermatitis, eczematous dermatitis,

psoriasis, rosacea, comedogenic acne and papular/pustular acne.
Physiologically, sensitive skin possesses one or more of the following anatomic
cutaneous changes: heightened neurosensory input, enhanced immune responsive-
ness and/or diminished barrier function. Various visual grading techniques and
biomechanical tests have been developed to quantify the changes associated with
sensitive skin. Of these, the lactic acid facial sting test seems to correlate best with
those patients who demonstrate objective and/or subjective symptoms of sensitive
skin. Cosmetic and skin care product formulation considerations for sensitive skin
include products with a paucity of ingredients, absence of sensitizers, minimum
number of irritants, and absence of cutaneous sensory or vasodilatory stimulants.
Sensitive skin products can minimize potential problems by including antinflam-
matory agents, improving barrier function and creating an exogenous barrier.
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Chapter 38
The ABCs of SPFs:

An Introduction to Sun
Protection Products
This chapter discusses the biological effects of sunlight, the
chemistry of common UV absorbers and factors to consider
when formulating and testing sun care products.
key words: sunscreens, UV, photoaging, PABA, sun block, sunburn
S unscreens are a special class of personal care products containing active ingredi-
ents that can absorb ultraviolet (UV) radiation to shield skin from the damaging
effects of the sun. These products are classified as OTC drugs and are regulated
by the Food and Drug Administration (FDA) in the United States.
UV Light and its Effect

Sunlight is composed of many wavelengths spread across the electromagnetic
spectrum. As this solar radiation passes through earth’s atmosphere, some of these
wavelengths are filtered out. The remaining radiation reaches the earth as UV and
infrared light. UV light is of particular concern because it can interact with skin
cells and cause a variety of damaging effects. It consists of wavelengths grouped
into the following three categories.
• UVC light ranges from 200–290 nm. This range has the lowest wavelength
and consequently the highest energy because wavelength and energy are
inversely related. Almost all light in this range is filtered out by the atmo-
sphere, although a small amount is produced by arc welders and certain
tanning lights.
• UVB light ranges from 280–320 nm and is called the burning or erythemal
region because it penetrates through the statrum corneum (SC) and the
epidermis. This type of light causes most of the skin damage that is imme-
diately apparent, like reddening, which is known as erythema or sunburn.
• UVA light is composed of wavelengths between from 320–360 nm. This range
has the lowest energy, but it penetrates deeper into the skin and interacts
with more skin structures. Low doses of UVA can penetrate into the dermis,
where it can stimulate the production of melanin, the pigment responsible
for tanning and protecting the skin from further damage.
373
374
The ABCs of SPFs: An Intro to Sun Protection Products Beginning Cosmetic Chemistry
While UVB is responsible for most sunburns, high doses of UVA can also cause
reddening.
Furthermore, the amount of UVA that reaches the earth’s surface is higher than
the amount of UVB. Higher doses of UVA can penetrate into skin structures and
cause damage to cellular DNA and structural components, such as the elastin and
collagen matrix. Chronic sun exposure, particularly to the UVA range, also results
in a condition known as UV-induced photoaging, which occurs when key support
matrix elements are damaged by radiation. This cumulative process contributes to
wrinkles, sagging and other signs of aging. The impact of photoaging can easily be
seen by comparing the difference in skin on the face to an area that is not exposed
to constant sunlight, such as the buttocks. While this skin is physiologically identi-
cal to the face, it appears smoother because it is exposed to less light. Studies have
shown intrinsic differences between photoaged skin and intrinsically aged skin.
In the United States, products that screen out this part of the spectrum can
make the antiaging claims that are extremely popular now. These products do
not just guard against sunburn and skin cancers, they also protect one’s youthful
appearance. In addition to dermal problems, data also suggests that UVA is one
possible agent causing certain types of cataracts.
Hair Damage
In addition to its effects on skin, UV light has also been shown to cause two
types of hair damage. When hair is exposed to enough UV light, it can become
discolored. Brown hair tends to fade, while blond and red hair tends to yellow.
This change has been attributed to photo-oxidative bleaching processes and the
photodegradation of amino acids, such as cystine, tyrosine and tryptophan. The
breakdown of amino acids is also responsible for the other types of hair damage
induced by UV exposure, namely the reduction in tensile strength. Due to short-
and long-term effects on health and beauty, it is desirable to protect skin and hair
from UV light. Of course, the most direct solution is to shield them from the sun
by physically blocking them with clothing, hats or umbrellas. However, this solu-
tion is not always practical or desirable. To protect exposed skin and hair from the
damaging effects of sunlight, scientists have developed various chemicals that can
absorb or block UV radiation.
The Chemistry of UV Absorbers

Certain chemical compounds are able to interact with UV light, defusing its
damaging energy. The chemical bonds in these molecules can absorb UV light and
remit or reabsorb it in a harmless form. These chemicals are typically aromatic
compounds that have a carbonyl group. In general, they also have an electron
releasing group, such as an amine or a methoxyl group in either the ortho- or
para-position on the aromatic ring. When UV light strikes one of these molecules
it causes a photochemical excitation; the molecule is stimulated to a higher energy
level. When the molecule returns to its original energy state, the excess absorbed
energy is emitted as light with a different energy state. Most sunscreens emit energy
in the infrared region and may contribute a minuscule heating effect to the skin.
375
Others emit in the blue range of visible light. In fact, products that use these types
of compounds give the skin a slight bluish cast. Each sunscreen molecule can repeat
this absorption-emission cycle multiple times before it decays.
A variety of compounds have been developed which have a molecular structure
capable of UV absorption. These absorbers can be formulated in appropriate vehicles
that can be conveniently applied to exposed skin to protect cells from interaction
with the radiation. Common UV absorbers include organic compounds, such as
para-amino benzoic acid (PABA) and its esters (salicylates cinnamates, benzophe-
nones, anthanilates, dibenzoylmethanes and camphor derivatives. In addition,
inorganic sun blocking materials, such as titanium dioxide, are commonly used in
sunscreen formulations.
Key Sunscreen Chemicals

PABA and its derivatives: PABA is an aromatic ring
with amino and carboxylic acid groups that has been used
in sunscreen products since the 1950s. PABA is an effective
sunscreen, but because of the way its functional groups are
positioned (the parastructure), the molecule is prone to oxi-
dation and discoloration. It also tends to form a crystalline
structure that can make the material hard to use in cosmetic
formulations. Furthermore, in recent years, concerns have Figure 38.1.
been raised about the safety of the material. Scientists have PABA
attempted to overcome some of these drawbacks by esterify-
ing PABA with other materials. For example, combining PABA with glycerin yields
glyceryl PABA that is more water soluble than the parent compound. Despite these
improvements, PABA-based sunscreens have gained a negative reputation with
certain consumers, and many formulators avoid using them. In fact, many products
are now labeled “PABA-free.” See Figure 38.1.
Salicylates: Salicylates were the first
sunscreen chemicals to be widely used in com-
mercial preparations, and they continue to be
popular today. Benzyl salicylate, octyl salicylate
and homomenthyl salicylate are among the most
popular. These molecules all contain functional
groups attached to the ortho position and are
Figure 38.2. Octyl Sylicilate
able to create internal hydrogen bonds. Because
they absorb UV radiation about 300–310 nm,
they are ideal for use as UVB screens. Although salicylates are less effective UV
absorbers than other sunscreens, they have an excellent safety profile and can be
readily incorporated into cosmetic vehicles. Due to their active groups interacting
with each other, they are less likely to react with the skin or other ingredients. See
Figure 38.2.
Cinnamates: Cinnamates, particularly benzyl cinnamate, were used as early
sunscreen compounds. They contain an extra unsaturated group conjugated to
both the aromatic ring and the carboxylic acid group. This structure gives these
376
molecules good UV absorbance in the 305 nm range.

Currently, octyl methoxycinnamate is preferred because
it is insoluble in water. This quality makes it ideal for use
in waterproof products. See Figure 38.3.
Benzophenones: Benzophenones are the only UV
absorbers belonging to the aroma ticketone category.
This unique structure allows them to absorb UV light
beyond 320 nm. Unfortunately, these materials are solids Figure 38.3. Benzyl
that are difficult to handle and hard to incorporate into Cinnimate
cosmetic products. See Figure 38.4.
Mexoryl: The trade name of the most recently
approved sunscreen in the United States. It is a
benzylidene camphor derivative and has the INCI
name terephthalylidene dicamphor sulfonic acid.
This material is specifically added to sunscreens to
filter UVA. It is particularly good for this application Figure 38.4.
because unlike other UVA blocking materials (like Benzophenone
avobenzone) it does not require photostabilizers to
maintain its effectiveness. Currently,
the use of this ingredient is restricted
due to patents held by L’Oreal. See
Figure 38.5.
Physical blockers: Other ma-
terials, such as titanium dioxide and
zinc oxide, do not absorb UV light
but are capable of reflecting light, Figure 38.5. Terephthalylidene
thereby preventing it from reaching Dicamphor Sulfonic Acid
the skin. These sun blockers are the
most effective way to chemically shield the skin as they block both UVA and UVB,
but they tend to leave a white film that can be esthetically unpleasing. A recent in-
novation in sun block technology has created micronized versions of these molecules
whose particles are reduced in size to the point where they do not reflect visible
light, but are able to scatter UV light. These micronized versions are a significant
esthetic improvement because they do not leave a noticeable film on the skin.
The most common form of titanium dioxide is rutile. When made into a finely
ground powder, rutile has a bright white color. Nanosized particles of rutile are
transparent but still maintain their ability to absorb UV light. This makes them ideal
for use as cosmetic sunscreens. Some consumer groups have expressed concern over
the safety of nanoparticles so their use may be controversial. The latest scientific
data suggests no harm, but research continues.
Sun Care Formulation

If a sunscreen ingredient is not properly incorporated into a cosmetic formula-
tion, it will not matter how well that ingredient blocks or scatters UV radiation. The
type of formulation depends on many factors, such as the desired product form and
377
function, the type of sunscreen ingredients to be used, the esthetic characteristics

and other factors like cost and manufacturing capabilities. Although these factors
are common to most formulating efforts, sunscreen ingredients also have their
own special considerations related to effectiveness, stability and regulatory issues.
In all cases, formulations that claim to be active against UV-induced damage must
provide a uniform sunscreen film on the skin or hair to be effective. Ideally, this
film will be thick yet invisible. For products designed to be used while swimming,
the film must be waterproof. Also, care must be taken to minimize the ingredient
interaction between the sunscreen active and the formulation. In some cases, the
improper mix of ingredients can result in a significant reduction in the effective-
ness of the sunscreen active. A variety of formulation vehicles that meet these
requirements are available. The most common include oils, emulsions, gels, sticks,
aerosols and ointments.
Oils: The simplest way to apply a sunscreen to the skin is by incorporating it
into an oil-based product. In fact, oils were one of the earliest forms of sunscreen
products. Evidence suggests that the ancient Greeks used mixtures of sand and oil
to prevent sunburn as early as 400 B.C. The sand could effectively scatter the UV
light while the oil allowed it to be distributed evenly on the body. Today, oils are
still used as formulation vehicles for sunscreen actives. This type of formulation
has various advantages and disadvantages. Because most sunscreen actives are
lipophilic, oils can be manufactured easily. In fact, they are typically produced in
a single phase. Additionally, oils can be spread readily on the skin and do not rinse
off. Oils also have excellent product stability profiles.
Unfortunately, oil-based products have some significant drawbacks. For instance,
their rapid spreadability results in a thin, transparent film. This film has a lowered
amount of active sunscreen reducing the product’s overall sun blocking effective-
ness. In general, oils have higher costs associated with them because no water is
present and more active sunscreen ingredients are needed. Esthetically, oils can
feel greasy and leave an unappealing coated feel. Also stability issues related to
putting an oil-based sunscreen product in certain types of plastic packaging may
occur. Products that use this type of formulation are tanning oils. These products,
designed to be worn while sunbathing, typically provide minimal UV protection
and are used merely to prevent serious burning.
Emulsions: Emulsions are the most commonly used delivery vehicle for sun-
screen actives. Made up of a mixture of oils and water and stabilized by an emul-
sifying ingredient, emulsions are used to produce both cream and lotion products.
While emulsion technology has been known for centuries it was not until the 1920s,
with the introduction of the first organic sunscreens, that they could be used as
sunscreen delivery vehicles. They are one of the best delivery forms because they
are the most versatile. Unlike oils, they can be used to create a product providing
an excellent sunscreen film on the skin and still have an elegant feel. Additionally,
emulsions are relatively inexpensive, especially compared to oil formulations. One
common drawback to the use of emulsions is their difficulty in stabilization. Over
time, any emulsion product will destabilize and separate into its component oil and
water phases. However, with careful formulation efforts and the right emulsifiers, an
378
adequately stable system can be made. From a manufacturing standpoint, emulsions

are more difficult to produce than oil-based products. Also, emulsions are limited in
the amount of protection they can provide. Because the UV active ingredients are
typically lipophilic, increasing the amount of oil phase is the only way to produce
products that protect better and last longer. However, the more oil in a system, the
more is difficult it is to stabilize. Products that use emulsions include sunscreen
creams and lotions. These products are designed to be spread on the skin, leaving
a film that is effective against sunburns. If formulated appropriately, they can be
made to last many hours and be waterproof.
Gels: Gels provide an alternative to the typical emulsion-based sunscreen
products. They are a thick, clear product, with an elegant look that appeals to con-
sumers. Various types of formulations can produce this effect, including aqueous
and hydroalcoholic gels and microemulsions. Aqueous and hydroalcoholic gels
are produced by incorporating acrylic polymers in the system for thickening. For
aqueous gels, water-soluble sunscreens are typically required to keep the formula
clear. More lipophilic actives can be used with hydroalcoholic gels because alcohol
is included to keep the system clear. While microemulsions are more technical
emulsions, they have significantly smaller particles making them transparent and
they appear more gel-like than emulsion-like.
The primary advantage gels have over emulsions is their clarity and unique look.
However, significant drawbacks limit their use. For example, they are typically lim-
ited to non-water-resistant applications because they produce water-soluble films.
Additionally, these films are not uniform, so they may not provide the expected
protection. The thickeners used in certain gel products can leave a sticky feel on
the skin. In general, microemulsion gels tend to be more irritating on the skin than
standard emulsions. Also, hydroalcoholic gels can negatively interact with certain
types of plastic packaging. In general, gel products cost more than emulsions, and
they can be more difficult to manufacture. Despite these drawbacks, gels do have
their place as sunscreen delivery vehicles. Perhaps the most promising are in hair
care. Many manufacturers have recently introduced styling gels with sunscreens
incorporated in them. It is hoped that these products will reduce hair damage
induced by UV exposure.
Sticks: Sticks are a solid form which have only recently been introduced as
a vehicle for sunscreens. They are typically made up of waxes and oils thickened
with petrolatum. They work well for sunscreens because they are stable and com-
patible with the ingredients. They are also more water-resistant than any other
delivery vehicle. Unfortunately, they often have a greasy feel and are generally
more expensive and difficult to produce. Sticks are used for lip or facial products.
For these applications they are useful because they can be applied easily to a small,
specific area.
Aerosols: Aerosols represent another type of formulation vehicle for UV
active ingredients. Aerosol mousses have gained popularity. These products are
essentially emulsion lotions that are put in sealed containers and have propellant
added to them. When the actuator is depressed, the product is released as a foam.
Because UV active materials can be readily added to the oil phase, mousses make a
379
convenient form for sunscreen products. They are easy to use and have good esthetic
characteristics. Because they are pressurized, they are not necessarily suitable for
products that will be left out in the sun. Other types of aerosols can be used for
sunscreen delivery, however, they have significant drawbacks. One problem is that
they are often oil based, so they are expensive and have lower SPF ratings. Also,
they produce a discontinuous film on the skin, reducing effectiveness. However,
they are a novel and convenient product form that has as recently as 2008 found
greater acceptance and market share.
Ointments: The last significant category of delivery vehicles are ointments. These
oily products are based on thickened mineral oil formulas. Their primary advantage
over emulsion-based products is that they are more water resistant and may be able
to provide more protection. Esthetically, they are generally not desirable.
Testing Sun Care Products

One of the primary measures for products designed to protect against the
damaging effects of UV light is the SPF. Simply put, a product’s SPF is equal to the
ratio of the time it takes to burn if wearing the product versus the time it takes to
burn without any product. For example, suppose a product has an SPF rating of 8.
This score means product users could stay in the sun about eight times longer and
get the same amount of sunburning than they would have if they were not wearing
any protection. The SPF value can be affected by a variety of factors including the
amount and type of sunscreen active, the type of delivery vehicle and the other
ingredients in the formulation. By increasing the amount of sunscreen active, sun-
screen marketers have found that they can increase the SPF rating. According to
the recently published FDA monograph on sunscreen drug products, a maximum
numerical SPF rating of 30 has been established. However, because the data are
not clear whether higher SPF values are possible, the FDA now allows the use of
the claim 30 plus for certain products.
Obtaining a Rating
To obtain any SPF rating in the United States, specific types of tests have been
developed. They include both biological and chemical evaluations. A variety of
methods are possible for determining the SPF of a formulation. One biological
evaluation involves the use of volunteers. In this test, the lower back of a non-
sunburned volunteer is subjected to UV light until a minimum amount of erythema
or redness develops. Light-proof barriers are placed around a measured section of
the skin so clear margins are visible. The amount of energy required to produce
this effect is determined and provides a base line for the SPF calculation. The next
day, the sunscreen formula is evaluated. It is first put on the volunteer’s skin and
allowed to dry. The skin is then irradiated with UV light at the estimated SPF value.
A preliminary value for this number is obtained by using a spectrophotometric
absorption estimation. The amount of UV light required is recorded and the SPF
is determined. In addition to SPF, other characteristics of the formulation can be
tested. For example, the water resistance of sunscreens can be determined.
380
To determine the water resistance capability of a sunscreen, in vitro testing

can be done. One method involves treating a hairless mouse with the product and
immersing it in a pool of water. The amount of sunscreen that is leached off the
animal is then measured. Another, more appropriate method using in vivo human
testing has been proposed by the FDA. In this method, sunscreen is applied to an
area of the body measuring at least 50 square centimeters. The static SPF is deter-
mined by various methods. The test product is reapplied and allowed to dry for 20
min. The subjects are then allowed to be active in an indoor pool for a period of 20
min, dry and rest for 20 min and then get back into pool for another 20 min. For
water resistance claims, an accumulative period of 40 min in the water is required.
For waterproof claims, accumulative time of 80 min in the water is required. The
SPF is determined again and if it maintains the value found initially, the claim is
allowed. Because sunscreens are an OTC drug in the United States, stability testing
is required to establish an accurate expiration date. According to the regulations,
if a product is stable and maintains its SPF rating after three months of stability
testing, a one year expiration date is required. If an entire year of testing is done, a
three-year expiration date is allowed. If the product maintains its SPF rating after
three full years of testing, no expiration date is required.
Future of Sunscreens
The FDA has issued a final OTC monograph that determines which materials
can be legally used in sunscreens in the United States. Even with a final monograph,
however, research into UV absorbers must continue. As the ozone layer continues
to decline and more damaging radiation reaches the earth’s surface, more effective
sunscreen molecules will be required to protect the public. The challenge will be
for regulatory concerns to keep pace with scientific discoveries to ensure the public
has safe and effective products from which to choose.
Published September 1999 Cosmetics and Toiletries magazine.
Additional Reading
1. J Lowe, Sunscreens Development, Evaluation, and Regulatory Aspects, N.&N Shaath
(Eds.), Marcel Dekker, NY (1990)
2. W Stevenson, Chemistry Saves Sun Worshipers, Today’s Chemist at Work, 10 47–52
(1998)
3. P&G, Gourley. Protect Your Life in the Sun, Highlight Publishing, Albuquerque (1993)
4. Formulation of Sun Protection Emulsions with Enhanced SPF Response, Cosm Toil 6
55–64 (1997)
5. Code Federal Regulations Parts 310, 352, 700, and 740. Sunscreen Drug Products for
Over the Counter Human Use; Final Monograph (May 21, 1999)
6. A Deflandre and G Lang Photostability assessment of sunscreens. Benzylidene
camphor and dibenzoylmethane derivatives,. Int J Cosm Sci 10(2): 53–62 (Apr 1988)
Chapter 39
Self-Tanners: Formulating
with Dihydroxyacetone
This chapter discusses the background behind the development
of self-tanning products using DHA. Its structure, chemistry,
self-tanning mechanism and formulation guidelines are also
discussed.
key words: dihydroxyacetone, DHA, self-tanner, self-tanning,

DHA dimers, Maillard reaction, DHA formulations
T he majority of cosmetic formulations are designed to improve biological surfaces

through some physical interaction. For example, shampoos help physically
remove oil and dirt from hair; makeup physically changes the color of skin. While
these products significantly modify the appearance of their targeted surfaces, the
effects are temporary because they do not chemically modify the surface.
However, a few cosmetic product types rely on chemical reactions with the
biological surfaces to create more “permanent” effects. In hair care, these types
include dyes, perms and relaxers. In skin care, the most common type is sunless
tanners.
A well-rounded cosmetic chemist must be familiar with the chemical reaction
involved in these types of cosmetics and the special formulating nuances that go
along with creating them. In this article, the primary active for sunless tanners,
DHA, is reviewed and described at length.
Background
The tanned look: The prevailing cultural esthetic among fair-skinned people
in many countries is to have tanned skin, which means skin with a light yellowish
brown or even deeper brown color produced by exposure to the sun or to an arti-
ficial source of ultraviolet light. The tanning of the skin is produced as a result of
the darkening of preformed melanin, accelerated formation of new melanin, and
retention of melanin in the epidermis as a result of retardation of keratinization.
For those individuals who wish to achieve tanned skin, the most readily avail-
able means for doing so is by exposing their skin to natural sunlight. However, this
method carries certain hazards. Chief among those hazards is the risk of sunburn,
which is an injury to the skin produced by excessive exposure to ultraviolet rays.
The injury is accompanied by erythema, tenderness and sometimes blistering.1
Furthermore, excessive exposure to ultraviolet radiation is considered by the
381
382
Self-Tanners: Formulating with Dihydroxyacetone Beginning Cosmetic Chemistry
medical community to be a leading factor in skin cancer and premature aging.2 So

a completely safe natural tan is out of the question.
The solution to achieving a tanned look is to use self-tanners. They are avail-
able in hundreds of brands of creams, gels, mousses and sprays at drug stores,
department stores and salons. They all work the same way. That is, they all have
the same active ingredient: dihydroxyacetone (DHA), also known as 1,3-dihydroxy-
propanone, according to International Union of Pure and Applied Chemistry
(IUPAC) nomenclature.
Discovery of DHA’s browning effect: The browning effect of DHA was
discovered by accident. In the mid-1950s, at Children’s Hospital at the University
of Cincinnati, Dr. Eva Wittgenstein was studying the effect of large oral doses of
DHA in children who had glycogen storage disease. Sometimes the children vom-
ited some of the sweet concentrated material, and it splashed on their skin. A few
hours later, it was noticed that the children had brown spots on their skin where
stray splashes hadn’t been wiped off.
Wittgenstein was able to do something with her observation other than berat-
ing the staff for not getting those kids cleaned up. Curious, she prepared aqueous
solutions of varying concentrations of DHA and was able to reproduce the pig-
mentation on her own skin. She was able to turn her skin brown.3 This accident
and self-experiment was the beginning of self-tanning products based on DHA.
Additional information on this subject has recently been reviewed.4,5
Acceptability of DHA’s cosmetic effect: The cosmetic acceptability of DHA
products seems to have improved in recent years. More natural-appearing brown
or golden hues are produced, as opposed to more off-color oranges observed with
older formulations. The shades obtained may be more acceptable to medium-
complexioned people than those with darker or fair complexions. Purer supplies of
DHA, refining of DHA-containing vehicles to allow better penetration, recognition
of the need for a lower pH, and more rapid color change with a lower concentration
of DHA may have all contributed to the improved outcome.
The US Food and Drug Administration has approved DHA as a permanently
listed colorant (21 CFR § 73.2150) exempt from certification for drugs and cosmetics.
It may be used only in externally applied drugs and cosmetics intended solely or in
part to give a color to the human body. A monograph for DHA has been included
in the ninth supplement of the United States Pharmacoepia 23.
The European Economic Community’s EEC Cosmetics Directive (76/768/
EEC) places no limitations on DHA. The Japanese Cosmetic Ingredient Diction-
ary (JCID-II-80) includes DHA as a cosmetic ingredient.
Structure and Chemistry

Structure: DHA is a simple three-carbon sugar. It is nontoxic. In fact, it is an
intermediate in carbohydrate metabolism in higher plants and animals, and is more
rapidly metabolized than glucose in the body. Specifically, this three-carbon sugar
is a physiological product (dihydroxyacetone monophosphate) of the body formed
and utilized during glycolosis. DHA used in self-tanners is prepared mainly by
fermentation of glycerol using Gluconobacter oxydans.6
383
DHA is a slightly hygroscopic material, which should be shipped and stored in

tightly closed containers under refrigeration (<6°C). Degradation of DHA increases
with higher temperature and higher pH.7 DHA can be assayed using periodic acid
by following the method described in the Official Monographs, USP 23.
In crystalline form, DHA is a mixture of one monomer and four dimers (Figure
39.1).8 The dimeric forms with 1,4-dioxane structure predominate;9 they result
from intermolecular hemiketal formation. The dimeric DHA in the form of a cyclic
ketal and trimeric DHA in the form of a bicyclic ketal have also been reported.10,11
The monomer is formed by heating or melting dimeric DHA or by dissolving it
in water. In aqueous solution, DHA occurs as a monomer that can gradually tau-
tomerize into glyceraldehyde. The equilibrium shifts to DHA at acidic pH or to
glyceraldehyde at alkaline pH.
Figure 39.1. Structures of monomeric and dimeric dihydroxyacetone
Interconversion of DHA and glyceraldehyde was studied in different solvents

and temperatures by FTIR spectroscopy.12 Dissolution in water and increasing
temperatures caused the dissociation of the dimeric forms of both compounds
into monomers and the subsequent inter-conversion of DHA and glyceraldehyde.
A five-membered ring form was predominant in aqueous solutions of the dissoci-
ated glyceraldehyde dimer, whereas a six-membered ring form was preferred in
aqueous solutions of dissociated DHA dimer. DHA predominantly converted to
the six-membered H-bonded conformation of glyceraldehyde when dissolved in
water. This conversion was attributed to the preferential formation of the trans- or
E-enediol as an intermediate. Temperature-dependent spectra have indicated that
increasing the temperature favored the formation of glyceraldehyde in the aqueous
equilibrium mixtures of dimeric glyceraldehyde and DHA.
384
Chemistry: The site of action of DHA in the skin is the stratum corneum.13 The
first step of the self-tanning reaction is the conversion of DHA to pyruvaldehyde
with the elimination of water (Figure 39.2). Then the keto or aldehyde function
reacts with the amine functionality of skin keratin to form an imine. Subsequent
steps of this reaction are a complex chain of reactions and are not fully understood.
However, it is well known that the resulting products are cyclic and linear polymers
having yellow or brown color.14,15
Figure 39.2. Self-tanning reaction of dihydroxyacetone
The self-tanning process takes place in the outer layers of the epidermis. Only
the monomeric form undergoes the Maillard reaction that leads to tanning. In
this process, named after Louis-Camille Maillard, who first described it in 1912,
amino acids interact with sugars to create brown or golden brown compounds. The
Maillard reaction is defined currently as the reaction of the amino group of amino
acids, peptides, or proteins with the glycosidic hydroxyl group of sugars,16 forming
brown products referred to as melanoidins.
Melanoidins are polymeric compounds, which are linked by lysine side-chains
to the proteins of the stratum corneum. Although the formation of melanoidins is
different from that of melanin, some of their properties are similar, especially their
absorption spectra.17 Melanins consist of aromatic amino acids, originating mainly
from tyrosine. Melanoidines, on the other hand, consist mainly of an aliphatic
moiety with very few aromatic functions in the side chains.
pH plays a very important role in tanning. To achieve a uniform tan, the skin
should be exfoliated to remove loose skin scales before applying DHA. The opti-
mum pH for the Maillard reaction is between 5 and 6, which is the normal pH of
healthy skin. When formulations with a higher or lower pH are applied, the skin
buffer adjusts the pH on the skin to the optimal tanning pH. Tests showed that un-
buffered formulations with a pH between 2 and 6 always lead to the same coloring
results. Only when the pH was above 6 was the brown intensity reduced. However,
the desired formulation pH for DHA is between 3 and 4.
385
Formula Types
Tanning products fall loosely into two categories: wash-offs and wear-offs. Wash-
offs are cosmetic tanning products in cream or gel formulas, without DHA, that give
the appearance of a tan, but wash-off in the shower at the end of the day. Wash-offs
exist in a wide range of products available from all major cosmetic companies.
Wear-off formulations containing DHA are the true self-tanning products.
They are available in creams, lotions, milks, gels or sprays. When these products
are applied on the skin, they develop a tan over a matter of hours and wear off
over a matter of days.
By far the most popular of all vehicles used for self-tanning products, the emul-
sion, offers a wide variety of options. DHA is most often formulated in o/w emul-
sions. Lotions are more popular than creams owing to their ease of spreadability
on the skin and dispensability from bottles. Creams can lead to more intense tan
than lotions because the applied film is thicker.
From an aesthetic viewpoint, emulsions are an elegant medium that can give
the skin smooth silky feel without being greasy or tacky. They can accommodate a
wide variety of raw materials. Sunscreens and other ingredients can be incorporated
in the emulsion to make additional product claims.
Due to high water solubility of DHA, aqueous or aqueous-alcoholic lotions
and gels can be prepared easily. By appropriate control of viscosity, spray lotions
or gels can also be developed.
Formulation Guidelines
The content of DHA in tanning products depends on the desired browning
intensity on the skin and is normally in the range of 4–8%. Depending on the type
of formulation and skin type, a tanning effect appears on the skin in approximately
two to three hours after use. During product storage, the pH of a DHA-containing
formulation will drift over time to about 3 to 4. At this pH, DHA is quite stable.
In order to ensure end-product stability, the following factors must be considered
before developing new formulations containing DHA.
Temperature: Heating DHA above 40°C for a long period of time must be
avoided as it causes rapid degradation of DHA (> 40% within three months). During
manufacturing processes involving heating, as in the case of emulsions, DHA should
not be added until the formulation has been cooled down to below 40°C. Products
containing DHA should be stored in an opaque and re-sealable package.
pH: When DHA is incorporated in a formulation, the pH of the formula-
tion drops to 3 and 4 within about two days from the date of preparation. In the
past, buffering was recommended to keep the pH at a level of 4 to 6. Recent
investigations in our laboratories revealed that storage stability of DHA could be
increased when the formulations are kept at pH 3 to 4. Buffering at a higher pH is
counterproductive, as it enhances degradation of DHA thereby reducing its stor-
age stability. pH 3, however, is not the optimal pH for the tanning reaction; skin
buffers bring the applied formulation to the optimal tanning pH (5 to 6) and then
the tanning occurs.
386
Buffers: Use of buffers to maintain the pH of a formulation above 4.5 is not

recommended. The pH of the formulation may be adjusted to approximately 3 to
4 by using a small amount of citric acid or using acetate buffer because they do
not affect DHA stability.5
Phosphate buffers are not recommended. At pH values above 7, brown-colored
compounds are produced via isomerization and condensation reactions, and tan-
ning efficacy is reduced.
Stability evaluation: The stability evaluation of self-tanning products is not
unlike that required for other cosmetic products because DHA is not stable above
40°C. The finished formulation, in the production package, must be subjected to
both high (40°C for three months or longer) and low (–10°C to 25°C, five freeze-
thaw cycles) temperatures. Color, odor, viscosity, pH and DHA stability must be
monitored to ensure a long-term storage stability of the final products. DHA content
in cosmetic formulations can be determined by converting DHA to glycerol using
glycerol dehydrogenase and NADH (reduced nicotinamide adenine dinucleotide)
and measuringa the absorbance of NADH at λmax 365 nm.
Selection of Ingredients
In order to have a stable DHA formulation, one must carefully select appropriate
ingredients for each formula because a potential for ingredient interaction always
exists. Certainly, all ingredients selected must be cosmetically acceptable, have a
good safety record, be stable, and must not interfere with the efficacy of DHA in
any way. The following are some comments on how to select ingredients.
Emulsifers: The use of nonionic emulsifiers is recommended over ionic emulsi-
fiers because of improved stability of DHA in the formulations.
Emollients: Emollients represent one of the most important classes of emul-
sion components. They provide a silky skin feel on application.
Many types of emollients exist: esters, waxes, fatty alcohols, mineral oils and
silicone materials. Esters are the most common classes of emollients used in self-
tanning products. Silicone-based oils have also enjoyed an increase in popularity
in recent years. Dimethicone and cyclomethicones are the widely used materials
of this type. All these emollients are compatible with DHA.
Thickeners: Thickening a formulation containing DHA, especially to produce
a clear gel, is relatively difficult because many conventional cosmetic thickeners
are not compatible with DHA. Scientists at Merck KGaA, Darmstadt, Germany
screened a wide variety of thickeners in the early 1990s. The simple method used
for this study called for a solution of 5% DHA and a thickener, storing at room
temperature and at 40°C for three months, and analyzing for DHA content and
solution colors.
Based on this and other studies, they determined that three good choices
for thickeners are hydroxyethylcellulose, methycellulose and silica. Additionally,
xanthan gum and polyquaternium-10 may also be used for thickening emulsions.
Carbomers, sodium carboxymethylcellulose, PVM/MA decadiene crosspolymer, and
magnesium aluminum silicate are not acceptable thickeners because they cause a
rapid degradation of DHA at 40°C.
387
Moisturizers: The natural water content of stratum corneum is not sufficient

to cause the tanning reaction. Therefore, water-free systems are not at all useful
for formulating tanning products. Moisturizers, like sorbitol or propylene glycol,
at a level of approximately 20% (w/w of formulation) help increase the tanning
intensity.
Preservatives: Aqueous solution or emulsion of DHA is susceptible to microbial
attack. For this reason, preservation of the final product as well as hygienically clean
manufacturing and packaging procedures are particularly important. Parabens and
phenoxyethanol, alone or in combination, are recommended preservatives.
Compounds containing nitrogen: Amines or other nitrogen-containing
compounds should be avoided in the final formulation. These compounds include
collagen, urea derivatives, amino acids and proteins.
The reactivity of DHA towards these nitrogen-containing compounds can lead
to gradual breakdown of DHA and, thus, to a loss of efficacy in use. However, many
of the available commercial formulations include amino acids. This combination
gives a perceptual advantage; customers begin to see a tanning effect within about
45 minutes due to the reaction between DHA and the amino acids. Only glycine
and histidine provide brown color. However, this tan is not substantive, and part
of it is easily washed off.5 In order to prevent the reaction from occurring before
application, two suppliers have patented a two-compartment dispenser; the amino
acids are in one compartment and the DHA in the other.18
Sunscreens: It must be noted that a tan achieved with DHA alone does not
offer sun protection comparable to that resulting from natural melanin production
during sunbathing. It is, however, possible to combine DHA with non-nitrogen-
containing sunscreens, such as ethylhexyl methoxycinnamate, ethylhexyl salicylate,
homosalate, benzophenone-3 or octocrylene. The combination delivers a product
with additional sun protection effect. Inorganic sunscreens, such as titanium di-
oxide, zinc oxide, and other metal oxides, must be avoided because they induce
rapid degradation of DHA.
Fragrance oils: The choice of a proper fragrance can enhance the aesthetics
of any self-tanning formulation. However, their use level must be kept as low as
possible because fragrance oils can be irritating. They can also discolor formula-
tions or degrade DHA. Their breakdown products can be photosensitizers. Thus,
great care must be taken in choosing them.
Tinting: To achieve a makeup effect with self-tanning products, we suggest
combining DHA with organic compounds such as carotene, D&C Blue No. 4,
staining dyes such as D&C Red No. 21, and other approved dyes. The use of iron
oxides must be avoided, because DHA will degrade rapidly.
Quantification of Tan
The human eye is able to differentiate colors very easily, including the color
obtained from self-tanning products. The challenges are to remember a color
difference and to quantify it. Color standards like the Pantone color cards can be
useful, but the number of colors in such a system is very limited.
388
One successful method to evaluate the tan is chromometric measurement,19,20

specifically, the L* value (lightness), a* value (indicates the color in red-green axis)
and b* value (indicates color in blue-yellow axis) system. With this method, L*
values for tanned skin were found to be too sensitive to different light conditions
or pressure forces, whereas a* and b* remained quite stable.21 From the a* and b*
values, one can calculate two additional parameters, which are the hue angle (h)
and the hue intensity (C):
h = arctan (b*/a*)
C = √a*2 + b*2
When the hue intensity (C) is higher, the tanning is more intense. The hue
angle (h) for Caucasian skin remained in the yellow-red area. A good correlation
between the visual impressions and the C or h values was demonstrated.21 The eye
still has a greater sensitivity than the chromometric method, but the latter has the
advantage of quantifying the difference in tan color and intensity.
Formulations
An investigation of several self-tanning products on the market revealed that
in some formulations, the content of DHA decreases considerably even when
stored at room temperature. An elevated pH appears to be the main reason for
DHA decomposition.
One can easily make a fairly good formulation if one follows the guidelines
above regarding temperature, pH, buffers, stability evaluation, and selection of
ingredients. Using those guidelines, Thekla Kurz of Merck KGaA, Darmstadt,
Germany prepared a self-tanning o/w lotion (Formula 39.1) and studied its stabil-
ity at room temperature storage for three and a half years. Only 10% of the DHA
was lost (5% to 4.5%).
Formula 39.1. Self-Tanning Lotion (O/W)

A. Glycerol stearate (Arlatone 983 S, ICI) 1.50% w/w
Ethoxylated fatty alcohol (Arlatone 985, ICI) 2.20
Steareth-10 (Brij 76, ICI) 1.50
Mineral oil (paraffinum liquidum), medium viscosity 5.00
Caprylic/Capric triglyceride (Miglyol 812, Huls) 5.00
B. Sorbitol (Sorbitol F liquid, Rona) 2.50
Preservative qs
Water (aqua), demineralized qs 100.00
C. Water (aqua), deionized 5.00
Dihydroxyacetone (Dihydroxyacetone, Rona) 5.00
100.00
Procedure: Heat A to 75°C and B to 80°C. Add B slowly to A while stirring.

Homogenize. Cool while stirring. Add C at 40°C.
Note: Viscosity 2,250 cps (Brookfield RV#3, 20 rpm @ 25°C)
389
Several recent patents claim to have developed self-tanning compositions with

improved stability. Estée Lauder scientists have developed a self-tanning composi-
tion using DHA and cyclodextrins.22 The composition was found to be stable and
have reduced odor associated with the reaction between DHA and the skin. They
have also shown that an effective amount of a long-chain a-hydroxy acid provides
enhanced stability of DHA in formulated products.23
Kurz et al. have developed a stable formulation that consists of DHA, meta-
bisulfite salts and magnesium stearate.24 The improved stability is achieved by the
action of the metabisulfite salts scavenging formaldehyde released from DHA.
Subsequent reaction products of formaldehyde, such as formic acid, are also re-
duced. Ordinarily, DHA and sodium metabisulfite cannot be combined because
they interact to form viscous brown substances. However, the addition of a small
amount of magnesium stearate forms a hydrophobic barrier that prevents the
interaction. Procter & Gamble scientists have obtained a US patent on a similar
composition.25
Pfizer scientists have developed an improved self-tanning composition that
combines DHA with a polyethoxyglycol and a polyol.26 Further improvements are
claimed if a soluble diol is included, and also if the pH is adjusted to approximately
4.0 with a mild organic acid like sorbic acid. The claimed improvements are due to
the equilibrium reaction between the ketone functionality of DHA and the polyols,
forming a cyclic ketal that is more stable than the ketone. The cyclic ketal structure
is stable as long as the pH of the composition remains between 3.5 and 4.5. This
formula will not undergo the Maillard reaction necessary to promote the tanning
reaction. However, when applied on skin, the higher pH of the skin surface converts
the cyclic ketal to the monomeric DHA, and tanning results.
The SPF Effect of DHA

We know that DHA can produce an artificial tan on human skin. We also
know that the reaction product of DHA and the skin protein that produces
the “tan” color is an effective sunscreen agent.27–30 Experimental and clinical
evidence show that skin that has been treated topically with 3% DHA solu-
tion overnight has a Sun Protection Factor (SPF) of at least 3 in the UVB
region. Likewise, a photoprotection factor of 10 in the UVA region has been
observed in skin treated topically with a 15% solution of DHA.
The advantage of this DHA-induced skin pigmentation is that it cannot
be removed by perspiration, swimming or washing. It can only be removed
by desquamation. It provides photoprotection both in the UVB and UVA
regions when the regular sunscreen has been lost. However, one will still
need plenty of sunscreen, sunglasses, and a big hat to remain protected.
This photoprotection property has been used in protecting uninvolved
skin by DHA during psoralene-UVA (PUVA) treatment of psoriasis.31 By
preferentially protecting uninvolved skin, DHA allows higher UVA doses
to be tolerated and delivered to the psoriatic plaques with acceleration in
clearing.
390
Formulas 39.2 through 39.5 show how DHA is used in different formula
types currently on the market.
Formula 39.2. Self-Tanning Lotion

A. Water (aqua), demineralized 39.10% w/w
Methylparaben 0.20
Propylparaben 0.10
Xanthan gum (Keltrol CGT, Calgon) 0.75
B. Glyceryl stearate (and) PEG-100 stearate
(Arlacel 165, Uniqema) 1.20
PEG-40 stearate (Myrj-52-S, Uniqema) 0.40
Steareth-2 (Brij-72, Uniqema) 0.70
Cetearyl alcohol (and) ceteareth-20 (Cosmowax J, Croda) 1.00
Cetyl alcohol (Crodacol C-70, Croda) 1.50
Cyclomethicone (Dow Corning 344 Fluid, Dow Corning) 5.00
Dimethicone (Dow Corning 200 Fluid, 100 cst, Dow Corning) 0.50
Isononyl isononanoate (Pelemol IN-2, Phoenix) 28.50
C. Citric acid, 50% soln 0.05
D. Water (aqua), demineralized 10.00
E. Phenoxyethanol (Phenoxyethanol, Nipa) 1.00
100.00
Procedure: Combine all ingredients of A except xanthan gum. Disperse xanthan

gum into A with agitation. Heat A to 70–75°C. Combine B and heat to 70–75°C. Add
B to A while stirring. Gently homogenize until 50°C. Cool down while stirring and
add C at 40°C. Adjust pH to 5 with C. Add D at 40°C. Add E. Mix until uniform.
Formula 39.3. Self-Tanning Lotion

A. Water (aqua), demineralized 58.80% w/w
Methylparaben 0.15
Propylparaben 0.05
Hydroxyethylcellulose (Natrosol 250 HHR, Aqualon) 0.25
Xanthan gum (Keltrol CGT, Calgon) 0.25
B. Steareth-10 (and) steareth-7 (and) stearyl alcohol
(Emulgator E2155, Goldschmidt) 2.00
Glyceryl stearate (and) ceteth-20
(Teginacid H, Goldschmidt) 2.00
Glyceryl stearate (Tegin M, Goldschmidt) 3.00
Cetearyl octanoate (Luvitol EHO, BASF) 5.00
Oleyl oleate (Schercemol OLO, Scher) 5.00
Microcrystalline wax (White Microcrystalline wax 1275W,
Frank B Ross) 1.00
Capric/Caprylic triglyceride (Myritol 318, Cognis) 3.00
Dimethicone (Dow Corning 200 Fluid, 100cst, Dow Corning) 0.50
C. Water (aqua), demineralized 10.00
100.00
391
Procedure: Combine water, propylene glycol, methylparaben and propylparaben

from A Disperse hydroxyethylcellulose and xanthan gum into A with agitation.
Heat A to 70–75°C. Combine B and heat B to 70–75°C. Add B to A while stirring.
Gently homogenize until 50°C. Cool down while stirring and add C at 40°C. Mix until
uniform.
Formula 39.4. O/W Self-Tanning Cream with UV Filter

A. Octyl methoxycinnamate (Eusolexa 2292, Rona) 5.00% w/w
Benzophenone-3 (Eusolex 4360, Rona) 2.00
Glyceryl stearate (and) steareth-25 (and) ceteth-20
(and) stearyl alcohol (Tego-Care 150, Goldschmidt) 8.00
Cetearyl alcohol (Lanette O, Henkel) 1.50
Stearoxy dimethicone (Abil Wax 2434, Goldschmidt) 1.60
Cetearyl octanoate (Luvitol EHO, BASF) 5.00
Isopropyl myristate (Emerest 2314, Henkel) 3.00
Caprylic/Capric triglyceride (Miglyol 812 neutral oil,
Huls America) 5.00
Dimethicone (Dow Corning 200, 350 cs, Dow Corning) 0.50
B. Propylene glycol (1,2-Propanediol, BASF) 3.00
Methylparaben 0.15
Propylparaben 0.05
Water (aqua), deionized 50.20
C. Dihydroxyacetone (Dihydroxyacetone, Rona) 5.00
Water (aqua), deionized 10.00
100.00
Procedure: Heat A to 75°C, B to 80°C. Add B slowly to A while stirring. Homogenize.

Cool down while stirring and add C at 40°C.
Note: Viscosity 38,800 cps (Brookfield RVT, Sp. F, 10 rpm @ 25°C)
Note: SPF (by Diffey method) = 19.0; UVA PF = 9.5
a
Eusolex is a registered trademark of Rona/EM Industries, Hawthorne, NY, USA.
Formula 39.5. Sunless Tanning Spray-Lotion

A. Glyceryl stearate (and) ceteareth-20 (and)
cetearyl alcohol (and) ceteareth-12 (and)
cetyl palmitate (Emulgade SE, Henkel) 4.50% w/w
Ceteareth-20 (Eumulgin B2, Henkel) 1.00
Dicapryl ether (Cetiol OE, Henkel) 5.00
Coco caprylate/caprate (Cetiol LC, Henkel) 5.00
B. Water (aqua), demineralized qs 55.00
C. Water (aqua), demineralized 20.00
Propylene glycol (and) DMDM hydantoin (and)
methylparaben (Paragon, McIntyre) 1.00
100.00
392
Procedure: Combine A, stir and heat to 80–85°C. Heat B to 80–85°C. Slowly add
A to B while stirring with a propeller mixer. Homogenize AB, allowing the mixture
to cool. Combine C at room temperature by stirring. Add C to AB, when AB
temperature has reached 30°C. Adjust pH to 3.5–4.0 with citric acid if needed.
Note: Viscosity < 100 cps (Brookfield RV#1, 50 rpm @ 25°C)
Emulsion Stability Freeze/Thaw - no separation after 5 cycles
Emulsion Stability 50°C - no separation after 4 weeks
Conclusion
DHA, used as a self-tanning agent for more than 30 years, is a safe product for
use instead of sun-induced tanning. We now have a much better understanding
how DHA works with skin protein to provide an artificial tan. We also know how to
formulate stable formulations with DHA by careful selection of ingredients, pH and
storage conditions. Experimental and clinical evidence have shown DHA-containing
product provides some photo-protection (for better photo-protection always use
in combination with non-nitrogen-containing organic sunscreens). This photo-
protective property of DHA has been utilized in the treatment of psoriasis.
References
1. D Meyers, IR Scott and NJ Lowe, in Sunscreens: Development, Evaluation, and
Regulatory Aspects 2nd edition LJ Lowe, NA Shaath and MA Pathak, eds, Marcel
Decker, New York 101 (1997)
2. LR Kligman and AM Kligman, in Sunscreens: Development, Evaluation, and
Regulatory Aspects 2nd edition, LJ Lowe, NA Shaath and MA Pathak, eds, , Marcel
Decker, New York 117 (1997)
3. E Wittgenstein and HK Berry, Science 132 894 (1960)
4. RK Chaudhuri, The Chemistry and Manufacture of Cosmetics, M Schlossman, ed,
Allured Publishing, Carol Stream, Illinois: (in print)
5. T Kurz, Cosmet Toil 109(11) 55–61 (1994)
6. US Pat 5,770,411, HL Ohrem and F Westmeier (1998)
7. C Aretz, R Buczys, K Buchholz and H Driller, Eurocosmetics, 7 32 (1999)
8. H Fuehrer, Seifen-Oele-Fette-Wachse 20 607 (1960)
9. T Kobayashi and H Higasi, J Molec Struct 35 85 (1976)
10. PA Levene and A Watt, J Biolog Chem 78 23 (1928)
11. AJ Showler and PA Darlet Chem Rev 67 427 (1967)
12. VA Yaylayan, S Harty-Majors and AA Ismail, Carbohyd Res 318 20 (1999)
13. L Goldman, J Barkoff and D Blaney, J Invest Dermatol 35 161 (1960)
14. M Angrik, Chemie in Unserer Zeit 14 149 (1980)
15. T Severin, Lebensm Unters Forsch 178 284 (1984)
16. GP Ellis, Adv Carbohydr Chem 14 63 (1959)
17. A Meybeck, J Soc Cosmet Chem 28 25 (1977)
18. EP 0547864A1, A Suares (1993)
19. RG Kuehni, CIELAB Color Difference and Lightness, Hue and Chroma Components for
Objective Color Control, Technical Bulletin No 1, Detroit Color Control
20. RM Johnson, Pigment Handbook, vol III, TC Patton, ed, John Wiley & Sons, New York
(2291973)
393
21. T Kurz, Proceedings of International Federation of Society of Cosmetic Chemists 361

(1995)
22. US Pat 5,514,367, PJ Lentini and JR Zecchino (1996)
23. US Pat 5,942,212, PJ Lentini, P Tchinnis and N Muizzuddin (1999)
24. DE 43 14 083 A1 T Kurz, S Hitzel, R Martin and R Emmert (1994); EP 0 622 070 B1
(1997); US Pat 5,656,262 (1997)
25. US Pat 5,514,437, CR Tanner and LR Robinson (1996)
26. EP 884045, JA Scott and EM Stroud (1998)
27. R Fusaro and JA Johnson, Dermalogica 150 346 (1975)
28. R Fusaro and JA Johnson, Dermalogica 172 53 and 58 (1987)
29. JA Johnson and R Fusaro, Dermatology 185 237 (1992)
30. RM Sayer, DL Torode, JA Johnson and RM Fusaro in Melanin: Its Role in Human
Photoprotection: A Melanin Symposium, L Zeise, MR Chedekel and TB Fritzpatrick,
eds, Valdemar, Overland Park, Kansas 1 (1994)
31. CR Taylor, C Kwangsuksith, J Wimberly, N Kollias and RR Anderson, Arch Dermatol
135 540 (1999)
21. US Patent 4,724,258, to Dexter (February 1988)
22. US Patent 6,338,042, to O’Lenick (December 2002)
23. US Patent 5,280,099, to O’Lenick (January 1994)
24. US Patent 5,300,666, to O’Lenick (April 1994)
25. US Patent 5,120,812, to O’Lenick (June 1992)
Chapter 40
The Dry Facts About

Wet Perspiration
Society today demands a means for controlling perspiration,
its resultant odor and effective deodorant and antiperspirant
formulations.
key words: perspiration anatomy, odor production, deodorants,

antiperspirants, efficacy
P erspiration is a body phenomenon of physiologic importance impacting both

personal hygiene and societal aesthetics. There are several dermatological dis-
eases (anhydrotic ectodermal dysplasia and its variants) where failure to perspire
results in the inability to maintain normal body temperatures in warm environments.
Thus, perspiration is an important body function allowing dissipation of body heat
through the phase change from liquid water to gas water vapor accompanied by
subsequent evaporation. This is an extraordinarily efficient method of prevent-
ing hyperthermia, or body overheating, allowing humans to survive temperature
extremes. Yet, many in modern society consider perspiration to be undesirable. It
can also be the source of emotional distress and personal embarrassment.
It is necessary to realize that certain sweat glands are temperature controlled
alone, while other glands are under both temperature and emotional control.
Specifically, sweat glands in the armpits and on the palms of the hands are primar-
ily under emotional control. In addition, sweat glands on the face may be under
emotional control and are also able to respond to the ingestion of spicy foods.
From the standpoint of a young cosmetic chemist, the sweat glands that are most
problematic to the general population are the axillary glands that contribute to
underarm wetness. Axillary sweating is considered to be unattractive and possibly
an unspoken signal that a stressful situation is occurring.
The remainder of this discussion will focus on the mechanisms of axillary per-
spiration and control.
The Anatomy of Perspiration

The are two types of sweat glands present on the body: eccrine sweat glands
and apocrine sweat glands. Two to 4 million eccrine sweat glands are found all over
the body and function in thermoregulation, as previously discussed.1 They are most
numerous on the foot and found in lower concentration on the back. Apocrine
sweat glands are the scent glands of the body, primarily located in the armpits,
395
396
The Dry Facts About Wet Perspiration Beginning Cosmetic Chemistry
around the eyes, on the scalp, and amongst the genitalia. These glands are well
developed in animals, such as the skunk and the deer, however, their importance
in humans is significantly reduced. Apocrine secretions may function to allow an
infant to identify its mother and may function in courtship, but otherwise these
glands have little value.
The body’s thermostat: Eccrine perspiration is produced by the secretory coil
in response to acetylcholine, a neurotransmitter of the sympathetic nervous system.
The sweat is actually squeezed from the gland by special myoepithelial cells in a
duct that carries the liquid to the skin surface. The initial fluid released is dilute
and plasmalike, but sodium and excess water are reabsorbed by the duct creating
a hypertonic solution. This reabsorption is important to maintaining the electrolyte
and water balance of the body. In addition to electrolytes (Na+, K+, Ca2+) and
water, sweat can contain heavy metals and some organic compounds, including lac-
tate, urea, ammonia, amino acids, glycoprotein, and acidic mucopolysaccharides.2,3
Sweat is produced in response to stimuli from the hypothalamus, a special part of
the brain, which acts as a thermostat for regulating body temperature.
Apocrine perspiration is a milky, viscous fluid without odor when it is first
secreted. Bacterial action is necessary for odor production. Little is known about
the composition of pure apocrine sweat, since it is always secreted in combination
with eccrine sweat and cannot be isolated. The secretion is squeezed again by
myoepithelial cells into a duct that carries the mixture to the skin surface. Secre-
tion is induced by emotive stimuli after puberty under the control of epinephrine
and norepinephrine, which are neurotransmitters.4
Mechanisms of Odor Production

One of the most bothersome aspects of axillary perspiration is the resultant
odor. As mentioned previously, sweat is a sterile, odorless, colorless fluid com-
posed of eccrine and apocrine secretions. Odor occurs as the bacteria count in
the armpit increases. Apocrine sweat, which is much less abundant than eccrine
sweat, is responsible for a large part of the odor. It is rich in organic material ideal
for bacterial growth. Eccrine sweat, on the other hand, is more dilute and does
not provide a high concentration of bacterial nutrients. However, eccrine sweat
indirectly promotes odor by dispersing the apocrine sweat over a larger area and
providing the moisture necessary for bacterial growth.
Another important contributing factor to armpit odor is axillary hair. The surface
area of the hair shaft also contributes to odor by acting as a collecting site for apo-
crine secretions and increasing the surface area suitable for bacterial proliferation.5
Many adolescents do not notice axillary odor until puberty triggers both armpit hair
growth and an increased production of apocrine perspiration.
The odor present in the axilla varies substantially from person to person. Odor
is inflenced by the mix of bacteria that colonize a given individual’s armpit and by
the composition of the sweat produced. Sweat composition is influenced by the
combined effect of the foods last eaten and the physical or psychological body state.
Foods, such as garlic, onion, and asparagus, are known for their ability to impart a
characteristic smell to body secretions, as the sebum mixes with the perspiration.
397
Certain disease states, such as renal failure and ketoacidosis, can be recognized by
physicians because of the characteristic smell.
Mechanisms of Odor Control

Now that an understanding of sweat composition, secretion, and odor production
has been obtained, it is important to consider mechanisms of odor control. Table
40.1 lists methods available to reduce axillary odor.6 Simply stated, if the sweat does
not remain in the armpit, odor is not produced. It would seem easiest to absorb the
perspiration as it is manufactured by wicking away the wetness. Unfortunately, this
is not possible, since tremendous variations occur in the amount of the secretions,
easily overwhelming any chemical capable of absorbing wetness. Perspiration can
vary from several liters per hour to 10 liters per day.
Table 40.1. Methods of reducing axillary odor
1. Reduce apocrine perspiration

2. Reduce eccrine perspiration
3. Remove the apocrine and eccrine gland secretions
4. Decrease bacterial growth
Another mechanism to prevent odor production is to prevent the perspiration

from being formed in the first place. Since perspiration is under control of the
central nervous system and peripheral nerves, it is possible to decrease sweating
by altering nerve pathways. Unfortunately, the neurotransmitters that induce the
release of sweat are the same that control the entire functioning of the body. Oral
medications that are used to control sweating also cause dry mouth, dry eyes, and
difficulty with urination. They may be taken episodically for a special occasion, but
are not practical for daily use.
Thus, control has focused mainly on preventing the sweat from leaving the gland
and flowing out on to the skin surface. This can be accomplished by somehow plug-
ging the gland, which is the mechanism of action of modern day antiperspirants.
Antiperspirants vs. Deodorants

Antiperspirants and deodorants are sometimes confused and the terms used
interchangeably, but these products have different functions and ingredients.
This article has focused on antiperspriants, which are designed to minimize the
release of sweat into the armpits. This can be accomplished through a variety of
mechanisms, discussed below. Deodorants, on the other hand, function to reduce
odor in the armpit. This can be accomplished through the use of fragrances, which
simply mask the armpit odor. Another mechanism is to destroy the bacteria in the
armpit through the use of antibacterial agents, such as triclosan or triclocarbon.
Most topical antiperspirant formulations also function as deodorants, since the pH
diminishes bacterial growth and the elimination of moisture also retards bacterial
398
reproduction. While antiperspirants can function as deodorants, deodorants cannot

function as antiperspirants.
Mechanism of Antiperspirant Action

There are 25,000 eccrine glands per axillary vault capable of producing large
quantities of perspiration in response to heat and emotional stimuli. The follow-
ing substances have been shown to reduce the amount of moisture present in the
armpit:7
1. metal salts (aluminum chlorohydrate, aluminum zirconium chlorohydrate)
2. aldehydes (formaldehyde, glutaraldehyde)
3. anticholingeric drugs
4. antiadrenergic drugs
5. metabolic inhibitors
6. botulinum toxin A (Botox)
The most commonly used substances to reduce perspiration are the metal salts.
Several theories have been advanced regarding the mechanism of sweat reduction
due to axillary application of metal salts. Papa and Kligman originally proposed that
the metal salts damaged the sweat duct causing the secreted sweat to diffuse into
the interstitial space.8 They have since retracted their theory. Shelley and Hurley
proposed that the metal salts combine with intraductal keratin fibrils to cause eccrine
duct closure and formation of a horny plug to obstruct sweat flow to the skin surface.9
A second paper by Papa, Holzle, and Kligman presented evidence demonstrating
that aluminum salt-containing antiperspirants alter the physiologic state of the
sweat duct by creating an aluminum-containing cast within the the duct.10,11 This
cast creates a physical blockage in the duct preventing the sweat from exiting. It is
assumed that the secretion is reabsorbed by the duct. This is not health problem,
since there are plenty of other eccrine glands to insure thermoregulation.
Aldehydes, such as formaldehyde and glutaraldehyde, are another category of
chemicals that can effectively decrease axillary sweating.12 ,13 It is believed that these
chemicals also result in blockage of the eccrine sweat duct like the metal salts. The
aldehyes are not generally used due to the sensitizing potential of formaldehye and
the brownish-yellow skin staining associated with glutaraldehyde.
Anticholinergic drugs are the most effective antiperspirant agents known.
Blockage of the cholinergic innervation of the eccrine sweat glands effectively
stops sweating. Agents such as scopolamine and atropine have been studied in
this regard, however, skin penetration is poor unless administered via injection or
iontophoresis, where low voltage electricity is used to force the chemical into the
skin. Furthermore, their use is accompanied by undesirable side affects such as
dry mouth, dry eyes, and problems with urination.
Antiadrenergic drugs theoretically could also decrease sweating. Adrenergic
neurotransmitters, such as epinephrine and norepinephrine, have been shown to
increase sweating in humans when they are injected intradermally. This is perhaps
due to some adrenergic nerve fibers providing dual innnervation to the sweat
glands in addition to the cholinergic fibers. But this aspect of sweating is poorly
understood.
399
Regulations of Deodorants and Antiperspirants

1. United States
In the US, underarm deodorants are regulated as cosmetics as long as they
do not make any drug claims. Antiperspirants are drugs1 and are subject
to the current monograph, which is the TFM published in the Federal
Register of August 20, 1982, Volume, 47 pages 36492-36505. A/P are
drugs as they effect the function of the body, i.e., stopping perspiration.
Deodorants are cosmetics as they cover or mask odors. If you claim this
is by bacteria action, this becomes a drug claim and subject to all of the
drug regulations.
Current drug regulations include following the monograph and now
labeling the products with the correct “Drug Facts” back labels.2 Other
requirements included registration of formulations and facilities with the
FDA, manufacturing by GMP’s, etc.
2. European Union
In the EU Annex I, “Illustrative List by Category of Cosmetic Products”
specifically lists deodorants and antiperspirants as cosmetics.3 In Annex III
many of the common actives used in A/P’s are listed with their maximum
permitted levels and restrictions. The major antimicrobial agents, which
also find use as preservatives or antibacterial agents for controlling odors,
are listed with their concentrations and restrictions in Annex VI.
All products sold in the EU must have proper labeling including listing
of all ingredients in descending order. You are also required to maintain
a product information package (also called a dossier). In this package you
are required to have proof of all claims, along with other data.
3. Japan
Underarm deodorants and antiperspirants are regulated in Japan as quasi-
drugs. This requires pre-market approval of your formulation before you
are permitted to market the product.
For more complete details on all of these regulations see Antiperspirants
and Deodorants edited by Karl Laden, 2nd Edition Chapter 10, Regulations
of Underarm Antiperspirants and Deodorants, pages 283–304. This can be
obtained from Marcel Dekker, Inc. in New York City.
References
1. TC-26 Feb 9, 1940
2. For more information on labeling “Drug Facts”see FDA/OTC Label Requirements
from Hirschhorn & Young, Inc, New York, NY
3. The Cosmetic Directive 76/768/EEC
400
Metabolic inhibitors may decrease perspiration. Since the process of sweating is

dependent upon a supply of energy, drugs that interrupt Na+/K+ - ATPase, such as
ouabain, might also be effective. These substances are only of academic interest.
A relatively new chemical, known as Botox (botulinum toxin A), is now finding
a use in palmar and axillary hyperhidrosis. This chemical actually blocks nerve
transmission and prevents innervation of the sweat ducts temporarily. It is injected
directly into the epidermis at 1–2 cm intervals until the entire area of perspiration
has been treated. Usually, the decreased sweating lasts three months to one year,
depending on location and the amount of medication injected.
For all practical purposes, metal salts remain the safest, most reliable, derma-
tologically safe method of decreasing armpit wetness.
Antiperspirant Efficacy
In order to be effective, an antiperspirant must reduce axillary sweating by
20% or more and decrease armpit bacterial colonization. The decrease in axillary
perspiration can be measured by collecting the moisture on armpit pads, which
are weighed before and after exposure to a hot room. The reduction in bacteria
count can be determined through bacterial culture plates and the sniff test. Ap-
plication of an antiperspirant formulation to a culture plate swabbed with human
perspiration can determine the percent reduction of bacterial growth. The sniff
test is performed by several individuals with highly trained noses to “sniff” armpits
before and after application of the product. In some regards, this test may be more
accurate than bacteria culture plates since it takes into account the actual environ-
ment of the armpit.
Many different antiperspirant formulations have been developed to meet con-
sumer preferences including aerosols, creams roll-ons, liquids, lotions and sticks.
The efficacy of these various formulations is summarized in Table 40.2.
Table 40.2. Antiperspirant effectiveness by form
US FDA OTC Antiperspirant Review Panel

Dosage form Average reduction (%)
Aerosols 20–33
Creams 35–47
Roll-ons 14–70
Lotions 28–62
Liquids 15–54
Sticks 35–40
Summary
The development of quality antiperspirants depends on an understanding of
the basic mechanisms operative in perspiration and body odor. Perspiration is a
401
complex physiologic and psychologic process that can be physically and emotionally
disabling. Children who sweat profusely from the palms when stressed typically get
lower grades on their messy papers than children who are not afflicted with this
problem. Most individuals, personally and professionally, who aren’t embarrassed or
encumbered by underarm wetness, feel more comfortable in their daily activities.
Antiperspirants represent a category of OTC drugs that have a profound impact,
even though they are topically applied.
Published August 2001 Cosmetics and Toiletries magazine.
References
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2. T Morimoto, RE Johnson, Ammonia and the regulations of activity in human eccrine
sweat; Nature 216:813-814, (1967)
3. JC Pallavinvini, et al., Isolation and characterization of carbohydratprotein complex
from human sweat; Ann NY Acad Sci 106; 330-338, (1963)
4. WB Shelley, Apocrin sweat; J Invest Dermatol 1725, (1951)
5. S Plechner; Antiperspirants and Deodorants in Cosmetics, Science and Technology,
(2), 2nd ed., Wiley-Interscience, New York, (1972), 373
6. JB Wilkinson et al; Harry’s Cosmeticology; 7th ed, Chemical Publishing, New York,
(1982), 125
7. RP Quatrale; The Mechanism of antiperspirant action in eccrine sweat glands, in
LadenK, Felger CB (eds) Antiperspirants and Deodorants; Marcel Dekker, Inc. New
York, (1988), 89-110
8. CM Papa, AM Kligman; Mechanisms of eccrine anhidrosis II; The antiperspirant
effects of aluminum salts, J Invest Dermatol 49, 139-145, (1967)
9. WB Shelley, HJ Hurley Jr., Studies on topical antiperspirant control of axillary
hyperhidrosis; Acta Derm Vernereol 55: 241-160, (1975)
10. CM Papa, AM Kligman, Mechanisms of eccrine anhidrosis, II, The antiperspirant effect
of aluminum salts, J Invest Dermatol 49:139, (1967)
11. E. Holzle, AM Kligman, Mechanism of antiperspirant action of alumninum salts, J Soc
Cosmet Chem 30: 279, (1979)
12. L Juhlin, Topical glutaraldehyde for plantar hyperhidrosis, Arch Dermatol 97:327-330,
(1968)
13. K Sato, RL Dobson; Mechanism of the antiperspirant effect of topical glutaraldehyde,
Arch Dermatol 100: 564-569, (1969)
Chapter 41
Improving the Appearance

of Facial Pores
In this study of pore size and sebum composition, the
authors report that topical application of polyoxyethylene/
polyoxypropylene dimethyl ether improves
skin texture and reduces parakeratosis in facial skin,
making large pores less visible.
key words: pore, parakera-tosis, unsaturated fatty acid,

polyoxy-ethylene/polyoxy-propylene dimethyl ether
C onspicuous pores are a perennial problem for women of various ages and concern
about them is increasing. In our own survey of 1,781 women in Japan, more
than half of women in their twenties or thirties complained of conspicuous pores.
An international attitude survey of women in their twenties revealed that enlarged
or highly visible pores are also a major concern among women outside of Japana.
In general, people who secrete a large amount of sebum have large facial pores.
However, there has been little scientific study of noticeable facial pores. Therefore,
we investigated the physiological characteristics of the cheek skin of healthy women
volunteers in their twenties and thirties.
Structure of Conspicuous Pores

Skin texture is created by furrows and ridges. Pores are located where furrows
intersect. Each pore is linked with a sebaceous gland as shown in Figure 41.1,
and sebum is secreted through it. It is probable that pore size is directly related to
sebaceous gland size. Large pores indicate larger glands, which will produce more
oil. It has been known that women with larger pore size may make more oil than
women with smaller pore size.
Pores are found all over the skin surface of the body, except for the palm and
sole. By examining conspicuous pores and inconspicuous pores under a magnifying
glass or microscope, we concluded that large cone-shaped hollows around seba-
ceous ducts seem to be shadowed and consequently appear as conspicuous pores.
To confirm the structure, we made replicas of cheek skin. In the replicas, the large
pores resemble mountains or barnacles (Figure 41.2).
403
404
Improving the Appearance of Facial Pores Beginning Cosmetic Chemistry
Figure 41.1.
Figure 41.2.
Next, we compared the condition of corneocytes around pores to that of corneo-

cytes in other areas. When nuclei were stained with hematoxylin or bisbenzimide
H 33342b, nucleated cells (see Nucleated Cells sidebar) were frequently found
only in the corneocytes around pores.
The significance of this finding will be described in a moment. In general,
approximately 90% of nucleated cells seem to be located around pores among
tape-stripped corneocytes.
We visually examined the cheeks of 20 healthy Japanese women and classified
them into two groups: those with conspicuous pores and those with inconspicuous
pores. We counted nearly five times as many nucleated cells around the conspicu-
ous pores as we counted around the inconspicuous pores (3500 versus 700 in an
area 23 mm x 34 mm around each measured pore). These results confirm that
skin with conspicuous pores has abundant nucleated cells compared to that with
inconspicuous pores.
405
Nucleated Cells
The term nucleated cells refers to cells that have nuclei. As described,
parakeratosis is a condition in which inflammation, stimuli or a similar cause
accelerates the keratinization process, giving rise to incomplete horny cells
with the nucleus retained. Horny cells developed through normal keratiniza-
tion do not have a nucleus.
This skin condition of abundant nucleated cells is called advanced parakeratosis.

In this condition inflammation, stimuli or other causes accelerate the keratinization
process, giving rise to abundant incomplete corneocytes in which the nucleus is
retained. Namely, the skin condition around such pores is relatively poor. Parak-
eratosis around pores is found especially in the cheek and forehead area, and is less
frequent in other places such as the arm, where pores are inconspicuous.
Effect of Sebum Components

We recruited 94 healthy volunteers (59 Japanese females and 35 Caucasian
females living in Japan) in their twenties and thirties and classified them into three
groups on the basis of apparent facial pores: A—inconspicuous pores; B—ordinary
pores; C—conspicuous pores (Figure 41.3).
Figure 41.3.
The relationships between noticeable pores and skin parameters such as tran-
sepidermal water loss (TEWL) value or the amount and composition of sebum
were investigated instrumentallyc. Because similar results were obtained in both
Caucasians and Japanese, only typical data obtained from Japanese are shown here.
The data were mainly analyzed by using the unpaired t-test.
Average TEWL values of subjects with unconspicuous and average pores were
slightly lower than those of subjects with conspicuous pores (22.3, 21.3 and 23.9 g/m2
per hr for groups A, B and C, respectively).
Sebum was collected with glass filter paper and extracted with acetone, and the
amount and components of sebum were analyzed by gas-chromatographyd.
The amount of sebum increased in parallel with the pore size (53, 100 and 135
µg of sebum for groups A, B and C, respectively). This result is consistent with
406
suggestions in cosmetics magazines and technical books that excessive sebum may
be related to noticeable pores.1 However, it is not known which component of
sebum is most associated with conspicuous pores.
We found no marked differences in components such as triacylglycerol, squalene,
wax and saturated fatty acids. However, unsaturated free fatty acids, such as oleic
acid and palmitoleic acid, were more abundant in sebum of women with conspicu-
ous pores (2.3, 3.4 and 4.4% unsaturated free fatty acids in the sebum for groups
A, B and C, respectively).
Oleic acid (C18:cis-9) is one of the major components among unsaturated
fatty acids in sebum. This material may be synthesized from saturated fatty acid
by desaturases or it may also be produced from triacylglycerides by lipases as
palmitoleic acid (C16:cis-9). These substances are known to cause roughness of
the skin surface, inflammation, acne and comedo.2, 3 Although the composition of
fatty acids on human face has been reported,4 this finding was the first of its kind
on the relationship between pore size and the sebum composition.
Effects of Unsaturated Fatty Acids on Human Skin

We next examined the effects of unsaturated free fatty acids on human skin
by applying 30% oleic acid to the human forehead for three days to induce par-
akeratosis. This concentration is very high compared to the content of the skin
surface lipid. Parakeratosis in the horny layer was then examined by tape-stripping
corneocytes and staining the nucleosomes. Many nucleated cells, stained purple,
were seen only in the forehead to which oleic acid had been applied. The TEWL
value also increased.
Next, we applied 3% oleic acid to human cheek for four weeks (twice a day); this
concentration is equal to that in sebum. The degree of parakeratosis of corneocytes
in the skin to which oleic acid was applied was greater than that in the skin to which
ethanol was applied (1100 versus 800 nucleated cells in a 12 mm by 34 mm area).
Because oleic acid was resolved in the final concentration 3%, not in water, we used
ethanol as a negative control. Similar results were obtained with palmitoleic acid,
which also contains a single double-bond in its structure, like oleic acid.
Other components, including squalene, triolein (a kind of triacylglycerol),
cholesterol and saturated fatty acids such as palmitic acid (C16) and stearic acid
(C18), did not cause parakeratosis or an increase of TEWL value. Linoleic acid
(C18: cis-9, 12), which has two double-bonds, caused weak parakeratosis. These
results suggest that fatty acids that contain one double bond, such as oleic acid and
palmitoleic acid, cause parakeratosis around pores on the cheek after being secreted
from sebaceous glands. The reason for this is now under investigation.
Unsaturated fatty acids cause damage to the skin texture. We applied 30% oleic
acid on human arm skin for six days (n=4), then took a replica of the applied area
and measurede VC1 (a measure of skin homogeneity).5
Compared to ethanol, oleic acid increased the value of VC1 compared to similar
ethanol treatment (VCI readings of 0.017 for ethanol versus 0.093), which reflects
increased anisotropy of the skin furrows (i.e., a deterioration of skin texture).
407
Furthermore, when the VC1 value is higher, the pores of the cheek are more
conspicuous. Among the 94 members of our three classifications based on pore
visibility, the VC1 values averaged 0.275, 0.330 and 0.425 respectively, for A, B
and C classifications. A possible explanation is that when the skin is plumped and
the skin texture pattern is well aligned, pores are inconspicuous. When the ridges
are flat and furrows are shallow, the skin texture is irregular, and the pores look
conspicuous.
The above results suggest that unsaturated free fatty acids, such as oleic acid, may
be one of the main causes of conspicuous pores through induction of parakeratosis
around the pores and impairment of skin texture (increase of VC1 value).
A Treatment for Conspicuous Pores

To treat conspicuous pores, we looked for compounds that suppress the ef-
fect of oleic acid on the skin. Among more than 50 kinds of substances examined,
polyoxyethylene (POE)/polyoxypropyrene (POP)-14/7 dimethyl ether was the most
effective.6 Its structure is shown in Figure 41.4. This compound contains both
hydrophobic and hydrophilic regions, and decreases the VC1 and TEWL values
raised by the application of oleic acid (Table 41.1).
Figure 41.4.
Table 41.1. VC1 and TEWL values raised by the application of oleic acid
VC1 value TEWL value
Oleic acid 0.094 2.33
Oleic acid +POP/POE-14/7 0.043 –0.45
The mechanism of the repression of parakeratosis and the improvement of skin

texture is not yet clear, but POE/POP-14/7 dimethyl ether may absorb oleic acid,
thereby suppressing the interaction between oleic acid and corneocytes.
Next, we prepared a solution of 5% POE/POP-14/7 dimethyl ether and applied
this for four weeks to the cheeks of 34 women volunteers in their twenties or thirties.
After the application, a decrease of nucleated cells and improvement of cheek skin
texture were again detected Figure 41.5. Visual examination was also carried out
and the rate of persons judged as having conspicuous pores was decreased from
21–3%, and those judged as having inconspicuous pores increased from 6–29%.
POE/POP-14/7 dimethyl ether was found to be an effective substance against
conspicuous facial pores. However, it did not produce a clear decrease of the area
of cone-shaped hollows. Further investigation to find more effective compounds
is in progress.
408
Figure 41.5.
Summary
Conspicuous pores are one of the most frequent skin problems for women of
various ages. A study of the relationship between the extent of conspicuous pores
and the skin condition revealed that females with conspicuous pores have a slightly
increased transepidermal water loss (TEWL) value, and a high skin sebum content,
especially in regards to unsaturated fatty acids. Experimental application of oleic
acid, an unsaturated fatty acid, to the forehead of humans promoted parakeratosis
and increased the TEWL value.
Polyoxyethylene (POE)/polyoxy-propylene (POP)-14/7 dimethyl ether was
effective in improving the parakeratosis caused by oleic acid, and reducing skin
roughness. Application of a solution containing POE/POP-14/7 dimethyl ether
improved skin texture and parakeratosis on human cheek, resulting in skin with
less obvious pores.
Published January 2004 Cosmetics & Toiletries magazine
References
1. G Plewig and AM Kligman, Acne and Rosacea, 3rd edn, T Jansen, ed, Springer-Verlag;
Berlin 32–33 (2000)
2. T Maeda, An electron microscopic study of experimentally-induced comedo and
effects of vitamin A acid on comedo formation, J Dermatol 18 397–407 (1991)
3. RE Kellum and K Strangfield, Studies in pathogenesis: Fatty acids of human surface
triglycerides from patients with and without acne, J Invest Dermatol 58 315–318 (1972)
4. A Kotani and F Kusu, HPLC with electrochemical detection for determining the
distribution of free fatty acids in skin surface lipids from the human face and scalp,
Arch Dermatol Res 294 172–177 (2002)
5. M Takahashi, Image analysis of skin surface contour, Acta Derm Venereol Suppl 185
9-14 (1994)
6. T Omori et al, Development of new multifunction cosmetic raw materials and its
applications, In: IFSCC Proceedings Book II 149–162 (2003)
Chapter 42
A Light-Diffusing Concept
for Antiaging Effects in
Makeup Formulations
An innovative light-diffusing concept for special optical effect
(nylon fibers) makes possible the immediate visualization of
the reduction of signs of skin aging while maintaining a natural
makeup and a youthful appearance.
key words: light diffusion, nylon fibers, skin aging, wrinkles
S kin aging is a natural phenomenon that only a few people accept without ap-
prehension. For many years, cosmetology has provided men and women with
appropriate tools for fighting aging. Numerous cosmetic formulations make it pos-
sible to reduce the visible signs of skin aging: skin care products have long-term
effects, but makeup gives more instantaneous results, perceptible immediately
after application.
In order to make the results more magic and spectacular, the current trend is for
products that leave a very transparent and thin film, in a word—natural. Previously,
mineral powders such as oxides, silicates and carbonates, were used extensively in
makeup formulations, providing high coverage, opacity and a mask-like effect on the
skin. Now, in order to achieve more lightness and transparency while maintaining
results, high-tech ingredients have been developed and consequently, talcs or others
minerals have been replaced by sophisticated substances for optical effects.
At LCW we define a “soft focus” effect to suggest the way light diffuses in the
skin of young people. Our studies indicate that light diffuses differently in the skin of
older people because their skin has less microrelief. We have found that by adding
nylon fibers to foundations and creams, we can achieve a “soft focus” effect on aging
skin. In this paper, the concept of light diffusion is evaluated according to two new
innovative methods: RSF (in vitRo Soft Focus) and VSF (in viVo Soft Focus).
Materials
Fibers are one recent significant development for creating optical effects in
makeup and skin care products. Many types of fibers are now available. They are
different in their nature, their size and their aspect. They can be classified as:
409
410
A Light-Diffusing Concept for Antiaging Effects in Makeup Beginning Cosmetic Chemistry
• Natural (such as cellulose fibers);

• Natural derivatives (such as rayon or viscose fibers);
• Synthetic (such as polyamide, polyethylene or glass fibers).
Figure 42.1 illustrates the physical differences between these types of
fibers.
Figure 42.1.
Nylon fibers: Polyamide fibers, and more precisely nylon-6, are the most
remarkable fibers. In a general way, nylon-6 is a linear polymer obtained by po-
lymerization of caprolactam. An optical microscope picture of nylon fibers is shown
in Figure 42.2.
Figure 42.2.
Nylon fibers present all the necessary physicochemical and optical characteristics
in order to create interesting optical effects. The nylon-6 properties are described
in Table 42.1 and its chemical resistance in Table 42.2.
411
Table 42.1. Nylon-6 properties
Water absorption—equilibrium ( % ) >8

Specific gravity (g cm-3) 1.13
Refractive index 1.53
UV resistance Passable
Table 42.2. Chemical resistance of nylon-6
Acids—concentrated bad
Acids—diluted bad
Alkalis good
Alcohols good
Ketones good
Oils good
Halogens bad
Aromatic hydrocarbons good
Regulatory status of nylon-6 is indicated in Table 42.3 and examples of sizes

of nylon fibers are shown in Table 42.4.
Table 42.3. Regulatory status of nylon-6
Chemical composition Poly[imino(1-oxohexane-1,6-diyl)]

CAS Number 25038-54-4
CTFA Nomenclature Nylon-6
JCIC 520835
Table 42.4. Examples of sizes of nylon fibers
Length (mm) Coarseness of fibers (decitex*)

0.4 0.5
2 2
3 6
2 10
5 10
*Decitex is a titration unit for textile fibers. It is the weight (in gram) of a 10,000-meter length of the
product.
412
Raw nylon fibers are white, but a special dyeing process has been developed to
create a wide range of colored fibersa (Figure 42.3a) able to cover almost all the
possible colors in color space. Those of higher interest for cosmetic formulations
are black, beige, white and X-white (with a fluorescent brightening effect under
UV light) (Figure 42.3b and 42.3c).a
Figure 42.3a. Figure 42.3b. Figure 42.3c.
Novel optical films: To evaluate the anti-aging effect of nylon fibers on light
diffusion, we developed novel optical films for both in vitro (RSF) and in vivo
(VSF) tests.
For the RSF test, a transparent film containing nylon fibers was developed to
evaluate the fibers’ optical properties and more precisely their blurring character-
istics. Formula 42.1 was developed to achieve a fast film hardening and to provide
a homogeneous repartition of fibers.
Formula 42.1. Film composition (TW 1419)

Ethylhexylhydroxystearate (and) triethylhexyltrimellitate
(and) C-30-45 olefin (Clearwax, LCW) 40% w/w
Macadamia ternifolia nut oil 57
Nylon-6 fibers (Fiberlon, LCW) 3
100
We also developed a novel optical film for measuring the VSF effect. The VSF
optical film corresponds to a thin layer of the cream shown in Formula 42.2 or
the foundation shown in Formula 42.3 on the skin. Specific formulations must be
developed in order to prevent the fibers from twining during hand application on
the skin surface. The two proposed formulas help to apply an even film of fibers
on the skin with a manual application.
Colored fibers: Fibers are colored in order to achieve specific targets for the
final application. For these studies we use X-white fibers and beige fibers manu-
factured by LCW.
X-white fibers help to visualize the RSF optical film under UV light and give a
whitening effect when applied on an ethnic skin under visible light. A fluorescent
brightening substance was precipitated on the fibers using the color lake technology
(patent pending). The fluorescent brightener is a stilbene derivative. The X-white
fibers are fluorescent under UV exposure.
413
Beige fibers are used for foundation. They are obtained by precipitating water-
soluble dyes such as FD&C Yellow 5 using a similar technique.
Formula 42.2. VSF Cream (TW 1420)

Isononyl isononanoate 8.0% w/w
Cyclomethicone 13.0
Sorbitan oleate (and) paraffinum liquidum (and) aluminum stearate
(and) polysorbate 80 (and) magnesium stearate (and)
BHT (Base W/O 126, LCW) 8.3
X-white Nylon-6 fibers (Fiberlon, LCW) 2.7
Water (aqua), purified 52.0
Sodium chloride 2.2
Glycerin 5.6
Propylparaben 0.1
Methylmethacrylate cross polymer (Covabead PMMA, LCW) 2.5
Methylmethacrylate cross polymer (Covabead LH85, LCW) 0.6
Silica dimethyl silylate (Covasilic 15, LCW) 0.6
Acrylates copolymer (Covacryl E14, LCW) 4.4
100.0
Formula 42.3. VSF Foundation (TW 1421)

Isononyl isononanoate 8.0% w/w
Cyclomethicone 13.0
Sorbitan oleate (and) paraffinum liquidum (and) aluminum
stearate (and) polysorbate 80 (and) magnesium stearate (and)
BHT (Base W/O 126, LCW) 7.0
Beige nylon-6 fibers (Fiberlon, LCW) 2.5
Water (aqua), purified 52.2
Sodium chloride 2.5
Iron oxide (and) propylene glycol (Covasop, LCW) 6.6
Propylparaben 0.2
Methylmethacrylate cross polymer (Covabead PMMA, LCW) 2.5
Methylmethacrylate cross polymer (Covabead LH85, LCW) 0.5
Silica dimethyl silylate (Covasilic 15, LCW) 0.5
Acrylates copolymer (Covacryl E14, LCW) 4.5
100.0
Measuring Optical Effects

Makeup formulations have long been used to blur wrinkles, blemishes and other
signs of skin aging. It has been difficult, however, to formulate a product able to
mask the wrinkles and at the same time give a natural appearance to the skin. The
application of “classic” foundations to aging skin imparted a grayish aspect to the
face incompatible with the translucence of youthful skin.
A close relationship exists between the skin’s optical properties (such as its viv-
idness) in general and its microtopography (i.e., skin relief at a microscopic level).
Young and aged skin present very distinct microtopographic structures and their
behavior with respect to light is different (Figure 42.4).
414
Figure 42.4.
Light reflection at the surface of young skin (Figure 42.5) is multidirectional.

Incident rays are transmitted in the skin at a very obtuse angle allowing the light
to propagate with an intense diffusion inside the epidermis. This diffusion of “soft
focus” type is the source of the matte appearance of young skin.
In aged skin (Figure 42.6), the absence of microrelief creates specular reflec-
tion in a given direction. The rays have mirror-type reflections and the skin looks
shiny. Furthermore, the incident rays are entering the skin at an acute angle which
does not allow the light to diffuse in the epidermis, going directly into the dermis
and hypodermis. This is a linear type of diffusion.
Figure 42.5. Figure 42.6.

415
In order to compensate for the changes in skin microstructure due to aging, the
introduction of ingredients generating optical effects in foundations allows the res-
toration of the translucence of younger skin while blurring wrinkles efficiently. The
substance on the skin surface must interact with light just as young skin does.
These ingredients with optical effects should have the following properties:
• To reduce the differences in glow of the skin surface without coverage or
masking effect between the wrinkles and the surrounding skin while main-
taining transparency. This is the non-covering matte.
• To diffuse the light and reproduce the “soft focus” effect of young skin. This
is the light diffusion property.
In Vitro Testing
In our experiments, the RSF optical film was poured into a plastic petri dish
containing a double-line cross-ruled background. This double-line cross-ruled
schema represents the microstructure of the skin. Thus, the two lines represent a
wrinkle (Figure 42.7).
Figure 42.7.
The first petri dish did not contain any fiber in the RSF optical film (Figure
42.8a). The second is composed of 3% of white fibers in RSF optical film (Figure
42.8b) and the third contains 3% of X-white fibers (Figure 42.8c). The X-white
fibers display a white bluish color under UV light. This demonstrates the good
homogenous repartition of fibers in the RSF optical film.
Figure 42.8a. Figure 42.8b. Figure 42.8c.

416
The film with 3% of fibers creates a blurring effect on the background. The visual
change from two lines to one single line is the consequence of the light diffusion
of the nylon fibers inside the film and demonstrates the RSF effect.
Another important point is that the film with fibers blurs the lines but doesn’t
hide them. The film keeps a good transparency and doesn’t become shiny. The
RSF optical film is matte.
Homogenous film, good transparency, matte aspect and change from two lines
to one line demonstrate the RSF effect of nylon fibers.
In Vivo Testing
The study was realized with a 20-year woman (young skin) and a 40-year woman
(older skin). The cream (Formula 42.2) and the foundation (Formula 42.3)
were spread on the upper side of the hand in thin layer on a clean and dry skin.
Moreover, in order to ensure a good reproducibility, the wrist of each woman was
immobilized with a clay mold. All the photography was done under artificial light
with a digital camera (magnification X 7.5).
One key parameter is the good repartition of fibers on the surface of the skin.
The application of the cream in an even layer on the young skin and its observation
under UV exposure (Figure 42.9) demonstrates the regularity of the repartition
of fibers on the skin. Although totally imperceptible under visible light, fibers are
well dispersed on the surface of the skin and there is no agglomeration.
Figure 42.9.
The VSF optical film was realized by spreading the foundation on the aged
skin. Figures 42.10a and 42.10b represent an aged skin on which a foundation
was applied with and without fibers.
Taken under the same experimental conditions, these pictures demonstrate
the matte effect of a foundation containing fibers. This formulation does not give
opacity to the skin when restoring a youthful appearance. Figure 42.10b can be
compared to Figure 42.5. Consequently, matte effect, transparency and luminous
restoration of aged skin demonstrate the VSF effect. This VSF effect also illustrates
the light-diffusing concept.
417
Figure 42.10a. Figure 42.10b.
Results
The uniform film of fibers at the surface of the skin reflects the light in all
directions giving the look of young skin (Figure 42.11).
Figure 42.11.
Conclusion
The surface of aging skin is characterized by an absence of microrelief and a
macrorelief (such as wrinkles and blemishes) in development.
It is often difficult to fight against these numerous transformations, but makeup
products can provide a remarkable improvement of the cutaneous aspect. However,
certain formulations cover the skin in a thick layer giving a mask effect.
Nylon fibers are an ideal solution to bring a natural appearance to makeup
formulations. They diminish the differences of shine between lines and the sur-
rounding skin, and reduce the appearance of wrinkles.
Nylon fibers diffuse light and restore the “soft focus” effect on aging skin.

418
References
1. GE Pierard, C Franchimont and CM Lapiere, Le vieillissement, son expression au
niveau de la microanatomie et des propriétés physiques de la peau, Int J Cosmet Sci
2 209–214 (1980)
2. PJ Tisnes, V.A.O. et Objectivation, Parfums, Cosmétiques, Arômes 72 67–71 (1986)
3. M Sakasaki, K Nishikata and N Nakamura, Optical investigation of aging skin and the
development of make-up that restores a youthful look, in Proceedings of the 21st
IFSCC Congress, Berlin 549–561 (2000)
4. U Hillgartner and R Anselmann, Optical wrinkle reduction, in Proceedings of the
Personal Care Ingredients ASIA Conference, Bangkok (2000)
5. M Kligman, P Zheng and RM Lavker, The anatomy and pathogenesis of wrinkles, Br J
Dermatol 113 37–42 (1985)
6. P Corcuff, JL Leveque, GL Grove and AM Kligman, The impact of aging on the
microrelief of periorbital and leg skin, J Soc Cosmet Chem 38 145-52 (1987)
7. K Nishikata, H Nishimura, K Mohri and N Nakamura, Optical properties of corneum
stratum and development of natural-looking makeups, in Proceedings of the 19th
IFSCC Congress, Sydney (1996)
Chapter 43
Cosmetic Product
Packaging
A variety of cosmetic packaging options and their uses are
important elements to be considered when formulating
personal care products.
key words: packaging, closures, plastics, glass
I magine how difficult it would be to use shampoo in the shower if it had to be

scooped out of a barrel. Or think about how hard it would be to use toothpaste
if, instead of squeezing the product neatly from its tube, it had to be scraped onto
a toothbrush.
Even though a cosmetic chemist’s primary concern is with the chemical com-
position and performance of a formulated product, packaging plays a critical role
in delivering formulations to the consumer in a convenient and useable manner.
Therefore, it is important for chemists to understand the many types and functions
of packaging available, the factors that influence which packaging is used, and the
chemical and physical effects of packaging on formulations.
Packaging
Definition: Simply put, the term packaging refers to the receptacle that holds
a product. It is typically made up of a container that houses the bulk of the product
with a closure that seals the container and controls dispensing. The primary pack-
age is sometimes enclosed in an outer wrapping or carton that is also considered
a packaging component.
Just by perusing the shelves at drug stores, supermarkets or department stores,
it is clear that cosmetic packaging is available in a wide array of sizes and shapes.
Personal care products are sold in bottles, jars, tubes and packets that are made of
plastic, glass, metal or combinations thereof.
Containers: Containers are produced in many forms and employ various materi-
als. A container for shampoo may take the form of a plastic bottle, while a perfume
package may be a stylized glass flacon. The container may be as simple as a plain
jar used to store cleansing cream or as complex as a multi-component swivel-stick
dispenser used for antiperspirants. Often companies will create a custom container
mold so they have a unique structure. Others use stock bottles and differentiate
themselves through labeling.
419
420
Cosmetic Product Packaging Beginning Cosmetic Chemistry
The closures for cosmetic packaging are as variable as the containers. Many
products use a simple lid or cap that screws onto the neck of the container, which
prevents the product from spilling, but these have little control on how the product
is dispensed. Other products, such as aerosols and deodorants, have more compli-
cated closures that actively control dispensing.
Bottles and jars: Bottles and jars are the most commonly used packages for
cosmetic products. They are formed from specially designed molds and can take
on a number of sizes and shapes, mostly tapered designs. Depending on the type
of material used to construct them, bottles can be rigid or squeezable, clear or
opaque, refillable or disposable. They are particularly well suited for dispensing
liquids with a wide range of viscosities. This characteristic makes them useful for
a variety of products, including shampoo, skin lotion, suntan oil, makeup remover
and mouthwash.
Jars are straight-walled and have a larger opening than bottles, which is more
appropriate for products like skin creams that are too thick to pour.
Tubes: Tubes represent another type of common cosmetic package. They
are primarily used for thicker products such as toothpastes, styling gels and some
high-viscosity creams. Unlike bottles and jars, tubes are usually sealed with a cap
at one end. The opposite end is left open at the manufacturing stage to fill with
the product. After filling, this end is sealed, usually by application of pressure and
heat. Various types of materials have been used to construct tubes, but aluminum
was originally the most popular, due to its flexibility. However, aluminum has sev-
eral drawbacks. It is expensive, hard to obtain, inconvenient because it has to be
crimped when sealed and requires delicate handling to avoid denting.
Subsequent improvements in packaging materials allowed plastics to be formed
into appropriate tubes. Plastic tubes offer a number of advantages, including heat
sealability and good water and oil barrier properties. Plastic tubes can be decorated
easily and are compatible with a variety of manufacturing lines. Researchers have
found that the performance of plastic tubes can be further enhanced by lining them
with special polymeric materials to reduce moisture or to avoid fragrance loss.1
Stick packaging: Unique cosmetic packaging has been developed to deliver
products in solid stick form, such as antiperspirants and lipsticks. Stick dispensers
are multi-component devices that rely on either a friction-fit, push-up plate or a
more sophisticated elevator platform that moves up the housing along a threaded
shaft. These packages can be used with products that have already been molded
into stick form, or they can be filled with molten product that then molds itself to
the shape of the package.
Pouches/packets: Another type of cosmetic package is the pouch in an en-
velope usually made of a combination of polyethylene, cellophane, vinyl, and/or
aluminum foil. Pouches or packets are useful for distributing small samples of
product to consumers. They are also used in high-viscosity treatments, such as
mud packs or facial masks.
Aerosol packaging: The aerosol packages commonly used for cosmetic prod-
ucts such as hairspray and deodorants need superior strength and burst resistance.
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Therefore, they usually consist of metal cans (tin-plated steel or aluminum) that are
pressurized with a liquified gas propellant after filling. See the chapter on Aerosols
for more information.
One package type related to the traditional aerosol is the bag in a can technol-
ogy. This features an outer container in which an accordion-pleated plastic bag is
inserted. The bag is filled with the formula and the liquid gas propellant is injected
into the space between the bag and the can. This type of package is not a true
aerosol and does not deliver an atomized spray of small droplets, but it is useful
for certain products like shaving gels. This approach may be useful in formulating
certain low VOC products.
Some alternative aerosol packages rely on a stretched rubber bladder to dispense
the product instead of propellant; others rely on piston cans to push the product out.
The chemist should be aware that aerosol products are among the most complex
of all packaging used in cosmetic science.2
Primary Objectives of a Cosmetic Package

The Packaging Primer cites five generalized objectives for any given
product:
1. Must assure cleanliness and uniform quality of the product it carries,
keeping it free from dirt, physical damage, etc.
2. Must convey key information such as the name of the product, manufac-
turer, specific ingredients, label copy, and comply with applicable state
and federal laws.
3. Must be attractive in appearance to appeal to wide number of buyers.
4. Must be convenient for consumer to handle.
5. Must be constructed so that it is suitable for display in stores where it is
sold.
Closures
While housing the formulation is a key function of packaging, sealing the
container and controlling dispensing are important as well. It is crucial that the
chemist be aware of the role of closures so the proper one can be selected during
product development.
Passive closures: Generally speaking, closures can be considered to have a
passive or an active role in product dispensing. Passive dispensing closures control
product flow by preventing the product from running out. When the closures are
opened or removed, the product is free to be either poured or scooped out. Such
closures can take many forms but the most common is a simple cap with a threaded
finish that screws onto the opening of the container.
Caps may have other finishes also, such as a lug, plug or crimp-sealer snap-on.
The latter provides a vertical movement, and a seal friction cap forms a seal by
interference fit between the closure and the neck section of the container.
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Dispensing closures: Dispensing closures have a slightly more active role in

product delivery. These closures have built-in orifices so the product can flow out
through the cap. Types of dispensing closures include flip-top caps, turret caps,
disk closures and push-pull spouts.
Active closures: Many types of closures play an integral role in delivering the
product. In some cases, the closure is also the pump that dispenses the product,
although an additional closure may be used in the form of an overcap that covers
the pump head. Such closures are common for dispensing liquid soaps, lotions,
and large quantities of shampoos and conditioners. Pump closures are also used
for toothpastes, styling gels and other products of similar viscosities.
In addition to pumps, other closures can actively deliver products. Some spe-
cialized examples include the roller ball in an antiperspirant roll-on and the brush
in a bottle of nail polish.
Aerosol closures represent another type of active dispenser but they also affect
the product’s performance. The shape of the orifice of an aerosol closure determines
many characteristics of the product, including the size of the droplet, the number of
droplets and the area covered. These factors are responsible for performance prop-
erties like drying time, how long a product lasts and film-forming properties.
Plastics
Plastic is the most commonly used packaging material in the industry today.
Plastics are economical, moldable, corrosion-resistant, visually appealing and adapt-
able to filling on a wide range of equipment. The plastics commonly employed for
making bottles include polyethylene, polypropylene, polyvinyl chloride and poly-
ethylene teraphthalate (PET). The type of plastic used on a given package depends
on the molding process used to form the package, the desired appearance of the
package, its required strength, and the nature of the formula it is to contain, along
with many other factors. The following section describes specific plastics and how
they are used.
Polyethylene: Polyethylene ([H2C=CH2]x), one of the most commonly used
plastics today, is made by polymerizing ethylene. It is used in great quantities be-
cause it is tough, chemically resistant, has a useful temperature range, is resistant
to environmentally-induced stress cracking and has good stiffness.1 It maintains
its strength after flexing that makes it good for use in squeezable packages. Poly-
ethylene is supplied in two primary forms: high density (HDPE) and low density
(LDPE). The desired stiffness and molding characteristics of the package deter-
mine whether high or low density is preferred. Polyethylene is commonly used to
make squeezable bottles for many hair- and skin care products such as shampoos,
conditioners and lotions.
Polypropylene: Polypropylene ([C3H6]n), or polymerized propylene, is useful
for making lightweight packaging because of its remarkably low density compared
to other thermoplastics. One advantage is its high melting point, which makes it
more resistant to elevated temperatures (up to 300ºF). Furthermore, it has excel-
lent gas- and water-vapor permeation properties. However, it is somewhat more
423
expensive than some resins and must be modified with other elastomers to improve
certain properties such as low temperature breakage.1 Due to its high degree of
stiffness, polypropylene is useful in making more rigid packaging components such
as caps and lids.
Polystyrene: Polymerized styrene ([C6H5CHCH2]n), is hard, somewhat brittle
and low on toughness. Therefore, it is usually copolymerized with butadiene and
acrylonitrile to increase strength. Properly formulated polystyrene has good resis-
tance to alkalis, alcohols and water, in addition to good physical characteristics.1
Polyvinyl chloride: Polyvinyl chloride, also known as PVC ([–H2CCHCl–]x),
is made by polymerizing vinyl chloride. PVC can be transformed into a variety of
package types due to its adaptability to plasticization, its unbreakability, its resistance
to chemical and water penetration, and its availability in clear, as well as a large
array of colors.1 It is also useful in making bottles for a variety of products.
Polyethylene teraphthalate: Another plastic that is gaining in popularity is
polyethylene teraphthalate ([C10H8O4]x), a thermoplastic resin more commonly
known as PET, formed from a catalyzed ester exchange between ethylene glycol
and dimethyl teraphthalate. PET and its counterpart, oriented polyethylene teraph-
thalate, are commonly used in clear soft drink bottles and are finding increased
application in the cosmetic industry.
Other Materials
Glass: Although plastic is the packaging material of choice, other materials
provide certain unique benefits. Glass has excellent barrier properties, for example.
Glass is more expensive to use than plastic; nonetheless, it still enjoys popularity in
certain product categories because it is capable of providing unique bottle shapes
and its weight and texture connote high quality. For instance, glass bottles are still
preferred for perfumes and for some skin care and color cosmetics, such as nail
polish. It is not typically used for hair care products because of the inherent danger
associated with having glass in the shower or on wet countertops.
Metals: Another common category of packaging material, metals have superior
strength. This makes them well suited to withstand the pressures needed to accom-
modate aerosol products. Though usually more costly than plastic, metal containers
can also be formed into an array of shapes and sizes. Aluminum tubes and tin-plated
steel cans are the most common types of cosmetic product packaging and have been
used to package many different types of hair care and skin care products.
Package Selection
Selection of appropriate packaging is not usually done by the formulation
chemist. Nonetheless, it is useful for chemists to understand the many formulating
considerations involved in package selection, as the product-development chemist
is often responsible for evaluating the options.
Stability: One of the most important criteria is to ensure that a package does
not negatively affect the product or, conversely, that the product does not hurt
the package. It is the responsibility of the development chemist to determine the
424
impact of the formulation on the package and to evaluate whether or not these
changes will have a significant effect on product integrity. This process can be done
by following the company’s stability testing procedures.
Depending on the package’s size, shape, and material, you may encounter vari-
ous stability problems. A general problem for all types of packaging is an excessive
loss of water or fragrance that can occur with an inadequately sealed closure or
from excessive permeability of the package.
Chemical effects: Plastic packages are prone to a variety of stability problems
depending on the type of resin and physical shape used. For example, water loss is
a function of the type and thickness of plastic in the packaging. Also, the formula
may react with resin components such as fillers and plasticizers that can cause
color loss in the product, change in fragrance character, and even the formation of
undesirable precipitates. Or, the package may craze or crack due to the formula/
package interactions, causing leakage. Correcting these types of stability problems
is usually done by changing the type of plastic used, but it may also require some
reformulation.
Metal packages are particularly susceptible to internal oxidation or corrosion,
especially when used with water-based formulas, such as the new, low-VOC hair
sprays. Often, the chemist must add corrosion inhibitors to the product to address
this problem. In the case of aerosol systems using plastic/foil packets to separate
product from propellant system, weight loss is of particular concern because the bar-
rier properties of the film may be inadequate or the pouch may have a poor seal.
Glass itself is unreactive with most formulations. However, plain glass does
not screen out light well, which can cause product discoloration or a change in
fragrance character. Fortunately, some light screening coatings can minimize some
of these issues.
Physical considerations: In addition to chemical interactions between formula
and package, the chemist must ensure the package is appropriate for the physical
form of the product. A bottle intended for use with a thick lotion must be of the
proper size and shape that the product will dispense properly. It should be made
of plastic that is adequately squeezable and must have an opening large enough
that the product can flow out easily. Conversely, a water-thin product may need a
restricted orifice to stop the product from flowing out too quickly. These critical
elements of shape, size of opening and appropriate closure must be correctly bal-
anced to ensure that the package is in harmony with the product.
Functionality: As already mentioned, the package must do much more than just
contain and deliver the product. It must protect the product from environmental
assault. It must also act as an advertising vehicle for communicating key informa-
tion about the product to the consumer. Evaluating these functions involves other
team members besides the formulating chemist, including packaging engineers,
creative services and art departments, and marketing.
Cost: Just as with formula development, packaging choice and development
has its cost limitations as well. Of course, a major consideration is the cost of the
materials chosen for the package. In the case of plastic bottles, that means the cost
425
of the plastic resin used; for aerosol cans it would include the cost of the metal plus
necessary sealing compounds and coatings.
The price of a package also includes the cost of its manufacture, whether it
is blow-molded, injection-molded or assembled from multiple components. This
price includes costs for coatings or special additives, like antistatic treatment or UV
absorbers, that may be added to the package. Likewise, the cost of decorating the
package (by glued or shrink-wrapped labeling or printing directly on the container)
is important. Finally, the cost of shipping the empty packages to where you intend
to have them filled may have an appreciable impact on the cost.
Esthetic characteristics: Any package must have appropriate esthetic char-
acteristics to support its positioning. The package must be the right size and shape
to impress the consumer, it must be colored correctly and easy to handle. Elegant
designs look impressive but they may increase cost and complicate manufactur-
ing and filling efforts. Therefore, the best package for the job may be a tradeoff
between the ideal design desired by marketing and the pragmatic alternatives that
will allow the package to be produced at a reasonable cost, sold to the desired target
consumers and conveniently used by those consumers.
Manufacturing issues: The team designing the final product must consider
whether or not the package will be compatible with available manufacturing equip-
ment such as conveyor systems and filling attachments. Customized containers
may require special tooling, known as change parts, to allow the packaging to
move smoothly along existing guide rails. If change parts are required, it may be
a significant expense to the manufacturer or contract manufacturer, which will
ultimately affect the cost to the consumer.
The Packaging Engineer’s Role

Most aspects of package design and selection are handled by packaging engi-
neers. These engineers are specifically trained in the details of packaging science
and are responsible for selecting appropriate materials for the package as well as
any coating materials, UV absorbers or colorants that may be required.
Packaging engineers also test the physical aspects of the package to ensure
they meet designated specifications. They conduct magnetic-field measurements
to determine wall thickness of bottles, perform drop testing to ensure containers
will not rupture during shipping, and evaluate leaching studies to make sure the
colorant does not migrate into the product. These tests and many others must be
completed before a package can be certified for use with a product. The chem-
ist must work with packaging engineers (making sure the engineers know of any
product/package interactions, for instance) to ensure that all appropriate testing is
done before qualifying a package to be used.
Engineers also consider issues related to the manufacture and decoration of
containers. The manufacturing requirements of a given package are extremely
important because they help determine the package’s cost and availability.
Decorating considerations are another important factor in package development.
Decorating techniques may involve labeling (vinyl and cellophane are common label
426
materials) or printing processes such as lithography, rotogravure or silk-screening.

The number of colors on the label affects the price by increasing the number of inks
used in the decorating process. Package decoration can be a challenge considering
one must balance such diverse factors as cost, package composition, color scheme,
package style and design, manufacturing lead time, and even manufacturer’s geo-
graphic location, as the shipping costs from the manufacturer to the decorator can
be passed to the end user by being added to the price of the completed package.
Conclusion
Helping evaluate the suitability of packaging for specific formulations is an
important part of the cosmetic chemist’s job. As industry trends evolve, packaging
and formulations must change accordingly.
In recent years, the safety of chemicals used in the production of plastic packag-
ing has come into question. In 2008, laws essentially banning the use of Bisphenol
A (BPA), a commonly used starting raw material, were proposed in various US
states and in Canada. These use limitations were reactions to preliminary studies
linking BPA to health problems.
The environmental impact of packaging materials has also come under increas-
ing scrutiny from various regulatory bodies. Consequently a push to reduce the
amount of packaging material, to make it more reusble, refillable or recyclable
continues. A trend toward use of child-resistant closures and tamper-evident or
tamer-resistant shrink bands for consumer protection is also ongoing. Trends such
as these will make interesting future challenges for cosmetic chemists and packag-
ing engineers alike.
Acknowledgement: The authors would like to thank Diane Haidle, Group Leader of Packaging
Development for Alberto Culver, for her help in researching this article.
References
1. RH Thomas, Cosmetic Packaging Technology, Columbia University College of
Pharmaceutical Sciences
2. MA Johnson, The Aerosol Handbook 2nd Edition, Wayne Dorland Co, Mendham, NJ
(1982)
3. M Howe-Grant (Ed.), Kirk-Othmer Encyclopedia of Chemical Technology, v 17 4h Ed,
John Wiley & Sons, NY (1996)
4. F Lewis, Sr. and I Sax (Eds.), Hawley’s Condensed Chemical Dictionary, 11th ed, Van
Nostrand Reinhold Co, NY (1987)
5. R Kelsey, Packaging in Today’s Society, 3rd ed, Technomicc Publishing Co, Lancaster,
PA (1989)
6. S Sacharow, A Packaging Primer, Books for Industry Division of Magazines for
Industry, Inc, NY (1978)
Chapter 44
Emerging Technologies
and the Future
of Cosmetic Science
In this chapter, the authors look forward to what cosmetic
science might be like in the future with what emerging
technologies, radio frequency identification (RFID) tags and
nanotechnology, may offer to the cosmetics industry.
key words: RIFD technology, nanotechnology, nanomaterials,

phospholipids, liposomes
A s regular readers of our columns know, we usually look to the past to provide
historical background on the basics of cosmetic science. But this chapter is dif-
ferent; it looks forward to what cosmetic science might be like in the future. While
our previous pieces have been designed as “informational entrées,” this column is
meant to be an appetizer of things to come. So bring your appetite for innovation
and join us for a lighthearted glimpse of the potential future of our industry.
For this discussion, we will consider two emerging technologies and how they
might one day impact cosmetic science. The first technology is radio frequency
identification (RFID) tags—the tiny electronic information tags that are making
their way onto products worldwide. Currently, the information on these microchips
is primarily limited to inventory control. But, in the future, who knows how this
technology might affect cosmetic science? The second scientific advance we will
explore is nanotechnology, which is being developed to fight viruses, repair blood
vessels, and provide targeted delivery of drugs. But what if RIFD and nanotechnology
were ready for cosmetic products today? What would the industry look like? Let us
explore these new technologies and, we hope, spark some ideas in the process.
RFID Technology Today

RFID tags are small magnetic media disks that are affixed directly to product
packages, cartons, and pallets. These tags are used to store data about the product
such as universal product codes (UPCs), expiration dates, etc., which are useful in
inventory tracking. The industry is split on its reaction to RFIDs; certain retailers
favor the additional information the technology provides but manufacturers are
concerned about the added cost. At the time of this writing, the controversy rages
on. Meanwhile, the technology continues to develop.
427
428
Emerging Technologies and the Future of Cosmetic Science Beginning Cosmetic Chemistry
Today, tags come in two forms—passive and active. The passive versions do
not contain a power supply of their own; instead, the tag is receptive to incom-
ing radio frequencies that induce a minute electrical current. Thus, scanning the
tag with a radio wave can provide enough power for the tag to send a response.
This approach allows the tags to be made very small; in fact, passive tags can
currently be made small enough to be embedded under the skin. The tiniest
devices commercially available as of 2004 measured 0.4 mm X 0.4 mm and are
as thin as a sheet of paper. However, there is a trade-off in performance. Small
size limits both the amount of information a tag can contain and the distance
from which it can be read. The range for passive tags varies from approximately
10 mm up to about 5 m.
Active RFID tags are quite different; they contain their own power source
that frees them from the limitations of passive tags. Therefore, they have lon-
ger ranges—they can be read from a distance of 10s of meters, they have larger
memories, and their battery life can last up to several years. They can also store
additional information that is sent to them by a transceiver. They are, however,
larger and heavier. Currently, the smallest active tags are about the size of a coin.
As you might expect, passive tags are more common today because they are cheaper
and do not require a battery. Even so, these tags can cost upwards of $0.40. The
industry estimates the costs needs to be $0.05 or less to make widespread RFID
tagging commercially viable. Because the technology is new, supply and demand
have not yet lowered the price to this level. In fact, analysts predict that a cost of
less than $0.10 will not be achievable for six to eight years, which is a hurdle to
widespread passive RFID use.
The technology behind RFID is rapidly advancing as the industry tries to solve
the problems with these formats. For example, already some research has been done
into the use of ink as a magnetic media for RFID. While this change would dramati-
cally reduce costs, it is still years away from fruition. New applications for RFID are
also being explored—one bold visionary proposed the creation of a refrigerator that
could track the expiration dates of the food products inside it via their RFID tags.
Even though few of these ideas have moved beyond the prototype stage, imagine
the possible uses for future RFID technology in personal care products.
RFID Technology Tomorrow

RFID technology could have a huge effect on the personal care industry by
changing not only the way consumers shop for products but also by the way they
use products in their homes. It even has the potential to change the way formulators
and marketers create new products. Let us explore a few of these exciting areas.
Shopping convenience: Imagine a not too distant future where RFID tech-
nology is so advanced that every personal care product consumers buy is equipped
with an active tag capable of sending and receiving information right from the store
shelf. Also imagine that their home computer can interact with a new generation
of smart appliances. For example, RFID-compatible cell phones and personal data
assistants (PDAs) could take inventory of the products in consumers’ bathroom
cabinets and prepare shopping lists for them. The cabinets could track their needs
429
and dispense products for them as necessary. These electronic toiletries managers
(ETMs) could constantly monitor their inventory of products frequently used (see
the RFID-Assisted Shopping Experience sidebar).
RFID-Assisted Shopping Experience

A shopping trip might start by downloading a shopping list to a personal
data assistant (PDA) or cell phone. The information stored there would
indicate not only the products needed, but also factors in changing circum-
stances, such as the weather, scheduled events on the calendar, and so forth.
It might be as simple as this: when a consumer reaches the store, his or her
cell phone reminds them to buy mouthwash, then automatically searches
the store shelves for an RFID signal from a mouthwash brand they usually
purchase or looks for something new, based on programmed preferences.
Once the connection is made between the product database and the product
on the shelf, a purchase can be made at the consumer’s discretion.
The PDA could even scan his or her electronic calendar and find an up-
coming wedding or other significant social event. This discovery might trigger
a scan of the store shelves for information on new lipsticks or eye shadows
to match a dress the consumer bought last week. Or, on a particularly cold
winter day the ETM might send an alert to the PDA to remind the consumer
to buy a more intensive skin moisturizer.
As he or she browses the aisles, smart RFID products would call out
to their PDA or cell phone. Data bytes would sing silently back and forth
looking for a match. The aforementioned intense moisturizer might beam a
signal to their phone to announce its presence. Once the connection is made,
the product would upload a description of itself including all the critical in-
formation needed to decide if the product is right for him or her. After the
match is made the PDA would direct consumers to pick up the appropriate
package, giving them the perfect product to fit their needs without having
to give it a thought.
Hair care needs would be met electronically as well. Consumers worried

about the right hair color could have their PDA connect to their salon’s database
to find out which color the stylist used and then search the shelves for the precise
maintenance shampoo and conditioner products needed. These products would
be matched against a personal database of preferred products before the PDA
would signal that it is time for a purchase. Similarly, PDAs would use RFID data
to self-select other products that go with hair type, skin color, and any other attri-
butes indicated by the consumer. Additionally, the shopping experience does not
have to happen in the store—the ETM could upload a product inventory to an
e-grocer, which would prepare and deliver the order. For products the consumer
uses regularly (e.g., contact lens solution), an automatic reorder could be placed
before the supply runs out.
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Does this scenario sound too good to be true? Well, here is the bad news: with
RFID technology, products could have the ability to market themselves more
aggressively. Shelves full of products would send regular alerts that they are new
and improved, or that they are on sale at half price. Products could alert consum-
ers that the company is changing the fragrance and ask them if they would like
to request a sample of the new one. As consumers walk down the aisles of their
favorite stores, products could “call out” to their Web-based cell phones. This next
generation “spam” could overwhelm PDAs unless they are equipped with the latest
firewall technology.
At-home convenience: Now consider what RFID technology could do in
conjunction with the smart household appliances of the future. The consumer’s
ETM would also serve as the information hub for all product activity. Products
could be stored in rotating “garages,” where they would be automatically selected
and presented, ready for use. They could communicate with the clothes closet to
automatically coordinate color cosmetics with a chosen wardrobe. Based on RFID
instructions, personal computers would monitor live local weather information and
use this information to make recommendations for daily hair and skin care products.
The intense moisturizer would notify consumers to use it on cold, dry days and the
humidity-resistant hair spray would “speak up” when it is muggy outside.
Products would work in tandem with a new breed of cooperative appliances.
For example, hair styling gel might interact with the consumer’s blow dryer or
curling iron to automatically inform it of the proper temperature setting. A bath
gel might contact microcircuits connected to the shower to dial up the correct
water temperature. And the facial makeup consumers select could electronically
change their bathroom lighting, depending whether the foundation is formulated
for use at the beach or for indoors. And what about oral care? The “smart” micro-
wave oven could send a wireless signal to a consumer’s electric toothbrush telling
it to dispense extra-strength fluoride toothpaste because he or she just prepared
a batch of tooth-decaying chocolate brownies. Or perhaps the microchip in the
coffeemaker, recognizing the consumer made two pots of extra strong coffee this
morning, would beam a request for a whitening toothpaste formula when they go
to brush later in the morning.
Benefits to product developers and marketers: Consumers are not the only
ones to potentially benefit from widespread use of RFID technology; product de-
velopers and marketers could find new opportunities through the use of these tiny
tags. RFID information could aid formulators in creating new products that might
otherwise be problematic. For example, today it would be a challenge to market
a truly natural cosmetic product because of issues with spoilage. But in the RFID
future, chemists could create a new generation of fresh, all natural products that
have a limited shelf life. RFID chips in the products would track the shelf life so
consumers know exactly when they expire. This technology could even be used to
record the temperature and other factors that could negatively affect the shelf life.
By eliminating concerns about shelf life, RFID tags could allow the formulator to
431
use a wider variety of raw materials. With a little thought, one could imagine many
examples where this technology could allow formulators to develop new products
that otherwise might be problematic.
Another application for RFID that would appeal to both formulators and
marketers alike would be real-time product usage data. In conjunction with com-
puterized ETMs, RFID tags could track specific data on how a product is used by
the consumer (e.g., information on how much product is dispensed for each use,
length of time of use, conditions of storage), could be collected and transmitted to
the company. By sharing this kind of use information with manufacturers, consum-
ers would be helping these companies to produce new products that would better
suit their individual needs. The consumer benefits by getting a more personalized
product and the company benefits by being able to target its product to specific
consumers. Of course, such an information exchange quickly raises issues involving
privacy and identity theft that will have to be resolved before the technology can
be fully implemented. While we have speculated on only few of the many areas of
personal care that could potentially benefit from RFID technology, we hope we
have given the reader a tantalizing taste of what could happen.
Now let us turn our attention to another one of today’s emerging technologies
and see where it’s headed for tomorrow.
Nanotechnology Today
Nanotechnology is another emerging area that has the potential to radically
change the way the cosmetics deliver their benefits. While some applications are
already being realized, the full potential is yet to be developed. But concerns over
safety are poised to sink this technology before it even gets afloat. Time will tell if
some of the possibilities of this technology will ever be realized.
What is nanotechnology? It should be obvious with a prefix like “nano” (from
the Greek “nanos,” meaning “dwarf”) that nanotechnology refers to that which
is incredibly small. A nanometer is one billionth of a meter and typical atoms
are about one third of a nanometer. So nanotechnology deals primarily with the
manipulation of atoms and molecules in this range to produce building blocks for
slightly larger structures.
However, nanotechnology is not only interested in the study of smallness but
also in the practical application of these structures. Currently, the three main areas
of development include the following:
1. Nanomaterials: building specialized structures whose dimensions are controlled
on a nanoscale
2. Nanobiotechnology: the manipulation of living systems using nanoscale en-
gineering or the construction of molecular scale materials inspired by biology
3. Nanoelectronics: related to the development of microelectronics for devices
such as RFID
Each of these fields could have an impact on the future of cosmetics, but most
promising is the area of nanomaterials.
432
Nanomaterials
The area of nanomaterials is currently receiving the most attention in the cosmetic
industry. Specifically, nanoparticles have been used to encapsulate a wide range
of ingredients that are intended to provide cosmetic benefits. In some respects,
nanoparticles have characteristics in common with both emulsions and liposomes.
Like these structures, they have a spherical shape. Their size, on the order of
1000–20 nm in diameter, is comparable with liposomes. However, nanoparticles
are typically composed of a single layered shell, whereas liposomes are made up
of bilayered membranes. An additional difference is that the inner content of li-
posomes is water based, while the content of a nanoparticle is oily. In this manner,
they are like emulsion micelles, only much, much smaller.
How nanoparticles are made: Nanoparticles are produced in an aqueous
medium using an emulsifier such as lecithin, lipophilic active ingredients, and high-
pressure homogenization techniques. The specially designed homogenizer can mix
the components together at pressures up to 1200 bar. Reportedly, the technique
produces 100% encapsulation of the active ingredients in the nanoparticles. To
achieve this impressive rate and to produce homogenous particles, multiple cycles
through the homogenization chamber are required.
Suppliers of nanoparticles suggest that they can be made to contain 40% oil.
The exact concentration and size of the structures depends on factors such as the
type of oil, the concentration and type of lecithin, the water phase composition, and
the pressures achieved during production. The smallest particles (under 50 nm),
can only be produced by using a high ratio of emulsifier to oil. For example, 4%
lecithin would be combined with 10% oil.
A wide range of ingredients have been incorporated into these nanoparticles but
all are typically lipophilic. They include the fat-soluble vitamins such as vitamin E
or vitamin A; natural oils like jojoba, macadamia nut, or wheat germ oil; and various
functional ingredients such as ultraviolet (UV) filters and fragrances. All of these
materials are said to be more resistant to oxidation (and thus more stable) when
incorporated into a nanoparticle.
Characteristics of nanoparticles: The size of the particles will have an impact
on their functional characteristics. For example, nanoparticles that are 100–200 nm
in diameter will be opaque or translucent. When the particle size is reduced to 60
nm, they become “invisible,” thus producing clear solutions. This property is most
useful when trying to incorporate nanoparticles into clear systems.
Application to cosmetics today: The stability of nanoparticles has made them
an appealing choice for cosmetic formulators, especially for skin care products. Lead-
ing skin care marketers have used nanoparticles to deliver antiaging ingredients to
the skin because they believe they are more efficient, effective, and longer lasting.
One can imagine these conjectures could deserve some merit. The phospholipids
used to produce nanoparticles do have an affinity for the stratum corneum, and
numerous studies on drug delivery have shown liposome delivery systems work
better than conventional emulsions. Since nanoparticles are made of nearly the
same ingredients as liposomes, they should work similarly. Now, whether antiaging
ingredients actually work is a different story.
433
Another skin care area that is making use of nanoparticles is sunscreens. Zinc
oxide is an excellent sunscreen ingredient but can have the unfortunate character-
istic of leaving a white coating on the skin. By incorporating it into nanoparticles,
the sunscreen can be made to spread more easily, cover more efficiently, and go
on clear.
For hair care, however, nanoparticles do not seem to offer much benefit except
perhaps for delivering active ingredients to the scalp. This use could be useful for
such applications as antidandruff compounds or sunscreens. Suppliers have also
suggested that nanoparticles can be produced with positively charged outer shells.
They will then be prone to attaching to hair at damaged sites, thus providing tar-
geted delivery for their payload. While the idea is intriguing, the proof of benefit
over standard emulsion technology is still lacking.
Future applications: The current state of nanoparticle technology is definitely
in its infancy. The production of the structures is a crude approximation of what it
potentially could be. In the future, molecular manufacturing could be employed
to produce more specific and better functioning nanoparticles. Unlike traditional
methods that rely on random collisions in a solution to create the structures,
molecular manufacturing involves assemblers that position molecules in specific
locations at specific times to create precise structures. Instead of single ingredient,
spherical shells, more complex particles could be produced.
These particles could be made to be much more substantive to skin and hair and
would have innumerable applications. For example, one could imagine nanoparticles
infused with fragrance bound to hair—to emit their essence each time the hair is
combed or touched. Or, a makeup could be designed with color incorporated into
nanoparticles that is invisible when applied but expresses color when rubbed with
a finger. If enough control over the structures could be achieved, it could even be
possible to rebuild hair by replacing cuticles.
Potential also exists for constructing nanomachines, thousands of which could fit
on the head of a pin. One could imagine these devices being placed on the surface
of hair or skin, patrolling up and down, repairing the surfaces as they go. Perhaps
the machines could be controlled electronically to emit color or reconfigure the
hair’s shape. Shampooing, conditioning, and styling could be a thing of the past,
and cosmetic chemists would have to turn in their mixing blades and beakers for
computer keyboards.
In the area of packaging, nanoparticles may also find extensive application.
Various nanoclays or nanocomposites are already being produced and sold as bar-
rier films. They could be incorporated into cosmetic packaging to reduce costs
(because less plastic would be needed) and improve stability. They could also
be used to create clever packages that change color or emit a specific odor. This
technology has the potential to significantly change the way people interact with
their cosmetic products.
Safety Concerns of Nanotechnology

Of course, with any new technology come concerns about safety. In 2004, the
British government commissioned an independent report by Britain’s Royal Society
434
and Royal Academy of Engineering to look at the health and environmental risks
of nanoparticles and nanofibers. This report concluded that the risks are great
enough that cosmetics with nanoparticles should be banned until their safety could
be determined. It suggested that nanoparticles behave in unpredictable ways and
could prove to be toxic in a manner that is different from the bulk ingredients. The
report went on to say, however, that that most of these ingredients will likely prove
harmless—but caution is urged.
Concerns from reports like these and articles in the popular press about the
dangers of nanotechnology in cosmetics prompted the Cosmetics, Toiletry and
Fragrance Association (CTFA) to respond. It suggested no risk is known to consum-
ers from nanoparticles currently in use, and the benefits are numerous. Whether
one or the other is right or wrong is unknown, but studies are already underway to
determine whether nanotechnology is safe. Only time will tell if regulatory concerns
will prevent the full potential of this technology from ever being realized.
Conclusion
Truly new technologies in our industry are rare. But the two examples the
authors discussed certainly have the potential to revolutionize our industry. Are
these notions ridiculous and far-fetched or just a little ahead of their time? As they
say, only time will tell.
References
1. K Bertrand, RFID, Chips Set to Make Big Waves, Brand Packaging 6–10 (Nov/Dec
2004)
2. P Jones, Don’t Tag Me!, GCI 23 (Jan 2005)
3. C Bolan, Is RFID’s Tag Too Pricey?, GCI 24–27 (Jan 2005)
4. K Drexler, The Future of Nanotechnology: Molecular Manufacturing, available at:
http://www.eurekalert.org/context.php?context=nano&show=essays. (April 2003)
5. R Weiss, Nanotechnology Precaution is Urged, Washington Post, A02 (July 30, 2004)
6. F Harvey, Can We Overcome Nano-fear?, Financial Times (Jan 15, 2004)
IV. Does It Work:
Product Testing,
Regulatory Compliance
and Claims Support

Chapter 45
Evaluating Raw Materials

and Finished Products
The types of tests with which the cosmetic formulator should
be familiar in order to successfully develop, maintain and
manufacture cosmetic products.
key words: raw material quality control, pH, viscosity,

safety testing, claim support, salon testing, consumer testing
I n previous chapters we have discussed the principles of formulating cosmetic

products and the process of evaluating their stability. This article focuses on the
types of tests with which the cosmetic formulator should be familiar in order to
successfully develop, maintain and manufacture such products. These tests fall into
two general categories: physiochemical tests, which involve the measurement of
some physical or chemical property of a chemical raw material or finished cosmetic
product, and performance tests, which are designed to measure how well the product
functions in some capacity. In both cases, the objective is to better understand and
predict the behavior of the materials involved in order to ultimately produce a final
product of high and consistent quality. The formulating chemist needs to be aware
of how such tests relate to both product development and to quality assurance of
raw materials and finished products.
Physiochemical Tests
Raw material quality control: Obviously, one way to better control the quality
of a finished product is to control the quality of its components. Since raw materials
may vary from lot to lot, a quality check prior to manufacture can catch problems
before they get into your finished product. On the most basic level, simply check-
ing the appearance of raw materials can be helpful. For example, certain cosmetic
raw materials, such as proteins, will tend to darken upon aging due to oxidation;
therefore, you can often spot a “bad” material by comparing its appearance with that
of a standard. Comparing the color, odor, or appearance of product to a standard
is the basis for qualitative tests commonly used in this industry.
A host of other analytical tests are also available which may be of use in control-
ling the quality of cosmetic raw materials (and to check composition of finished
products). Such tests include infrared spectroscopy (IR), gas chromatography (GC),
high pressure liquid chromatography (HPLC) and a multitude of wet chemistry
evaluations too numerous to mention here. Almost any analysis that provides
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Evaluating Raw Materials and Finished Products Beginning Cosmetic Chemistry
quantitative or qualitative information about cosmetic materials may be of potential

use. By adding to the bank of available physiochemical data, results of these tests
can help detect future problems which may affect your product.
Determine pH: Measurements of pH can reflect the stability of a product be-
cause they indicate chemical reactions taking place. For example, compounds such
as esters may hydrolyze and release free acid that could produce adverse effects.
Such chemical changes may be monitored by measuring the pH. Furthermore,
pH measurements can provide information about the quality of the product or
incoming raw materials. Typically, when chemical raw materials are manufactured,
a certain amount of unreacted material remains. Often, this unreacted material will
produce a difference from the expected pH and may negatively affect your final
product. Knowing the pH alerts you to such potential problems and provides you
some control over these possibilities.
Finally, pH measurements can also give you clues as to the functionality of your
product. Some materials will function differently as the pH changes. For example,
betaines are molecules with both positive and negative charge. They are more sub-
stantive to hair and skin at a specific pH range. Therefore, it is to your advantage
to ensure your final product is held at the appropriate acid/base balance to ensure
maximum functionality of its components.
Measure viscosity: Another revealing parameter commonly used to evaluate the
quality of finished products and raw materials is viscosity. Viscosity measurement,
one of the true “work horses” of this industry, can help determine if your product
is of the proper consistency and can indicate product stability. In technical terms,
Isaac Newton defined the viscosity of a fluid as the force per unit area required to
maintain a unit difference of velocity between two parallel layers a unit distance
apart. (A complete treatise on this subject is beyond the scope of this article; anyone
who is interested can refer to Reference 1 for a more complete discussion.) For our
purposes, viscosity measurement can be thought of as an indicator of the “thick-
ness” and flow properties of a product. Methods of viscosity measurement abound,
but perhaps the most common employs a Brookfield viscometer. This instrument
measures the torque required to rotate a spindle immersed in a given fluid.
Information gained from such measurements has two uses. First, it helps ensure
your product is the appropriate consistency by allowing you to establish a range
of acceptable viscosity values corresponding to a range of rheological (or flow)
characteristics. In other words, if the viscosity measurement is within the proper
range you know the material will have the right consistency. Second, proper viscosity
measurement can also provide an indication of how a product is changing over time.
For example, the stability of emulsions is generally dependent on the viscosity of the
system—the higher the viscosity the better the droplets of the dispersed phase are
held in place. In many cases, a large increase or decrease in viscosity may indicate
that the emulsion has become destabilized. Repeated measurement of viscosity
over time could provide an early warning of emulsion instability.
Other assays: At best, pH and viscosity measurement provide general ranges of
physiochemical properties. These values aid in the establishment of specifications
439
which help you ensure that incoming raw materials and batches of finished prod-
uct vary as little as possible. But sometimes additional testing is required to learn
more about your product. One very important area of consideration is microbial
preservation testing. Since many water-containing cosmetic products are good
growth media for bacteria, testing is required to ensure the component materi-
als and final product are adequately preserved. The specifics of such testing are
discussed in Reference2.
Product Performance
In addition to assuring the continued physiochemical integrity of the products
and the raw materials which comprise them, it is critical that testing be conducted
to determine that products themselves perform as required. Such testing may take
the form of functionality testing (i.e., testing to determine if a product successfully
does what it is sold to do—or just as importantly, if it is perceived as doing what it
sold to do—such as testing a hairspray to determine if it really holds hair in place)
and compliance testing (i.e., testing to ensure your product complies with any and
all restrictions placed on the product for legal or safety reasons—such as medical
safety testing or, in the US Food and Drug Administration (FDA) monograph
compliance testing).
An example of the former might be the testing of a hairspray to determine if it
really holds hair in place under certain conditions. The latter might be as involved
as the testing of an antiperspirant to confirm that it meets monograph requirements,
or as simple as the testing of a shampoo to determine if the bottle really delivers
the net weight as stated on the label.
Compliance
Regulatory considerations: Today it’s not enough for your product to simply
do its job. It must also comply with any relevant regulatory considerations. Although
compliance testing may involve aspects of functionality testing, it also incorporates
many other factors. For example, in the United States, certain products (such as
antiperspirants and dandruff shampoos) must comply with specific FDA issued
over-the-counter (OTC) drug monograph conditions before they are considered
“functional.” And although other personal care products, such as hairsprays and
conditioners, may not have specific mandated performance requirements, they must
comply with the US Bureau of Weights and Measures guidelines for dispensing.
While you may have to clinically test the performance of your antiperspirant, to
ensure it produces dryness as claimed, you may also have to measure the amount
of antiperspirant your can delivers to make sure it makes minimum legal delivery
weight.
Additional clinical testing may be required to determine the safety of
cosmetic products you have developed. The US Code of Federal Regulations dis-
cusses safety testing of cosmetic products sold in the United States. [see refer-
ence 21 CFR 740.10 (a)]. In any event, consult your management team to decide
what medical safety testing should be conducted for any given product.
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Evaluating Raw Materials and Finished Products Beginning Cosmetic Chemistry
Functionality
For the purposes of this discussion we will loosely classify such tests as belong-
ing to one of three categories:
1. Laboratory (in vitro) functionality testing;
2. Salon (in vivo or “clinical” consumer testing); and
3. Consumer (home-use consumer testing).
These categories differ by the degree of control over experimental variables
they offer and by the different degrees of “technical” data and “consumer” data
they supply.
Laboratory testing: Of these three, laboratory functionality testing offers the
most control over experimental variables and provides the most technically precise
data. For example, measuring fiber tensile strength of hair provides hard, numeri-
cal data related to a very specific property of the hair shaft. Such a test may help
you answer the question, “Does my product really strengthen hair?” The answer is
an important facet of claim support. It does not, however, provide information on
consumer perception of the product. A hair- or skin care product can be the most
effective product on the market and still not be successful if it is not perceived
that way by the consumer. To gain information on consumer perception, you must
expose consumers to the product and evaluate their response.
Salon testing: This method evaluates your product during actual usage on
consumers while maintaining a measure of control. In salon testing, trained tech-
nicians (usually licensed cosmetologists) generate data on product characteristics
such as (for a shampoo) how well the product foams, the feel and texture of the
foam, how easily it spreads through the hair, how easily it rinses and how it leaves
the hair feeling.
Typically, the cosmetologists will evaluate the test product in comparison to a
designated control product. This evaluation is done by using the product on volun-
teers and recording all impressions the operator may have of these characteristics on
standardized rating scales. The formulating chemist still controls many variables in
the evaluation (such as amount of product used, temperature of water and length of
treatment time), but must sacrifice control in other areas (such as the exact condition
of the hair of the volunteers and the inherent personal biases of both volunteers and
operators.) This testing does provide preliminary information related to product
performance on consumers, but it does not provide a complete indication of how
the product will be perceived by a consumer using the product at home.
Consumer testing: Sometimes called home-use testing, this method provides
you with “real life” information. Panelists selected according to specific demo-
graphics are given the test product to take home and use for a specified time. They
then complete a questionnaire designed to gauge their perception of key product
attributes. This testing gives the formulating chemist feedback on product perfor-
mance under realistic consumer use conditions. Of course, the tradeoff is that the
chemist has relinquished most of the control over experimental variables. You can
no longer control, or even determine, such details as exactly how much product
was used per application, or the temperature of the water that was used to rinse
441
away the product. But at least you can establish whether, in the consumer’s mind,
your product is performing up to their expectations.
Other concerns: Finally, specialized testing may be required to determine
that certain products will not stain clothes or otherwise damage materials through
incidental contact. Once all the appropriate tests are completed and you have es-
tablished that your product functions properly and complies with all regulations,
you’re on your way to having an “ideal” product.
Summary
In the formulator’s ideal world, nothing ever changes and every time a product
is made it is exactly the same. In reality, a multitude of things can be different every
time a product is made. Suppliers may change chemical feedstocks, processing
conditions—such as mixing speed or temperature—may not be duplicated exactly,
or a near-infinite number of other unforeseeable events may surprise you. And
although there are a near-infinite number of “preventative” tests that can be done
to counter these problems (only a few of which were discussed here), it is physi-
cally impossible and impractical to identify and test for every one of these factors.
The best approach is try to exert control over as many critical factors as you can
identify. Some of the tests discussed above are typically employed by formulating
chemists to help identify which factors are critical and establish this control during
the product development process.
References
1. M deNavarre, Chemistry and Manufacture of Cosmetics, v1, D Van Nostrand Company
Inc, Princeton NJ 315–338 (1962)
2. D Orth, Handbook of Cosmetic Microbiology Marcel Dekker Inc, New York (1993)
Chapter 46
Preservative Efficacy
Testing: Accelerating
the Process
A preservative efficacy testing method, called the accelerated
double challenge, can assess the ability of a product or
material to resist microbial contamination in only 14 days. It
also maintains a high degree of correlation with longer-term
preservative challenge protocols.
key words: preservative, efficacy, testing,

accelerated double challenge
T he accurate and reproducible determination of the degree of microbial con-

tamination resistance of preserved personal care formulations is a critical
element in the development of safe and effective consumer products. Various ap-
proaches to preservative efficacy testing (PET) have been developed throughout
the years by regulatory agencies, standards organizations, industry organizations
and individual companies. Of the various protocols and approaches proposed and
developed, the microbial challenge test has evolved as the most commonly used
and accepted evaluation criterion.
The fundamental principle of the microbial challenge is based on the concept
of measuring the survival ability of selected microorganisms that are purposely
introduced into a preserved test product system. Conventional PETs or preser-
vative challenge test methods generally require microbial assays at multiple test
points throughout extended periods of time. Test durations typically range from a
minimum of 28 days to 12 or more weeks.
The prolonged four-week test cycle originally evolved via the United States
Pharmacopeia (USP) for application in the pharmaceutical industry. It has since
been adopted in one form or another for evaluating the efficacy of preservatives in
cosmetic and other consumer product formulations. The belief is that by extend-
ing the test time, slow-growing or preservative-damaged microorganisms would
have ample opportunity to recover and grow if they were capable, according to a
revitalizing phenomenon known as “the phoenix effect.”
Based on considerable research and the accumulation of extensive comparative
test data during the past 10 years, the current authors have determined that these
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Preservative Efficacy Testing: Accelerating the Process Beginning Cosmetic Chemistry
conventionally held concepts and beliefs regarding preservative test duration may
not be the only reliable approach for measuring the microbial resistance of preserved
formulations. This chapter will present an alternative testing approach using a con-
ventional microbial challenge technique that is capable of reducing the test cycle time
from four weeks to 14 days without the loss of sensitivity or impeding the predict-
ability of long-term preservative efficacy effects. Because standard microbiological
techniques similar to those employed in longer-term generic challenge protocols are
involved, no special equipment or training is necessary to perform the assay. In fact,
this accelerated double challenge (ADC) assay is currently being used in its basic form
or in variations at numerous laboratories for a variety of applications (see Current
ADC Applications sidebar).
Current ADC Applications

Currently, the ADC method or one of its variations is being applied at
more than 40 companies worldwide to evaluate a variety of cosmetic, per-
sonal care, household and industrial products at various stages of product
development:
• New product preservative system development
• Product preservative stability studies
• Package compatibility studies
• Batch scale up or pilot batch evaluation
• Process modification preservative effects
• Formula change/modification effects
• Post in-use study preservative evaluation
• Alternative ingredient preservative effects
• Verification of preservative system integrity
• Raw ingredient susceptibility studies
Standard PET Methods

Standard PET methodologies have been developed by numerous organiza-
tions and countries, including the Cosmetic, Toiletry, and Fragrance Association
(CTFA), the American Society for Testing and Materials (ASTM), the Association
of Analytical Communities (AOAC), Japanese Pharmacopoeia (JP), European
Pharmacopoeia/British Pharmacopoeia (EP/BP) and the USP.
Duration: These standard methodologies recommend PETs that require
minimum test durations of 28 days after inoculation. In the case of the CTFA and
ASTM methods, an additional 28 days (i.e., a 56-day test duration) is proposed if
a reinoculation step is included. The test duration requirements and suggested
test sampling times for each of these standardized methodologies are presented
in Table 46.1.
445
Table 46.1. Method requirements
Method Test Duration Sampling Times

AOAC 28 days 7, 14 and 28 days
CTFA 28 days or 56 days* 2, 7, 14, 21 and 28 days
ASTM 28 days or 56 days* 7, 14, 21 (optional) and 28 days
USP 28 days 14 and 28 days
JP 28 days 14 and 28 days
EP/BP 28 days 2, 7, 14 and 28 days
ADC 14 days 1, 3, 7 and 14 days
*Additional 28 days for reinoculation
Although the sequence of individual test days may vary somewhat from protocol
to protocol, the key indicator points where specified reductions are required are
essentially the same (i.e., 7 and/or 14 days with no increase in the recovered number
of microorganisms within 28 days). In terms of test applicability to specific product
forms, the pharmacopoeia methods generally have application for the full range of
parenteral, ophthalmic, topical and oral preparations.
Application: The AOAC, ASTM and CTFA methods are somewhat more re-
stricted in their application. The CTFA method is recommended for the evaluation
of water-miscible topical cosmetics, toiletries and eye-area products, as well as for a
number of OTC formulations such as sunscreens and antidandruff preparations.
The AOAC protocol, on the other hand, specifies application for “non-eye
area, water-miscible cosmetic and toiletry formulations” only. No recommendation
is suggested for eye-area preparations, although there does not appear to be any
significant reason why the method could not be applied to such formulations. It
is possible that the method has not been validated for those product forms or that
the proposed criteria of acceptability may not be applicable.
The ASTM method, which has recently been re-approved, was designed primarily
to determine the suitability of preservatives for use in cosmetic products. Although
it was not specifically developed for the evaluation of preservative effectiveness in
cosmetic products, it has been used for this purpose.
Organisms: In regard to the organisms recommended for inclusion in the
various preservative efficacy tests, all, with the exception of the EP/BP protocol,
include the same five indicator organisms: Pseudomonas aeruginosa, Staphylococ-
cus aureus, Escherichia coli, Candida albicans and Aspergillus niger. The EP/BP
excludes Escherichia coli. The CTFA, AOAC and ASTM methods that are only
applicable to cosmetic formulations go one step further and suggest a variety of
additional microorganisms and, if appropriate, environmental isolates.
The AOAC method specifies pooling groups of like organisms for inoculation
whereas the CTFA and ASTM methods allow either inoculation of product with
individual challenge organisms or inoculation of test product with compatible
446
mixed cultures. The various challenge organism options for each of the specified
methodologies are presented in Table 46.2.
Table 46.2. Challenge test organisms
For bacteria, the abbreviated genus names are Acinetobacter, Burkholderia,

Escherichia, Klebsiella, Pseudomonas and Staphylococcus. The exceptions are
Enterobacter gergoviae and Enterobacter cloacae.
For fungi, the abbreviated genus names are Aspergillus, Candida and Eupenicillium.
Method Bacteria Fungi
AOAC 1. S. aureus, S. epidermidis A. niger, C. albicans
2. K. pneumoniae, E. coli, E. gergoviae
3. P. aeruginosa, B. cepacia, A. baumanii
CTFA 1. S. aureus or S. epidermidis A. niger or P. luteum

2. Two from: C. albicans or C. parapsilopsis
K. pneumoniae, E. coli, E. gergoviae,
E. cloacae, Proteus species
3. P. aeruginosa and one from:
B. cepacia, P. fluorescens, P. putida,
Flavobacter species, Acinetobacter species
ASTM S. aureus, P. aeruginosa, B. cepacia, A. niger, C. albicans,

E. coli, E. gergoviae E. levitum
USP S. aureus, P. aeruginosa, E. coli A. niger, C. albicans

JP S. aureus, P. aeruginosa, E. coli A. niger, C. albicans
EP/BP S. aureus, P. aeruginosa A. niger, C. albicans
ADC S. aureus, P. aeruginosa, B. cepacia, A. niger, C. albicans,

E. coli Penicillium species
In-house PET Methods

Although a number of cosmetic and personal care companies have been known
to use the pharmacopoeia or either the CTFA or AOAC test methodologies, the
vast majority of companies have developed and adopted their own in-house PET
protocols. Oftentimes, these procedures can be far more stringent than those speci-
fied in the standard methodologies and may even include simulated or real-time
“in-use” preservative challenge evaluations.
In most cases, however, these methods are essentially modifications or varia-
tions of the standard PET procedures. Some of the more common differences
from the standard PETs include: test points, test duration, specified challenge
organisms, inoculum content/mixtures, reinoculation and criteria of acceptability.
447
It is interesting to note that even with all of these variations of the basic theme,
most protocols in use, whether they are in-house or standard methods are capable
of identifying both well-preserved products and those that have weak preserva-
tive systems. The potential issue with some of these methods generally arises in
detecting formulations that have a marginal spectrum of activity, weaknesses in
activity against a particular category of organisms such as mold, or have a reduced
antimicrobial capacity or robustness.
With a single challenge protocol and inappropriately designated test points,
these difficulties could go undetected or, at best, not recognized until very late in
the testing cycle. Since the duration of many of the more rigorous in-house test
protocols generally is in excess of the 28-day minimum, as specified in the con-
ventional methodologies, and in many cases as long as 12 or more weeks, the late
detection of a potentially problematic issue could ultimately have a major negative
impact on the formulation development process.
PET Primary Objectives
The primary objective of any PET is to accurately and reproducibly measure
the ability of a product or formulation to resist both normal and abnormal microbial
insult. This objective may or may not necessarily be compatible with the precon-
ceived notion of passing some arbitrary criteria of acceptability, such as those speci-
fied in some of the standard methodologies, but rather with the goal of ensuring
that the product is properly and effectively preserved. The selected methodology
should be capable of predicting both the risk potential for product recontamina-
tion as well as the long-term continued efficacy of the preservative system during
its shelf and use life. In order to accomplish this end, the method must encompass
a means of measuring and determining two key preservative challenge predictive
elements—rate of kill or death rate, and robustness or capacity to continue to resist
subsequent recontamination.
Accelerated Testing Benefits and Concerns

The benefits of using an accurate and verifiable accelerated challenge protocol
are numerous.1 Reducing the time to evaluate the preservative capability of new or
revised formulations allows for significantly more flexibility within the development
cycle. Successes or potential failures can become obvious in a more reasonable
period of time, allowing for rapid feedback to development personnel.
Data developed in a shorter time frame allows for formulation adjustments or
modifications to be initiated weeks before data from longer-term testing can be
made available. The selection of alternative preservatives and preservative sys-
tems can be further facilitated by allowing for many more formula variations to be
evaluated over a shorter period of time. The dollar and labor savings involved in
using protocols having reduced testing time can obviously be substantial2 because
decisions and product direction can more efficiently be managed.
Chief among the concerns of employing accelerated testing protocols are ques-
tions concerning the ability of accelerated tests to predict long-term preservative
448
efficacy and the degree of correlation of these tests to conventional standard or

in-house preservative efficacy methods. The issues related to slow-growing fungi
and damaged organisms also have been bothersome, as have the potential difficul-
ties involved in properly interpreting test data.
Some published accelerated protocols introduce foreign materials to the test
product system3 or serial dilute the formulation.4 Each of these approaches radi-
cally alters the substance and integrity of the formulation so that the test material
may differ from the original test formulation in its chemical makeup or its physical
makeup or both. Although these approaches may be suitable for selected product
forms, there are questions about the general reliability of testing significantly modi-
fied product systems and meaningfully relating the data developed to predicting
intact product contamination.
An alternative approach for rapid PET, based upon linear regression (D-values),
was proposed by Orth in a series of publications.5–6 The basic concept of this direction
definitely has merit; however, the protocol addresses only rate of kill, which is only
one of the two key predictive preservation test elements. Product preservative system
robustness or the capacity of the product to resist recontamination does not appear
to be easily measured or predicted using the D-value approach as defined.
Accelerated Double Challenge PET

In order to meet the requirements for an all-inclusive predictive accelerated
PET protocol, a method must be capable of determining and measuring both
the rate of kill and the robustness or resistance capacity of a product preservative
system. Through extensive research, numerous method comparison studies, and
real-time practical product preservative evaluations, Bio-Control has established
that the accelerated double challenge (ADC) testa is a meaningful predictive tool
that measures both kill rate and product robustness.
The method originally was developed to provide a rapid screening procedure
for the identification of poorly preserved or marginally preserved cosmetic for-
mulations. Once the accuracy and reproducibility of the process were established
for generic cosmetic creams, lotions and liquids, the method was applied with
appropriate variations to other product and material forms such as w/o emulsions,
wet wipes,7 household products and preserved raw materials. In all these cases, the
ADC protocol rapidly—in 14 days—assessed the ability of a product or material to
resist microbial contamination while maintaining a high degree of correlation with
longer-term preservative challenge protocols.
The protocol: The ADC protocol allows for flexibility with regard to the use
of pure cultures, mixed cultures or pooling groups of like organisms and any of
these inoculation approaches can be applied to the protocol. Although the basic
procedure includes the standard list of indicator organisms, the final selection of
challenge organisms can vary and include environmental or product contaminants
as well as other organisms that may have significance for the product form being
evaluated.
In most cases, the current authors found that using separate, previously deter-
mined compatible, mixed cultures of bacteria and fungi provides meaningful and
449
reproducible results with conclusions comparable to those of pure-culture or pooled

like-culture techniques and with a reduction in labor and materials.
The basic ADC protocol involves preparing aliquots of each test preparation and
inoculating them with separate mixed cultures of bacteria and fungi or, alternatively,
with individual pure cultures or pooled like-cultures of the selected challenge mi-
croorganisms. Test units are then inoculated at time 0 in a manner similar to that
used for other recognized challenge protocols. Inoculum levels are ~106 for the
mixed or pure bacterial cultures and ~105 for the mixed or pure fungal cultures.
What distinguishes the ADC protocol from other similar challenge protocols is
the reinoculation of the same sample test units at seven days using the same concen-
trations of inoculum. The reinoculation at seven days is designed to severely stress
the product preservative system in an effort to determine the product’s robustness
or innate ability to resist significant repetitive microbial insult.
Conventional plate counts to determine survivors are performed using appropri-
ate neutralizing diluents and recovery media on each of the inoculated test units after
1, 3, 7 and 14 days of incubation at room temperature. Evaluating the inoculated
test samples at days 1, 3 and 7 is, in addition to the 7-day re-challenge, the other
key predictive element and sensitive comparative indicator for determining and
measuring the rate of kill or potency of a product preservative system.
The ADC method uses three data points such as 1, 3 and 7 in developing rate-
of-kill trends. Use of three points enhances the reliability of the data obtained—
especially in the case of nonlinear death curves/rates—and allows for a more
informative picture when comparing the preservative efficacy of two or more test
product variations.
The total test duration is 14 days not counting an additional five days for the
incubation of the fungal plates.
Results: ADC results generally are presented as the number of surviving organ-
isms present at each time interval per gram of product inoculated.
Acceptability: Because the ADC protocol is significantly more rigorous than
the standard recognized methodologies, the interpretation of the data developed
may be somewhat more challenging. A tester may use any reasonable interpretive
guideline appropriate to the tester’s needs and the product form being evaluated,
but the authors’ experience with the protocol suggests the following minimum
criteria of acceptability:
Bacteria (pure or mixed cultures): recovery of <10 cfu per gram 7 days after the
first inoculation plus a 5 log reduction after the second inoculation at 14 days.
Fungi (pure or mixed cultures): a 3 log reduction 7 days after both the first and
second inoculations with no increase in counts.
Reliability: Based on criteria for predicting product preservative efficacy, the
conclusions drawn from the ADC-generated preservation data were essentially
comparable to the conclusions drawn from data developed using the standardized
methodologies. For those situations where the data or conclusions drawn did not
correlate, the differences were largely a result of the greater rigorousness of the
ADC method.
450
ADC was significantly more sensitive in detecting marginally or weakly preserved

formulations. Products that were marginally preserved failed the ADC criteria of
acceptability while passing the longer-term single inoculation protocols. In-house
data from a number of studies on different product forms suggest that there appears
to be a >99% positive correlation with the longer four-week test protocols such as
the CTFA or USP. Some of those studies are described next.
Comparative Studies: USP versus ADC

The authors undertook two studies whose purpose was to verify that the accel-
erated double challenge preservative evaluation testing procedure was equivalent
to or better than the 28-day single challenge mixed culture USP protocol for the
demonstration of preservative effectiveness in multiple dosage cosmetic and OTC
product forms. The selected product forms were an SPF cream in the first study
and a medicated lotion in the second. Each study was conducted in triplicate.
Methods and materials: The protocols described here are procedure briefs
and were to be used for the purposes of these studies only. The procedures are
not intended to be detailed representations of the official protocols that they
represent.
For the modified USP (MUSP) protocol, aliquots of each model test preparation
were inoculated with separate mixed cultures of bacteria and fungi at time 0 only.
Plate counts to determine survivors were performed at time 0 and after 7, 14, 21 and
28 days of incubation at room temperature. Results are presented as the number
of surviving organisms per gram of tested product present at each time interval.
Inoculum levels were ~106 for the individual bacteria and ~105 for the individual
fungi. Specific inoculum counts for the inoculations at time 0 are presented later
in Tables 46.3 and 46.5. The reader should note that USP requires sampling and
testing only at days 14 and 28 for Category 2 products. For the purposes of these
studies, two additional test times at 7 days and 21 days were included.
For the ADC protocol, aliquots of each model test preparation were inoculated
with separate mixed cultures of bacteria and fungi. Samples were inoculated at time
0 and reinoculated at 7 days. Plate counts to determine survivors were performed at
time 0 and after 1, 3, 7 and 14 days. Results are presented as the number of surviving
organisms per gram of tested product present at each time interval. Inoculum levels
were ~106 for the mixed bacteria and ~105 for the mixed fungi. Specific inoculum
counts for both the time 0 inoculation and the 7 day reinoculation are presented
later in Tables 46.4 and 46.6.
For the inoculata in both protocols, the following microorganisms were used:
• Pseudomonas aeruginosa ATCC #9027
• Escherichia coli ATCC #8739
• Staphylococcus aureus ATCC #6538
• Candida albicans ATCC #10231
• Aspergillus niger ATCC #16404.
For the MUSP protocol, individual pure cultures of each of the organisms
were used. With the ADC protocol, separate mixed cultures of the same bacteria
and fungi were used.
451
Results: The results from the comparative challenge studies conducted in trip-
licate are presented in Tables 46.3 and 46.4 for the SPF cream and Tables 46.5
and 46.6 for the medicated lotion. Microbial counts are recorded as the number
of cfu’s recovered per gram of inoculated test material.
Table 46.3. MUSP Protocol: SPF cream trials

(all microbial counts in cfu’s per gram of inoculated test material)
Microbe Inoc 7 Days 14 Days 21 Days 28 Days

Trial 1
P. aeruginosa 2,100,000 10 <10 <10 <10
E. coli 1,320,000 <10 <10 <10 <10
S. aureus 1,200,000 <10 <10 <10 <10
A. niger 210,000 720 240 <10 <10
C. albicans 320,000 600 200 <10 <10
Trial 2
P. aeruginosa 2,100,000 <10 <10 <10 <10
E. coli 1,320,000 <10 <10 <10 <10
S. aureus 1,200,000 <10 <10 <10 <10
A. niger 210,000 610 280 <10 <10
C. albicans 320,000 560 190 <10 <10
Trial 3
P. aeruginosa 2,100,000 <10 <10 <10 <10
E. coli 1,320,000 <10 <10 <10 <10
S. aureus 1,200,000 <10 <10 <10 <10
A. niger 210,000 590 310 <10 <10
C. albicans 320,000 640 240 <10 <10
Table 46.4. ADC Protocol: SPF cream trials

Microbe Inoc 1 Day 3 Days 7 Days* Reinoc 14 Days

Trial 1
Bacteria 2,300,000 81,000 1,500 10 1,900,000 880
Fungi 310,000 2,250 1,100 460 205,000 150
Trial 2
Bacteria 2,300,000 51,000 1,200 <10 1,900,000 900
Fungi 310,000 1,600 900 480 205,000 100
Trial 3
Bacteria 2,300,000 64,000 1,350 <10 1,900,000 850
Fungi 310,000 1,400 980 360 205,000 300
*Reinoculated at 7 days
452
Table 46.5. MUSP Protocol: Medicated lotion trials

Microbe Inoc 7 Days 14 Days 21 Days 28 Days

Trial 1
P. aeruginosa 2,100,000 <10 <10 <10 <10
E. coli 1,320,000 <10 <10 <10 <10
S. aureus 1,200,000 <10 <10 <10 <10
A. niger 210,000 50 30 <10 <10
C. albicans 320,000 10 <10 <10 <10
Trial 2
P. aeruginosa 2,100,000 20 <10 <10 <10
E. coli 1,320,000 <10 <10 <10 <10
S. aureus 1,200,000 <10 <10 <10 <10
A. niger 210,000 60 20 <10 <10
C. albicans 320,000 <10 <10 <10 <10
Trial 3
P. aeruginosa 2,100,000 10 <10 <10 <10
E. coli 1,320,000 <10 <10 <10 <10
S. aureus 1,200,000 <10 <10 <10 <10
A. niger 210,000 60 30 <10 <10
C. albicans 320,000 30 10 <10 <10
Table 46.6. ADC Protocol: Medicated lotion trials

Microbe Inoc 1 Day 3 Days 7 Days* Reinoc 14 Days

Trial 1
Bacteria 1,300,000 50 <10 <10 2,200,000 <10
Fungi 370,000 5,000 1,200 50 210,000 120
Trial 2
Bacteria 1,300,000 100 10 <10 2,200,000 <10
Fungi 370,000 1,600 900 20 210,000 60
Trial 3
Bacteria 1,300,000 60 <10 <10 2,200,000 <10
Fungi 370,000 1,400 980 40 210,000 80
*Reinoculated at 7 days
Discussion of the results from the SPF cream: Based on the results ob-
tained from the three MUSP trials (Table 46.3), the SPF cream passed the USP
criteria of acceptability and appears to be adequately preserved. A 6 log reduc-
tion in numbers was observed for each of the bacterial species within 14 days and
there was no increase in microbial counts thereafter. In terms of the fungi, both
453
the C. albicans and the A. niger demonstrated a 3 log reduction in 14 days with
no increase thereafter.
The data generated in the three ADC trials (Table 46.4) demonstrated similar
results at the 7-day test point; however, it also identified an apparent weakness in
antibacterial preservative capacity after reinoculation. A 6 log reduction in 7 days
after the first inoculation for the mixed bacteria was observed, whereas only a 4 log
reduction in bacteria was apparent after the second inoculation.
Fungal reductions for the two methodologies were essentially the same with
3 log reductions demonstrated in both situations. Both protocols demonstrated
excellent procedural reproducibility as was evident from the triplicate data gener-
ated. Comparatively, one could conclude that, in this particular study, the ADC
protocol was more capable of defining product preservative system vulnerabilities
than was the MUSP single challenge methodology.
Discussion of the results from the medicated lotion: Data generated by
the three MUSP trials on the medicated lotion (Table 46.5) clearly demonstrate
that this model formulation is well-preserved and easily passes the acceptability
criteria for adequate preservation. A 6 log reduction in numbers was observed for
each of the bacterial species within 14 days and there was no increase in microbial
counts thereafter. In addition, a very respectable 4 log reduction was observed for
both of the fungal inocula.
Data developed in the three ADC trials (Table 46.6) also appears to sup-
port the well-preserved status of this formulation even after the second microbial
challenge. Excellent 6 log bacterial reductions were observed 7 days after each
of the mixed bacteria inoculations whereas a similarly acceptable 4 log reduction
was observed after each inoculation for the mixed fungi. From the additional kill
time data points at days 1 and 3, there is also the suggestion that the fungal rate of
kill, although acceptable, may be somewhat slow with low level survivors detect-
able at each test point through day 7. Depending on product recommended use
characteristics and final package configuration, this slower rate of kill could be a
potential vulnerability.
Conclusions: Based on the data developed during the comparative challenge
testing trials to determine equivalency between the USP 28-day PET and the de-
scribed 14-day ADC PET, it appears that both methods are essentially equivalent
and arrive at similar conclusions in determining preservative system effectiveness
for well-preserved product systems.
With marginal or reduced-capacity systems, however, it appears that the ADC
PET protocol has the capability of detecting preservative vulnerabilities or potential
weaknesses in efficacy that could go undetected by using only the USP methodol-
ogy. This additional ability to detect and measure robustness and rate of kill can be
an invaluable tool when evaluating the preservative capability of multiple dosage
cosmetic and OTC product forms.
Summary
On the basis of the comparative studies described here and the established history
of successful application of the accelerated double challenge test to the evaluation
454
of multiple product forms, it would appear that this methodology provides a reliable
and viable alternative option for conducting preservative efficacy testing.
The method is relatively easy to conduct using traditional microbiological prac-
tices and requires no specialized equipment. Obviously, it is strongly suggested that
before adopting this or any other testing methodology, appropriate qualification
and comparative verification studies must be conducted.
The current urgency to replace preservatives viewed as unacceptable by con-
sumers places high value on the use of accelerated preservative efficacy testing
methods to bring reformulated products more quickly to the marketplace.
References
1. GK Mulberry, MR Entryup and UR Agin, Rapid screening methods for preservative
efficacy evaluations, Cosmet Toil 103(12) 47–53 (1987)
2. DS Orth and CM Lutes, Adaptation of bacteria to cosmetic preservatives, Cosmet Toil
100(2) 57–64 (1985)
3. J O’Neil, CA Mead and EJ Scibienski, Presented at the annual meeting of the Society
of Cosmetic Chemists (December 1981)
4. M Chan and HN Price, A rapid screening test for ranking preservative efficacy, Drug
Cosmet Ind 129 34–37, 80, 81 (1981)
5. DS Orth, Linear regression method for rapid determination of cosmetic preservative
efficacy, J Soc Cosmet Chem 30 321–322 (1979)
6. DS Orth, “Evaluation of preservation in cosmetic products” In Cosmetic and Drug
Preservation, JJ Kabara, ed, Marcel Dekker, New York Chap 22, 403–421 (1984)
7. JI Yablonski, The microbiology of wet wipes, presented at the New Jersey SIM
meeting in Newark, Sept 18, 2002
For Additional Reading

ASTM E 640-78 (Reapproved 2006), Standard test method for preservatives in
water-miscible cosmetics, American Society for Testing and Materials, West
Conshohocken, PA, USA: (2006)
CTFA Microbiology Guidelines, M-3, Determination of preservative adequacy
in cosmetic formulations, The Cosmetic, Toiletry, and Fragrance Association,
Washington, D.C.: (2006)
Antimicrobial effectiveness testing, Section 51 in United States Pharmacopeia,
28th edn, United States Pharmacopeial Convention, Rockville, MD, USA:
(2005)
Method 998.10, Efficacy of preservation of non-eye area water-miscible cosmetic
and toiletry formulations, Official Methods of Analysis of AOAC International,
17th edn, Gaithersburg, MD, USA: AOAC International (2000)
JI Yablonski, Preservatives—Microbial guidelines for the manufacture of non-
sterile products, Section #12, prepared for the Proprietary Association of
Canada and the Canadian Toilet Goods Manufacturing Association (1973)
455
JI Yablonski, Strategies for cosmetic preservation, Cosmet Toil 92(3) 22–31

(1977)
JI Yablonski, Preservative efficacy testing—accelerating the process, Presented
at the CTFA technical conference, NJ, November 8, 2005, and the Midwest
SCC meeting, Chicago, April 23, 2005
Chapter 47
The Century of Progressive

Regulation
This article reports some of the key progress made in ingredient
regulation by the FDA and CTFA in the United States over the
past 100 years, leading to today’s standards and progress.
key words: CTFA, FDA, preservatives, additives, testing, labeling
T echnology transfer across industries carries with it the good and the bad;
innovation, the lifeblood of progress, as well as concern for safety. It is inter-
esting to note that 100 years ago, as the US Agriculture Department’s Bureau of
Chemistry (the predecessor to the US Food and Drug Administration) launched
an investigation of ingredients used to preserve food, The American Perfumer (the
predecessor to Cosmetics & Toiletries magazine) examined the use and manufacture
of ingredients for the perfumery, perfumed soap and toiletry markets. This chapter
reports some of the key progress made in ingredient regulation in the United States
over the past 100 years.
Establishing Roots
The number of US perfumery and toiletry manufacturers grew from 67 in 1880
to 262 in 1900, representing nearly a 400% increase. The value of products rose
from $2.2 million in 1880 to more than $7 million in 1900.1
As the industry grew it became more competitive, and manufacturing costs
became a major concern. The early Cosmetic, Toiletry, and Fragrance Associa-
tion (CTFA) manifest in 1894 as the Manufacturing Perfumers’ Association of the
United States (MPA) and primarily was the work of five individuals led by New
York perfumer Henry Dalley. It also included Bowles Colgate, president of Col-
gate & Company.1 According to the CTFA, Dalley’s motivation for initiating MPA
was pending Congressional legislation proposing an increased tariff on imported
raw materials, which would affect the cost of producing toiletry goods. With sup-
port from the group, Dalley coordinated industry opposition to the legislation. By
1894, Dalley saw the need for a permanent organization and persuaded a group
of colleagues to join him. The MPA was established at Delmonico’s Hotel in New
York in October 1894. During its first 10 years, the group focused on furthering
the industry’s interests regarding tariffs and taxes. In 1941, an intensive lobbying
effort was made by the association, but the tariff was enacted, imposing a 20% duty
on 90% of the raw materials used in perfumes and toiletry goods.1
457
458
The Century of Progressive Regulation Beginning Cosmetic Chemistry
In the end, World War I created a timely “push” for the industry’s growth,
according to the CTFA. Although the war exposed nearly five million American
soldiers to French perfume and other toiletry articles and created a demand for
them, exports to the United States from France declined because of the war, open-
ing an opportunity for the growing American perfume and toiletries market.
Defining Cosmetics
The FD&C Act defines the term “cosmetics” as articles intended to be
applied to the human body for cleansing, beautifying, promoting attractive-
ness or altering the appearance, including the components of such articles.2
Examples are perfumes, lipsticks, makeup and hair dyes. Under the law, the
term “cosmetic” includes both finished products and ingredients.
If a product’s intended use is to cure or prevent disease or to affect the
structure or function of the body, however, it may be a drug under the law.
Some products are designed to be both drugs and cosmetics. For example, a
dandruff treatment is a drug; however, the same product, a shampoo designed
to clean and beautify hair, is a cosmetic, according to its intended use.
Ingredients: A Federal Case

Interest in the raw materials that consumers were putting into and on their
bodies peaked with the United States release of Upton Sinclair’s book, The Jungle,
which exposed the public to toxic food preparation conditions in meat packing
plants. Prompted by concerns for untested chemicals being used as food preserva-
tives, Harvey Wiley, M.D., chief chemist of the Bureau of Chemistry, initiated an
investigation to determine if the preservatives being used were safe, and if so, at
what levels they were safe. Congress approved funds for his studies in 1902.2
Wiley’s tests consisted of a group of volunteers sampling foods containing mea-
sured amounts of borax, salicylic acid, formaldehyde and other preservatives. The
tests ceased after the volunteers became ill. In the end, Wiley concluded that the
ingredients should be used only when necessary, and he placed the responsibil-
ity for food safety on food producers. He also supported consumer awareness of
ingredients on product labels.2
Labeling Concerns
With the rising concern for public safety, the original Pure Food and Drugs Act
passed in 1906, prohibiting misbranded and adulterated foods, drinks and drugs
from being introduced to the public. The act also prohibited the addition of color
additives to mask inferior products and the use of poisonous colors in confection-
ary applications. In 1913, the Gould Amendment was added to the Pure Food
and Drugs Act, requiring that contents be plainly marked on the outside of food
packages; however, it was not until the revised act of 1938 that manufacturers were
required to self-regulate the products they made.
459
Deceptive, Dangerous Products

In 1930, the Bureau of Chemistry became the US Food and Drug Administra-
tion (FDA), and in 1933 it recommended a revision of the 1906 act because several
deceptive, dangerous and non-effective products remained on the public market.
These products fell within the distinctive name proviso, which allowed manufactur-
ers to market foods with distinctive names.
For example, Bred-Spred was a jellylike product that would have been considered
misbranded under the 1906 act because it contained no fruit.
Typical jelly or jam would have consisted of half sugar and half fruit, but the
distinctive name proviso allowed the product to remain on the market because the
label technically did not claim the product was jelly or jam.2
In one case, a product called Elixir Sulfanilamide that contained a toxic ingredient
was found to have caused the deaths of 107 people. In response to these fatalities,
the agency pushed the 1938 Food, Drug and Cosmetic (FD&C) Act through. A key
aspect of the revised bill was that for the first time, manufacturers were required
to provide evidence that new drugs were safe prior to marketing them.3
Batch Certification
The 1938 FD&C Act also extended regulatory control to cosmetic manufactur-
ers for the first time. Before the new act, a coal tar-based eyelash dye marketed as
Lash Lure had caused serious eye injuries and blindness to consumers.
Under the new act, this product was one of the first cosmetic seizures by the
FDA. By mid-1939, the FDA had seized more than 65 lash and brow dyes contain-
ing the dangerous paraphenylenediamine chemical.3 The new act required colors
to be pre-approved before being used in foods, drugs and cosmetics. In addition,
colors made from coal tar sources had to be batch-certified.2
Reconciling Cosmetics
By 1938, the MPA became known as the Toilet Goods Association (TGA). The
TGA identified the New York World’s Fair as an opportunity to counteract the nega-
tive publicity plaguing the industry. Seventeen companies leased exhibit space in a
cosmetic pavilion, including Revlon, Chanel and Coty. According to the fair guide,
the pavilion demonstrated how cosmetic products had contributed to American
“loveliness by enhancing the natural beauty of women.” The exhibits also were
said to have shown “that the preparation of cosmetics is scientific, although much
phatasy (sic) and imagination are associated with their glamorous results.”1
Alternative Thought
When World War II hit in 1939, the TGA convinced the US government to allow
the industry to continue manufacturing products as long as alternative sources of
raw materials could be obtained. Efforts to develop suitable alternative ingredients
became the focus of the association’s scientific advisory committee. Meeting ap-
proximately every two weeks during the war, the committee developed substitutes
for critical raw materials, packaging and closures. For example, the group developed
more than 30 proposed substitutes for glycerine.1
460
During the war, the association also established a scientific division, which
brought technical and production personnel together to present and discuss sci-
entific papers. Out of World War II came much of the modern food technology
and medicinal chemistry that helped pave the way for many of today’s scientific
advancements in the cosmetic industry.1
Food, Color Additives under Fire

In 1950, a House Select Committee, chaired by Rep. James Delaney D-NY,
was formed to investigate the safety of additives used in food and cosmetics. This
group laid the foundation for the food and color additive amendments. The com-
mittee held extensive hearings before issuing a report in 1952 recommending that
legislation be developed to protect consumers from harmful chemicals in food and
cosmetics.1 Terms of the Food Additive Amendment called for manufacturers of
food additives to prove an ingredient’s safety to the FDA before it could be placed
on the market.
Delaney later proposed a change to the bill—the Delaney Clause—which
prohibited the approval of any food additive shown to induce cancer in humans
or animals in studies with a relevant route of exposure.2 The Delaney anti-cancer
clause was included in the final Food Additive Amendment of 1958. Some experts
have commented that this clause is misinterpreted by today’s legislation and that
it is partially the basis for California’s new Safe Cosmetics Act.
In 1958, the FDA also published the first list of substances “generally recognized
as safe” (GRAS). This list contained nearly 200 substances including ascorbic acid,
papain and propylene glycol.
Reaching the Public

An increasingly affluent middle class emerged after World War II, and the in-
dustry saw an unprecedented period of growth, according to the CTFA. Industry
sales reached the $1 billion mark in 1952 and continued to rise. For the TGA, this
baby boom era was marked by challenges on a number of fronts. For example,
consolidations in job functions in the industry resulted in a decrease in association
membership, even though sales were on the rise.1
At that time, the industry and the association focused on educating outsiders
about cosmetics—advertising agencies, retail sales clerks and the public. Educational
initiatives also targeted younger audiences; the association produced educational
booklets to persuade the Boy and Girl Scouts of America to establish a merit badge
for good grooming.1 On the legislative front, this era was marked by a series of new
regulatory issues spurred by a wave of concern for safety.
Pre-market Clearance
The cosmetic industry faced new regulations in color with the passing of the Color
Additives Amendment in 1960. Color additives had to gain pre-market clearance
before use in food, drugs and cosmetics,1 and until they could be approved by the
FDA, these additives were put on a provisional list for use on an interim basis.
461
Under the terms of the statute, the industry had to demonstrate the safety of both
coal-tar and non-coal-tar colors. Because of the costs involved in the process, the
industry was forced to forego testing on certain colors that were deemed expendable
to the industry. The colors chosen were based on a TGA polling of its members. A
program then was established to employ an independent testing laboratory funded
by the industry (on a voluntary basis) and based on certified color poundage used.1
Today, approximately half of the original 200 color additives are permanently listed
for use in foods, drugs, cosmetics and medical devices. Recent additions include
D&C Black No. 2 and mica-based pearlescent pigments.2
TGA Becomes CTFA

In March 1967, the TGA moved its headquarters from New York City to Wash-
ington, DC, to increase its influence on legislation. Two years after the move, the
association formed a public relations committee that made a thorough study of the
need for a name change. In September 1970, the board approved the association’s
current name, The Cosmetic, Toiletry, and Fragrance Association (CTFA).
Self-regulation
In the 1970s, consumer and environmental concerns captured the attention of
legislators and the media. The CTFA found itself in a 10-year struggle to convince
regulatory agencies and consumer groups that the industry’s commitment to product
safety and self-regulation precluded the need to introduce new legislation.1
In 1970, Virginia Knauer, President Richard Nixon’s special assistant for consumer
affairs, urged the cosmetic industry to support a voluntary registration program.
According to the CTFA, the call for such a program emerged at a time when ingre-
dient labeling of finished products was not yet required and when both consumers
and the FDA voiced concern over the industry’s lack of disclosure of ingredients,
registration of manufacturers and reports of adverse reactions to products.
At a December 1970 meeting with the CTFA, the FDA staff stated that if the
industry agreed to voluntarily provide this data, the agency would not seek to legislate
such a program. In 1971, the CTFA proposed a first-of-its-kind program represent-
ing the industry’s cooperation with the government to better protect the consumer.1
Under the program, both member and nonmember companies voluntarily provided
the FDA with information concerning their operations. The program entailed: (1)
registration of manufacturing establishments; (2) submission of data on composi-
tion of finished products; and (3) annual filing of consumer product experiences,
detailing the number of complaints received by participating companies.
Ingredient Dictionary
Following the Voluntary Reporting Program was the publication of the first
edition of the Cosmetic Ingredient Dictionary in 1973. The dictionary was the first
authoritative source for commonly accepted names of cosmetic ingredients, and
it evolved out of an association effort in 1970 to compile a list of chemicals used
in cosmetics and personal care. Working with representatives from the FDA and
462
the medical community, the CTFA cosmetic ingredient nomenclature committee

researched existing nomenclature systems and developed comprehensive guidelines
for consistency in name assignment.1
The first edition of the dictionary listed 5,000 trade and chemical names with
their CTFA adopted names, definitions, structures, Chemical Abstract Service
registry (CAS) numbers and other information. According to CTFA, the work lead-
ing up to the first edition of the Cosmetic Ingredient Dictionary greatly facilitated
the industry’s compliance the ingredient labeling standards adopted by the FDA
under the Fair Packaging and Labeling Act in 1975. The FDA soon recognized the
dictionary as the source for proper nomenclature for cosmetic ingredient labeling.
Each successive edition of the dictionary reflected the increasingly high demand
for more sophisticated information.1
The Eagleton Bill

In 1973, Sen. Thomas F. Eagleton D-MO, introduced a landmark bill that pro-
posed drastic changes to the federal oversight of the cosmetics industry. Eagleton’s
bill became the focus of CTFA activity for the next four years. Specifically, the bill
mandated: (1) pre-market clearance of cosmetics by the FDA and the establishment
of specified tests the industry would be required to perform prior to marketing a
product; (2) deletion of both the soap and hair dye exemptions of the 1938 FD&C
Act; (3) mandatory registration of cosmetic products; (4) detailed ingredient label-
ing requirements; (5) compiling and maintaining consumer complaints; and (6)
expanding FDA access to company records.1
The CTFA strongly opposed this bill, which it viewed as an attempt to remove
self-regulation from the cosmetic industry. In response, the CTFA proposed a new
regulation, issued in November 1975, including a provision that manufacturers
either substantiate the safety of their product or include a warning statement on
the product to indicate that the product’s safety had not yet been determined.1
During the time of the Eagleton bill, the industry planned another self-
regulatory program—the Cosmetic Ingredient Review (CIR). According to the
CTFA, CIR’s origins can be traced to a proposed FDA program for the specifica-
tion and toxicological examination of cosmetic ingredients. After a review of the
proposed program, the CTFA scientific advisory committee drafted a proposal for
a CTFA-sponsored “reasonably expected as safe” (REAS) ingredient evaluation
program. The CTFA Board approved this concept in 1975, and the following year
the program was named the CIR.1
International Affairs
The emergence of a global marketplace in the 1970s initiated a new area of
concern for the CTFA. In 1974, the CTFA participated in the launch of the Inter-
national Information Center for Cosmetics, a clearinghouse for the collection and
exchange of information. This center offered the industry an opportunity to access
valuable information concerning regulations, technical and scientific documenta-
tion, advertising and regulation of competition.1
463
In the 1980s, the CTFA’s involvement in international issues expanded signifi-

cantly with major initiatives undertaken in Europe, Japan and Latin America. The
CTFA’s International Committee, formed in 1977, nearly tripled in size by 1982.
In addition, the CTFA formed an international department in 1984.1
In Europe, the CTFA established close-working ties with Colipa, the Eu-
ropean federation of cosmetic trade associations, within the European Economic
Community (EEC). The CTFA and Colipa collaborated to ensure that ingredi-
ents used or manufactured by US companies were included on the EEC’s list of
substantiated products and that cosmetic sunscreen and preservative ingredients
used in the United States also were permitted in the EEC. This relationship allowed
the United States and Europe to work together to develop a common position on
new cosmetic regulations.1
For the Japanese market, the CTFA formed a task force in 1980 with a primary
objective to eliminate non-tariff trade barriers. These efforts included publishing
a consolidated list of approximately 2,400 ingredients approved for use in Japan
in 1984.1
Animal Testing
The issue of animal testing emerged in the 1970s as a major concern for the
cosmetic industry. Animal welfare and animal rights groups criticized using the
Draize eye irritancy test to substantiate the safety of ingredients and products. In
the summer of 1970, the CTFA prepared an official position paper on animal testing
titled, “Animal Testing: What Are the Choices?”1 Picketing of the CTFA headquarters
and its member companies in 1979 pushed the issue to the forefront.
As pressure continued to mount, the executive committee ordered CTFA’s
science committees to continue exploring the issue and directed the drafting of
a detailed legal position. In April 1980, the CTFA’s pharmacology and toxicology
committee established a task force to review the Draize test, explore alternative
testing procedures, and recommend research programs for the development and
validation of alternative testing procedures. In 1981, the CTFA board approved a
program for the industry to fund a national center for the development of alterna-
tives to animal testing. It awarded The Johns Hopkins School of Hygiene and Public
Health a $1 million three-year grant, supplemented with an additional $700,000
in 1984, and continued funding in subsequent years. In cooperation with the Bat-
telle Memorial Institute, the CTFA has conducted an evaluation of the alternatives
program since 1988. Although the industry was able to greatly reduce the number
of animals used in safety testing, animal rights groups continued their offensive
throughout the 1980s.1
Colors Revisited
A long-running effort by the CTFA to permanently list color additives that
provisionally were listed under the 1960 Color Additive Amendments continued
into the 1980s. In March of 1983, the group set out to establish the safety of several
provisionally listed color additives and urged the FDA to adopt a “de minimis”
standard, whereby the FDA could approve color additives posing a minimal cancer
464
risk.1 Subsequently, the US Court of Appeals ruled in 1987 that the FDA did not
have the authority to apply the de minimis policy, thereby mandating a strict in-
terpretation of the Delaney anti-cancer clause.1
California’s Proposition 65
In November 1986, California voters approved Proposition 65, the Safe Drink-
ing Water and Toxic Enforcement Act. The legislation required manufacturers to
either prove that ingredients in their products posed no significant risk of causing
cancer or reproductive toxicity or they would be required to include a warning
label on products containing an ingredient “known to the state” to cause cancer
or reproductive toxicity.1
The CTFA responded to this initiative on a number of fronts. First, it petitioned
the state to exempt cosmetics from the statute on the ground that cosmetics are
comprehensively regulated by the FDA. It also met with state officials and testi-
fied at various hearings in an effort to convince the state to adopt acceptable “no
significant risk” levels for several chemicals of interest to the industry. In addition,
CTFA attempted to convince both the FDA and Congress that the law undermined
the federal regulatory scheme.1
Wyden Hearings
In July and September 1988, hearings by Rep. Ron Wyden, D-OR, initiated
new charges concerning cosmetic safety and federal regulations. Specifically, the
Wyden legislation, which was drafted but never introduced, included a pre-market
testing requirement; increased FDA access to safety and consumer complaint data;
mandatory registration of manufacturing establishments, products and ingredients;
and mandatory ingredient listing for professional products.1 In response to the
Wyden hearings, the CTFA launched three initiatives: (1) a voluntary ingredient
labeling program for cosmetic products sold exclusively in salons; (2) an effort to
increase industry participation in the Voluntary Reporting Program; and (3) the
preparation of a report listing the status of approximately 1,000 chemicals alleged
to be toxic.1
Methylene Chloride in Hair Spray
During the “big hair” days of the 1980s, the FDA banned the use of methylene
chloride in all hair sprays, effective at the end of August 1989. This decision was
based on studies indicating that inhaling the chemical caused cancer in animals
and could be carcinogenic to humans. Methylene chloride was used in hair sprays
as a quick-drying solvent and flame retardant. The agency proposed the ban in
December 1985, after a study showed significant increases in the incidence of lung
and liver cancer in mice when the chemical was inhaled.4
“Antiaging” Challenged
In 1987, the term antiaging spiked interest from the FDA, which objected
to claims that certain cosmetics reversed the effects of aging. In response to the
marketing of several products by major cosmetic companies, the FDA sent letters
465
citing violations of the Federal FD&C Act, stating, “A review of the labeling (of
the cited product) reveals what the FDA believes are drug claims.”4
Environmental Concern
As the 1980s came to a close, environmental concerns occupied a growing por-
tion of the CTFA’s time on legislative, regulatory and scientific fronts. The group
faced various attempts to restrict the volatile organic compound (VOC) content of
personal care products in an effort to reduce emissions from consumer and com-
mercial products. The state of California placed restrictions on certain categories
of products and set future VOC limits placing certain products at serious risk in
coming years. With other states considering similar regulations, the CTFA worked
to convince these states to defer legislating VOC limits until after the US Environ-
mental Protection Agency adopted standards for these products.1
The CTFA also began to focus on environmental packaging and claims issues
before state legislatures. Several states enacted regulations or statutes designed to
reduce packaging, encourage re-use or incorporate recycled content into packaging.
The CTFA generally opposed proposals mandating certain percentages of recycled
content in packaging by certain dates. Rather, the CTFA endorsed an integrated
waste management approach. In addition, the industry made a significant investment
in testing the safety of packaging with recycled material; changing to different types
of plastics and reducing the amount of packaging for finished products.1
Building Self-esteem
The “Look Good…Feel Better” program, funded by the industry through
the CTFA Foundation, was introduced to help female cancer patients overcome
appearance-related side effects resulting from chemotherapy and radiation, thereby
helping to improve their self-esteem. Launched nationally in 1989, this CTFA
partnership with the American Cancer Society and the National Cosmetology
Association and “sister” programs now is offered in all 50 states and the District
of Columbia, as well as in 14 other countries. Approximately 50,000 women are
served by the program each year.5
Bleaching Agents for Teeth
In 1991, the FDA ruled that it considered products designed for tooth-whitening
via a bleaching mechanism to be drugs. Thus, those products could not legally
be marketed without FDA approval. According to the agency, tooth-whitening
products affect the structure of teeth through the bleaching process. These prod-
ucts proliferated between 1989 and 1991, even though their safety had not been
established. According to the FDA, the main ingredient used in teeth bleaching
was peroxide.4
Nutrition, Drug Facts Labeling

A change in labeling occurred with the Nutrition Labeling and Education Act
published in the Federal Register in January 1993. The regulations, announced
December 2, 1992, established new rules for labeling of virtually all foods.4
466
Also in 1992, over-the-counter (OTC) drug manufacturers would be required

to display the FDA’s new, easier-to-read drug facts label on their products. The
OTC regulation finalized in March 1999 and required a standardized format for
the labeling of drugs used in the United States.
FDA on Cosmeceuticals
In 1995 and 2000, the FDA announced its position regarding cosmeceutical
products. It stated that “while the Food, Drug, and Cosmetic Act does not recognize
the term cosmeceutical, the cosmetic industry uses this word to refer to cosmetic
products that have medicinal or drug-like benefits.” The FDA elaborated that the
act defines drugs as products that cure, treat, mitigate or prevent disease or that
affect the structure or function of the human body, and that while drugs are subject
to a review and approval process by FDA, cosmetics are not approved by the FDA
prior to sale. According to the FDA, “If a product has drug properties, it must be
approved as a drug.”4
Sunscreen Product Ruling of 1999

The FDA announced it finalized regulations for OTC sunscreen drug products
in 1999. The regulations listed the sunscreen active ingredients that could be used
in the products as well as labeling and testing requirements. According to the FDA,
the regulations provide for uniform, streamlined labeling for all OTC products
intended for use as sunscreen products to assist consumers in making decisions
on sun protection.
The FDA has been involved with the development of regulations for OTC drug
products since 1972, and sunscreens are one of many categories of OTC drug prod-
ucts for which monographs were finalized. Highlights of the new ruling included
a list of 16 allowed sunscreen active ingredients, with zinc oxide and avobenzone
being the two most recent additions. Additionally, a new SPF category of 30-plus
(or 30+) for SPF values above 30 was added.4
AHAs and UV Sensitivity

FDA-sponsored studies in 2000 stemmed from the use of alpha hydroxy acids
(AHAs) in skin care products. According to the FDA, the use of AHAs grew dra-
matically from 1990–2000. Advertising and labeling for these products claimed
that they reduce wrinkles, spots and other signs of aging. Despite the claims that
AHAs would bring changes to the skin, there was little information available about
their long-term safety. The FDA’s Office of Women’s Health confirmed that apply-
ing an AHA to the skin could make consumers more susceptible to the damaging
effects of the sun.4
Spray-on Tanning
In response to consumer questions about the safety and legality of sunless
tanning booths in which consumers receive an application of the color additive
dihydroxyacetone (DHA) in the form of a mist or spray, the FDA released a state-
ment in 2003 regarding commercial spray tanning booths. According to the FDA,
467
DHA is listed in the regulations as a color additive for use in imparting color to the
human body. However, its use in cosmetics—including sunless tanning products—is
restricted to external application. In addition, no color additive may be used in cos-
metics intended for use in the area of the eye unless the color additive is permitted
specifically for such use. The FDA explained that, when using DHA-containing
products as an all-over spray or mist in a commercial spray tanning booth, it may be
difficult to avoid exposure in a manner for which DHA is not approved, including
the area of the eyes, lips, or mucous membrane or even by inhalation. Thus, the
FDA warned that consumers needed to be protected around the eye and lip areas
and from inhaling or ingesting the product.4
Bovine Scare
In 2004, a form of spongiform encephalopathy that occurs in humans (vCJD)
was thought to result from the same protein (a prion) that causes bovine spongiform
encephalopathy (BSE) in cattle. According to the FDA, although it was likely that the
primary source of exposure was due to the ingestion of beef and other food derived
from cattle, it was feared that other routes of exposure should be considered.4
Cosmetics containing protein derived from bovine sources were considered
a potential source of exposure. As a result, the FDA concluded at that time that
there was some risk of occurrence of vCJD from the use of cattle-derived protein
in cosmetics.
As scientific information became available during the interim final rule’s com-
ment period, the FDA amended its ruling, stating that it no longer was necessary
to designate the entire small intestine as a prohibited cattle material, and that the
use of the small intestines in human food and cosmetics would be allowed.6
Phthalates
Advancing into 2005, the FDA continued to monitor potential exposure of
consumers to phthalates from the use of cosmetic products. The FDA’s Center
for Food Safety and Applied Nutrition announced plans to develop an analytical
method for the determination of phthalates in cosmetic products and to conduct a
survey of products to determine the contribution of phthalates to human exposure.
Presently, the FDA states that it does not have compelling evidence that phthalates
in cosmetics pose a safety risk.4
Nanoparticles
Most recently, the FDA announced plans to hold a public meeting in the fall of
2006 to discuss the current developments in uses of nanotechnology materials in
FDA-regulated products. A Federal Register notice invited all who are interested
in presenting at or attending the meeting to inform the agency of their interest.
According to the FDA, nanotechnology is a branch of science devoted to the design
and production of extremely small matter, and due to the small size and special
properties of nanotechnology materials, they have great potential for use in a vast
array of FDA-regulated products. The FDA will hold this meeting to further its
understanding of developments in nanotechnology.
468
C&T magazine’s Vantage

From the birth of the industry through its maturing technologies, the regulatory
challenges faced by the industry as well as regulating bodies have been tracked
through the pages of C&T magazine; and the pages of progress in regulatory affairs
reported here are merely samplings. Directed by the regulatory bodies looking
out for consumer safety—from the FDA and CTFA, to international groups such
as Colipa, the Canadian CTFA, the Japanese Cosmetic Industry Association and
others—the road ahead offers new paths of discovery.
Published June 2008 Cosmetics & Toiletries magazine
References
1. A Centennial History of CTFA, available at: www.ctfa.org/Content/ NavigationMenu/
About_CTFA/History/History.htm (Accessed Jun 2, 2006)
2. M Meadows, A Century of Ensuring Safe Foods and Cosmetics, in FDA Consumer,
7–13 40 1 (Jan–Feb 2006)
3. C Rados, “FDA Law Enforcement: Critical to Product Safety.” In FDA Consumer, 15–20
40 1 (Jan–Feb 2006)
4. The FDA Web site, available at www.fda.gov (Accessed Jun 21, 2006)
5. Look Good…Feel Better website available at www.lookgoodfeelbetter.org/general/
facts.htm (Accessed July 7, 2006)
6. Cosmetics & Toiletries Web site, available at: www.cosmeticsandtoiletries.com/
news/1822327.html (Accessed Jun 21, 2006)
Chapter 48
Mind Over Matter:

Cosmetic Claim
Substantiation Issues
Facing the Future
It is generally accepted by the public that effective cosmetic
products can positively influence the well-being of individual
consumers. Whereas we can easily measure the skin
moisturizing properties of a cosmetic formulation, measuring its
precise effects on well-being is much more complex.
key words: matter claim, mind claim, mind-body skin care,

quality of life, fMRI
I n the past, companies could say almost anything about the performance of
cosmetic products. But today the industry is relatively modest both in what is
expected from products and in what is promised to consumers. Kerryn Greive gives
some beautiful examples of cosmetic claims made for soap in her 2002 Maison G.
de Navarre Essay Prize winning article.1 In the 1920s, soap claims related mainly to
safety: “Don’t make your face an experimental laboratory, say 250 skin specialists.”
Efficacy claims started to emerge in the 1930s: “Tests run under scientific conditions
prove conclusively that Lava Soap removes more dirt then ordinary toilet soap and,
therefore, removes more germs.”
In the 1940s, more sensory-related claims started to appear: “Two out of three
women can get more beautiful skin in 14 days! Palmolive beauty plan tested on 1,285
women with all types of skin.”
The experiments supporting these statements were no doubt performed, but
certainly no system was in place for consumers to verify the validity of the experi-
ments performed and claims made.
Cosmetic Claims
The European Cosmetic, Toiletry, and Perfumery Association (COLIPA) de-
fines a cosmetic claim as any public information—primarily provided for marketing
purposes—on the content, the nature, the effect, the properties, or the efficacy
of the product. A claim may constitute words, images, illustrations, marks, or
469
470
Mind Over Matter: Cosmetic Claim Substantiation Issues Beginning Cosmetic Chemistry
descriptions that may appear on products (packaging, labels, inserts, etc.), or in

advertising (e.g., at sales points or circulated by different media).2 This latitude
allows for a wide variance in cosmetic claims. Indeed, various types of claims do
exist that all require different levels of cosmetic claim substantiation.
Emotive statement: Wiechers and Wortel3 described three different types of
claims. First of all, the emotive statement—e.g., L’Oréal’s famous “Because I’m
worth it”—is not a cosmetic claim in the strict definition given above. This type of
claim therefore does not need to be substantiated.
Ingredient claim: The second type of claim is the ingredient claim—product
X containing Y that is known to do Z, in which Y is a cosmetic active ingredient and
Z a cosmetic efficacy—implying that the activity of the ingredient is maintained
in the cosmetic product in which it is incorporated. Evidence may come from the
scientific literature or from the supplier of the ingredient.
Product claim: The third type of claim is the product claim—product X is
reducing wrinkles by Y% in Z days. The company claims that the cosmetic product
itself does deliver the effect, although these claims are often softened by the use
of the words “helps to.”
Another example of clever wording comes from Beiersdorf where the company
claims that, “Based on the natural plant extract Alpha Flavon, a powerful and ef-
fective antioxidant, it acts as a shield against the damaging effects of daylight. And
it’s proven to activate the skin’s antiaging defenses.” Here it is not clear whether
the “it” refers to the product or the ingredient.
For these claims, the manufacturer must have generated the evidence for the
claimed activity on the marketed product itself.3
Until very recently, all cosmetic claims related to one or more different aspects
of cosmetic products: their (analytical) content, physical or physicochemical proper-
ties, performance, or the customer’s preference for the claimed product. “Contains
1/4 moisturizing soap,” is an example of a chemical claim, whereas “transparent
sunscreen” is an example of a claim based on the physical properties of a cosmetic
product. The wrinkle-reduction claim given above, for instance, is an example of a
performance claim. “Ninety percent of women prefer our product over any other
shower gel,” is an example of a preference claim.
Traditionally, most attention has gone to the substantiation of performance
claims as these tend to be the technically more difficult, but marketing-wise more
powerful, claims. Four practical claim substantiation principles exist that have been
extensively described:3
1. Start with the claim to select the test in order to design the most optimal test;
2. Know the test substrate so that you know what changes and therefore what you
should measure;
3. Know the measuring principles of bioengineering equipment so that you know
that it can indeed measure what changes in the substrate; and
4. Know the clinical trial design in order to enhance the changes of obtaining a
statistically significant result at lowest costs.
What unites the analytical content, the physical/physicochemical property, and
the product performance claim is the fact that all are measured on hard physical
471
matter, i.e., on a physical product or physiological substrate (such as skin or hair).

The resulting claims referred to as “matter” claims represent the hard physical
matter on which they are based.
With preference testing, however, the claim no longer relates to hard physical
matter, but to an interpretation of a physical experience (i.e., a perception) that
involves our brain. This chapter will therefore refer to this type of claim as a “mind”
claim. Because people have different personal experiences and the context in which
the product is experienced may differ, the resulting perception of the same physi-
cal experience may differ. This personal element raises the question how one can
objectively substantiate mind claims.
A Different Type of Product

Recently, a new type of cosmetic product has appeared on the market. The
qiora skin care range from Shiseido, Yokohama, Japan, is a product range based
on a new concept, that of the connection between body and mind.
Although it is well known that stress adversely affects the condition of the body
(the so-called psychosomatic disorders) and that an individual’s mental condition
has a major impact on recovery from illness, the exact nature of the relationship
between skin and the mind was not established until 1993. Investigators of the
Massachusetts General Hospital/Harvard Cutaneous Biology Research Center,
in collaboration with scientists from Shiseido, showed the contact point between
Langerhans cells in the skin and nerve cells, confirming the mind and body were
indeed connected to one another in skin.4 Langerhans cells, which play a vital role
in the cutaneous immune reaction in the epidermis, frequently contact cutane-
ous nerves that contain calcitonin gene-related peptide (CGRP) as a transmitter
to regulate the antigen-presenting function5 of the Langerhans cells. Moreover,
Langerhans cells were capable of influencing nerves by producing factors that af-
fect neuron differentiation.4 These findings, superbly explained by Ozawa,6 clarify
the existence of a bidirectional regulatory mechanism between the nervous system
and the immune system in skin (see Figure 48.1).
Figure 48.1
472
Putting this knowledge to the practical test, Shiseido scientists were able to
demonstrate that stress delayed the rate of recovery of skin barrier function by ap-
proximately 20%. They were also able to demonstrate that prolonged anxiety and
tension promote the secretion of adrenocorticotropic hormone (ACTH) from the
anterior pituitary gland, which promotes the secretion of cortisol, leading to a reduc-
tion of immunological functions of Langerhans cells and rough skin.
This, in turn, led to the NICE concept—in which our nervous, immune, cuta-
neous, and endocrine system (NICE) all work together to internally activate our
skin physiology via the secretion of homeostasin. Products like this “mind-body”
skin care that contain elements to improve the homeostasin secretion balance will
stimulate the mind-body connection from the outside, augmented by fragrance
that might have favorable effects on the mind.
The efficacy of the described skin care was shown in a one-month clinical study,
in which the skin condition of an arm to which no product was applied was equally
improved as the arm where it was applied. This result suggested that the skin pro-
tection was the result of an improvement of the balance of the whole body rather
than only a local improvement of skin condition. Treatments using the so-called
“fragrance element IP” were able to counteract the effects of stress on skin via an
increase of the skin’s immunological effects.7 An advertisement for such a holistic
treatment product is shown in Figure 48.2.
Figure 48.2.
The Mind Claim

Novel products that make mind claims influence, in one way or another, the
quality of life. Until now, these claims have been more apparent in the East than in
the Western world. As John A. Parrish, M.D., writes, “Western scientists avoid the
topic (the nature of the connection between mind and body) because of the absence
473
of firm quantifiable linear-logic data explaining mind-body connections in terms of

physics and chemistry.”8 These mind claims are also starting to emerge in the West.
An example is given in Figure 49.3.
Figure 48.3.
“Two quick sprays to your tongue release the positive energy you need to find
your inner calm again, restoring your center and focus, even after you’ve reached
the end of your tether.” This claim says more about the impact of the use of this
product on your mind than on any hard physical matter. Such a claim raises the
question of how it is being substantiated, as the four rules described above for
matter claims3 will no longer work, but an accountable and trustworthy company
should still provide the same level of scientific, firm quantifiable linear-logic data,
underpinning this mind-body connection.
Can claims that relate to quality of life be verified in ways other than the secre-
tion of homeostasin alone?
Quality of Life
The concept of Quality of Life (QoL) originates from cancer pain relief studies in
the 1980s. Since that time, it is an important aspect in medical studies, in particular
in oncology and dermatology. QoL is a much broader concept than “health.” The
World Health Organization (WHO) developed a new proposal in May 1999 for
the definition of health and described it as “a dynamic state of complete physical,
474
mental, spiritual, and social well-being, and not merely the absence of disease
or infirmity.” The proposal is still not adopted because of considerable variation
among the United States and Islamic, former communist European, and East Asian
countries in regards to views of health. The words “dynamic” and “spiritual” were
new relative to the old adopted 1946 health definition.9
Roughly at the same time, the WHO also defined QoL to be “an individual’s
perception of their position in life in the context of the culture and value systems in
which they live and in relation to their goals, expectations, standards, and concerns.”
Six different domains can be distinguished in QoL issues: physical, psychological,
social relationship, level of independence, environment, and personal belief/religion/
spirituality. It will be clear that not all of us will favor the same domains of QoL to
the same extent and with the same priority, as exemplified by differences in our
culture and value systems.
An interesting example of this is the fact that the Japanese value items such as
sleep, vitality, and human relationships highly while family relationships and leisure
were ranked lower—in contrast to Western countries where such items were given
more importance.9 As a consequence, the concept of QoL, in contrast to a well-
hydrated skin, is not globally universal and therefore it is also unlikely that QoL or
mind claims will ever be universal.
Having assessed QoL, a next step must be to identify how this notion can be
measured. Questionnaires have been developed to measure this concept, and
with time, they have been simplified so that the currently used version has been
condensed from 15,000 to about 100 questions.10 The above-mentioned regional
differences in the emphasis on different aspects of QoL have been identified via
such questionnaires. More specific questionnaires do exist that identify, for example,
the impact of specific dermatological diseases.11,12
Cosmetic Examples Measuring Quality of Life

QoL can be measured via questionnaires, but skeptics might argue that ques-
tionnaires might be written in such a way that the desired answer can always be
obtained. Cosmetic preparations will not necessarily affect all six domains of QoL
and therefore, more specialized questionnaires will be needed. And with that this
chapter returns to the desire of Western scientists for firm quantifiable linear-logic
data.
One of the most spectacular examples of measuring the perceptions of cosmetic
product application in the human brain is from the work of Bernard Querleux, Ph.D.
L’Oreal Research, Paris, France, using functional Magnetic Resonance Imaging
(fMRI). FMRI is a technique that identifies precise areas in the brain where actions
are controlled, where thoughts take place, and even where emotions are felt—and
to watch the brain activities as they happen.13
In the 1998 IFSCC Best Paper Award winning presentation, Querleux et al.
outlined how the brain was stimulated following the application of a cosmetic prod-
uct on one’s hand and the imagination thereof. Touching one’s hand, or applying a
cosmetic product to one’s hand, resulted in a contralateral activation of the brain
whereas the imagination thereof resulted in an ipsilateral stimulation. Following the
475
use of questionnaires, they observed that people with a strong contralateral stimula-
tion were characterized in cognitive analysis as “rationale” and “reactive,” whereas
those with a strong, ipsilateral stimulation were characterized by the psychological
descriptors “sensitive” and “imaginative” (see Figure 48.4).14
Figure 48.4.
In a subsequent study, Querleux and co-workers subjected volunteers with

and without sensitive skin to cosmetic product stimulation and were able to show
that lactic acid resulted in a main activation of the primary somatosensory cortex
for both groups (contralateral), but that bilateral extensions (i.e., to the ipsilateral
side) only occurred in associative areas for the sensitive group.15
In this way, Querleux and group beautifully demonstrated that self-perception of
sensitive skin—for which the evidence can hardly be demonstrated by the more con-
ventional skin bioengineering techniques such as transepidermal water loss (TEWL),
corneometry and laser-Doppler flowmetry16—matches what happens in the brain (as
measured by fMRI) and that questionnaires were able to predict self-perception and
brain activity. The conclusion is that brain activity following topical application of a
cosmetic product can be measured objectively but that this information can also be
obtained accurately via questionnaires.
The Future for the Substantiation of Mind Claims

The issues facing the future of the industry in order to substantiate mind claims
for cosmetic products can be subdivided into at least three themes: those relating
to technology, to access to measurement capability, and to marketing.
Technology: The examples of the work performed by Shiseido and L’Oréal
demonstrate that objective technology is available to substantiate mind claims of
cosmetic products. But many people will find it difficult to make a translation from
476
these technologies to cosmetic products. Querleux illustrated how fMRI may be

used to measure the influence of an effective product for sensitive skin. If a person
with sensitive skin (therefore with both contralateral and ipsilateral brain activation)
used the product, it should result in significantly less ipsilateral brain activation,
possibly even only contralateral activation—similar to what happens in the brains
of people with non-sensitive skin people. Such type of work is probably already
ongoing in the more innovative cosmetic companies.
Neuroscience Links the Mind and Body

An increasing number of studies have shown that the immune system is
connected to the nervous and endocrine systems—and it appears that their
three-way communication is vital for an adequate defense of the body and
brain. This discovery leads to insight on how emotions can influence illness;
a clearer understanding of how the immune system fights foreign invaders
and how disturbances in the circuit lead to disease; and earlier diagnosis
of diseases. More recently, researchers determined that hormones of the
endocrine system help the immune and nervous systems defend the body;
for example, stress hormones can initiate actions in the brain and immune
system in response to injury or germs to act as an immune system regulator.
Scientists also recently discovered that immune molecules, known as cytok-
ines, can initiate brain actions. The immune molecules can trigger feelings
of sluggishness, sleepiness and loss of appetite. The increasing number of
links that researchers are discovering between the immune, nervous and
endocrine systems is leading them to investigate whether excess stress or
too little stress can abnormally alter the immune defenses.
Source: Society for Neuroscience Web site. Available at: http://apu.sfn.org/content/

Publications/BrainBriefings/mind.body.html. Accessed July 5, 2005.
Access to measurement capability: Whereas for the general public the

skin-mind connection is almost an obvious one—think, for instance, of the expres-
sion that “our skin is a mirror of our soul”—technically it has been very difficult
to demonstrate this connection. The methods used to demonstrate this link are
technologically very advanced but the work of Querleux et al.14,15 has elegantly
demonstrated the relevance of well-designed questionnaires. In fact, specialized
questionnaires are already extensively used in medicinal practice17 and to a minor
extent in more cosmetic applications.18,19 Despite the fact that current QoL ques-
tionnaires have been greatly reduced in size, the cosmetic industry must modify
them even further to make questionnaires relevant for cosmetic claim substantiation
without losing their meaning.
One of the few papers describing cosmetic claim substantiation work of mind
claims is that of Masson et al.,20 whose use a combination of: questionnaires to
identify product preference, effect of product on mood change, and perception of
477
improvement of well-being; bioengineering techniques such as corneometry and

skin temperature; and immunological and hormonal measurements such as salivary
human secretory immunoglobin A and cortisol, an immunosuppressive hormone.
The researchers were able to demonstrate a correlation between bioengineering
and immunological and hormonal measurements, but only for those subjects that
judged their mood to be positively influenced. This result confirms the work of
Querleux et al., suggesting that people who perceive themselves to be different
in one way or another (e.g., sensitive, instead of normal skin; their well-being
positively/negatively influenced by product use) show measurable signs of this dif-
ference in their brain activity. With some imagination, it can therefore be argued
that this work demonstrates that the efficacy of a mind product is all literally “in
the mind of the believer.”
As more evidence emerges and would confirm such results to be indeed cor-
rect, this finding will have an impact on the selection of volunteers for mind claim
studies.
Marketing: Because of the differences around the world in the emphasis in QoL
domains, it is very unlikely that mind claims can be globally universal. Moreover,
if it appears to be the case that mind claims will only be applicable to those that
have an open mind about this type of cosmetic claim, then creating hard evidence
will be at the heart of the matter. Without this evidence, mind claims will become
a matter of conscience!
Conclusion
The industry is about to enter a new era in its continuous development, namely
that of the mind claim. Although good quality science has been performed that
has demonstrated the proof of principle of the skin-mind connection, more clini-
cal work is necessary before general rules for the substantiation of cosmetic mind
claims can be drawn.
Published May 2008 Cosmetics & Toiletries magazine
The author expresses his sincere thanks to Dr. Tatsuya Ozawa of Shiseido, Yokohama, Japan, and Dr.
Bernard Querleux, L’Oréal Research, Paris, France, for interesting, useful, and mind-blowing discussions
on this matter—and their permission to use some of their data to substantiate my claims. Both scientists
have great minds that will impact future cosmetic claims.
References
1. K Greive, Cosmetics and life sciences: A continuing courtship, IFSCC 5 4 303–305
(2002)
2. COLIPA, Guidelines for the evaluation of the efficacy of cosmetic products, 2nd edition,
4
3. JW Wiechers and VAL Wortel, Creating effective claim support packages, Cosmet Toil,
114 7 51–57 (1999)
4. J Hosoi, GF Murphy, CL Egan, EA Lerner, S Grabbe, A Asahina and RD Granstein,
Regulation of Langerhans function by nerves containing calcitonin gene-related
peptide, Nature 363 159–163 (1993)
478
5. H Torii, Z Yan, J Hosoi and RD Granstein, Expression of neurotrophic factors and

neuropeptides receptors by Langerhans cells and the Langerhans cell-like cell line
XS52: Further support for a functional relationship between Langerhans cells and
epidermal nerves, J Invest Dermatol 109 588–591 (1997)
6. T Ozawa, “Prologue for the 21st century.” In: H Tagami, JA Parrish and T Ozawa (eds.),
Skin: Interface of a Living System. Perspective for skin care system in the future,
Elsevier, Amsterdam, The Netherlands, 177–190 (1998)
7. Customer Satisfaction Research Center, Shiseido Co., Ltd., Latest R&D from Shiseido
Corporate Communications Division, Public Relations Department, Shiseido Co., Ltd.,
Tokyo, Japan (January 2002)
8. JA Parrish, “Introduction.” In: H Tagami, JA Parrish and T Ozawa, (eds.), Skin:
Interface of a Living System. Perspective for skin care system in the future,. Elsevier,
Amsterdam, The Netherlands, vii (1998)
9. K Tsutani, “What cosmetics can contribute to health including Quality of Life (QoL),
individual satisfaction, subjective feelings and preference in their evaluation.” In: K
Takeda, S Harada and M and Ando, (eds.), Functional Cosmetology—Substantiation
of Cosmetics Efficacy: Recent Progress and Future Promise, Yakuji Nippo, Ltd.,
Tokyo, Japan, 28–36 (2003)
10. M Tazaki and Y Nakane, WHO QOL Brief version—User’s Manual and Interpretation
Guide, Kanekoshobo (1997)
11. S Chamlin, D Cella, M Williams, I Frieden and M Chren, Validity of the childhood
atopic dermatitis impact scale (CADIS): A quality of life measure for young children
with atopic dermatitis and their families, Society for Investigative Dermatology, 66th
Annual Meeting, St. Louis, MO USA (May 4–7, 2005), poster 304, J Invest Dermatol,
124 A51 (2005)
12. H Alexander, NN Shah, GB Poindexter, YM Monthrope, S Bendeck, RA Swerlick and
SC Chen, Responsiveness of ItchyQoL: A pruritis-specific quality of life instrument,
Society for Investigative Dermatology, 66th Annual Meeting, St. Louis, MO USA (May
4–7, 2005); poster 318, J Invest Dermatol, 124 A53 (2005)
13. R Winston, Human Instinct, Bantam Books, London, UK, 47 (2002)
14. B Querleux, G Gazano, O Mohen-Domenech, J Jacquin, Y Burnod, P Gaudion, O
Jolivet, J Bittoun and H Benali, Brain activation in response to a tactile stimulation:
Functional magnetic resonance imaging (fMRI) versus cognitive analysis, Int J Cosmet
Sci, 21 107–118 (1999)
15. B Querleux B, R Jourdain, K Dauchot, Y Burnod, J Bittoun, P Bastien and O de
Lacharrière, Sensitive skin: Specific brain activation revealed by functional MRI, 20th
World Congress of Dermatology, Paris, France, Book of Abstracts, 1S42, (July 1–5,
2002)
16. F Distante, L Rigano, R. D’Agostino, A Bonfigli and E Berardesca, Intra- and inter-
individual differences in sensitive skin, Cosmet Toil, 117 7 39–46 (2002)
17. J Unaeze and RS Stern, Impact of psoriasis on the psychological aspects of quality
of life decreases over time but physical and sociologic impact is stable: A 10-year
prospective study, Society for Investigative Dermatology, 66th Annual Meeting, St.
Louis, MO USA May 4-7, 2005; poster 273, J Invest Dermatol, 124 A46 (2005)
18. WH Boehncke, F Ochsendorf, I Paeslack, R Kaufmann and TM Zollner, Decorative
cosmetics improve the quality of life in patients with disfiguring skin diseases, Eur J
Dermatol, 12 577–580 (2002)
19. C de Belilovsky, B Chadoutaud, JC Choulot and P Msika, Cosmetics and quality of
life, Society for Investigative Dermatology, 66th Annual Meeting, St. Louis, MO USA,
poster 912 (May 4–7, 2005)
20. P Masson, F Merot, MJ Albin, C Simonet, S Flauto and P Pommez,
Psychoneuroimmunological effects of a cosmetic product: Benefits of a multifactorial
approach, IFSCC Conference 2005, Florence, Italy (September 2005)
Chapter 49
The Regulatory Interface:

When is it a Cosmetic and
When a Drug?
Defines a cosmetic and a drug, while explaining the
importance of compliance.
key words: FDA, cosmetic, drug, CFSAN
B oth the cosmetic industry and the Food and Drug Administration (FDA) have
had a long and interesting history. FDA’s history began in 1906 with the enact-
ment of the Pure Food and Drug Act. This act was the first attempt to regulate the
safety of products (or additives). For almost 100 years Congress has set the stan-
dards and published them in the United States Code (USC). The FDA and other
federal agencies promulgate regulations through notice and comment rulemaking.
Proposed regulations are published in the Federal Register (FR) and the public is
given an opportunity to comment. The agencies then publish in the Federal Register
final regulations together with a preamble discussing each comment. Industry and
regulatory scientists eagerly follow these changes and access them on the Web. Final
regulations are compiled in the Code of Federal Regulations (CFR).
The role of cosmetics is best described in a 1986 speech by former FDA
Commissioner Frank Young, M.D., Ph.D., to the Scientific Conference of the
Cosmetic, Toiletry and Fragrance Association (CTFA): “Although our first aim in
consumer protection has always been product safety, the law also requires us to
protect consumers from misbranded products. We don’t want to over-regulate; we
just want (cosmetic) labels that are free of false and misleading claims (and that)
make cosmetic claims, not drug claims. If a label claims to prevent or treat disease
or otherwise affect the structure or function of the human body, it is deemed to be
a new drug, and the marketer carries the burden of proving it is safe and effective
before it can be legally marketed.”
Cosmetic and Drug Defined

Cosmetic: The Food, Drug and Cosmetics Act (FD&C Act) of 1938 defines
cosmetics as “articles intended to be applied to the human body for cleansing,
beautifying, promoting attractiveness, or altering the appearance without affect-
ing the body’s structural function.” A cosmetic is a preparation, such as powder or
479
480
The Regulatory Interface: When a Cosmetic and When a Drug? Beginning Cosmetic Chemistry
a skin cream, designed to beautify the body by direct application. Although most
people recognize hair, skin and nail products as cosmetics, they are surprised to
find other products, such as vaginal lubricants, fitting the description of a cosmetic.
The definition of a product that is applied to the human body is broad. Even some
generally recognized as safe (GRAS) oils advertised to enhance sex fit into this
definition of cosmetic. Therefore, the term cosmetics refers not only to women’s
makeup but to any skin-care creams, lotions, powders, sprays, perfumes, fingernail
polishes, permanent waves, hair colors, deodorants, baby products, bath oils, bubble
baths, or mouthwashes.
Drug: The FDA clearly distinguishes a cosmetic from a drug. The FD&C Act
defines drugs by their intended use, as “(A) articles intended for use in the diag-
nosis, cure, mitigation, treatment, or prevention of disease and (B) articles (other
than food) intended to affect the structure or any function of the body of man or
other animals.”1
The interface: The interface between cosmetics and drugs can be confusing
for industry. Occasionally, a product is developed both as a cosmetic and a drug. In
fact, small companies may have to decide whether they are developing a cosmetic
with no claims or whether they need to make claims and, therefore, develop a
“drug.” Clearly, there are times when it is advantageous commercially to develop
scientific claims and indications for a compound that could otherwise be marketed
as a cosmetic. In some cases safety concerns may help make this decision.
The Importance of the Label

The Center for Food Safety and Applied Nutrition (CFSAN) provides a glimpse
into a world where products have minimal regulatory oversight. By law FDA does
not have the authority to approve cosmetic products or ingredients, except for color
additives. Regulations do prohibit or restrict the use of several ingredients because
of safety concerns and require that the product carry the following warning on the
label: Warning—The safety of this product has not been determined. With
the exception of colors and certain prohibited ingredients, a cosmetic manufacturer
may use essentially any raw material in a product and market it without prior FDA
approval. (However, as discussed in the sidebar on wrinkle removers, the FDA may
be considering a regulatory change that would require pre-market review of certain
cosmetic products. See the Cosmetic Product Warning Statements sidebar.)
Congress intends to safeguard the health and economic interests of consum-
ers but it also means to protect a manufacturer’s right to market a product free
of excessive government regulation. Registration and reporting of cosmetics are
essentially voluntary. Although cosmetic claims, even those considered puffery, are
allowed without scientific substantiation. However, if a cosmetic makes a medical
claim, such as removing dandruff, the product is regulated as an over-the-counter
drug for which scientific studies demonstrating safety and effectiveness must be
submitted to FDA.
The labeling of ingredients is an important part of the process. Federal regula-
tions require cosmetic ingredients to be listed on product labels in descending order
by quantity, but often the list is not user-friendly. Because cosmetic ingredients are
481
often complex chemical substances, the list may be incomprehensible to the prod-
uct’s average user.2 However, if all manufacturers use the same name, consumers
can compare different products and make reasonable value judgments.
Cosmetic Product Warning Statements

Here is the language of 21 CFR, Chapter I, Section 740.10 regarding the
labeling of cosmetic products for which adequate substantiation of safety
has not been obtained.
(a) Each ingredient used in a cosmetic product and each finished cosmetic
product shall be adequately substantiated for safety prior to marketing. Any
such ingredient or product whose safety is not adequately substantiated prior
to marketing is misbranded unless it contains the following conspicuous
statement on the principal display panel:
Warning—The safety of this product has not been determined.
(b) An ingredient or product having a history of use in or as a cosmetic may

at any time have its safety brought into question by new information that in
itself is not conclusive. The warning required by paragraph (a) of this section
is not required for such an ingredient or product if:
(1) The safety of the ingredient or product had been adequately sub-
stantiated prior to development of the new information.
(2) The new information does not demonstrate a hazard to human
health.
(3) Adequate studies are being conducted to determine expeditiously
the safety of the ingredient or product.
(c) Paragraph (b) of this section does not constitute an exemption to the
adulteration provisions of the Act or to any other requirement in the Act
or this chapter.
The law requires that color additives used in food, drugs and cosmetics must
be tested for safety and approved by the FDA for their intended uses. A cosmetic
containing an unlisted color additive (i.e., a color additive that has not been ap-
proved by the FDA for its intended use) is considered adulterated and subject to
regulatory action. The color additives approved for use in cosmetics are listed at
21 CFR 73, 74 and 82.
Occasionally the FDA will raise concerns and provide guidance documents.
These guidance documents address special labeling considerations for industry,
and they are often intended to help consumers. One such example resulted from a
June 2000 citizen petition from the CTFA requesting that FDA issue a regulation
under 21 USC 362(a) establishing labeling requirements related to sun protection
482
with use of cosmetic products containing AHAs. This example is but one of FDA
guidance that benefits the consumer.
For all of FDA, the label is the most important regulatory issue. It is the label of
a cosmetic or drug that can render a product misbranded. If the safety of a cosmetic
is not adequately substantiated, the product may be considered misbranded and
may be subject to regulatory action unless the label bears the following statement:
Warning—The safety of this product has not been determined.3 (See the
Warning—The Safety of this product has not been determined sidebar on
warning statements.)
Compliance and Substantiation

Compliance and substantiation are important regulatory requirements that
protect both the customer and the manufacturer. Compliance can be identified as
a company meeting any and all regulatory guidelines and requirements. Substan-
tiation means that credible evidence exists that any medical or therapeutic claim
can be verified.
The safety of all ingredients used in a product should be substantiated prior
to marketing. If ingredients are not adequately tested prior to marketing, the
product is considered as misbranded unless the principal label clearly displays the
statement: Warning—The safety of this product has not been determined.4
Substantiation of claims and pre-marketing testing must accurately assess efficacy
and safety issues with important implications for total body health.
Although the FD&C Act does not require that cosmetic manufacturers or mar-
keters test their products for safety, the FDA strongly urges cosmetic manufacturers
to conduct whatever toxicological or other tests are appropriate to substantiate the
safety of their cosmetics. Consumers must be protected from false advertising. Unfair
and excessive claims lead the consumer to disbelieve all cosmetics claims.
With harmonization, issues of compliance and substantiation will become
even more important, especially for companies with products in many countries.
Compliance issues are international. Japanese and Canadian guidelines on safety
substantiation are a priority at this time. Canadian guidelines are modeled after
those used by the EU.5
From Cosmetic to Drug

The regulatory pathway for new drug development is more extensive and
stringent. Both safety and efficacy must be established in well-designed clinical
trials. Drugs must be manufactured in accordance with current good manufactur-
ing practice regulations as codified at 21 CFR 210 and 211. The FD&C Act also
requires that drug manufacturers register every year and update lists of all manu-
factured drugs twice annually.6
Two important laws applicable to drugs, but not to cosmetics, are the Drug
Price Competition and Patent Term Restoration Act of 1984 (Hatch-Waxman
Amendments to the Federal Food, Drug and Cosmetic Act) and the Prescription
Drug Marketing Act of 1987 (PDMA).
483
Table 49.1. Useful Web sites for regulation of cosmetics and drugs
Web site Contents

www.fda.gov FDA Home Page
www.access.gpo.gov/nara/cfr/ Code of Federal Regulations
www.cfsan.fda.gov/~dms/cos-218.html What is a cosmetic?
http://vm.cfsan.fda.gov/~dms/cos-ch00.html Cosmetics Harmonization and
International Cooperation –
May 2000
www.fda.gov/cber/guidelines.htm or Guidance for Industry – CDER –
www.fda.gov/cder/guidance/index.htm Good guidance practices
(Feb 1997)
www.cfsan.fda.gov/~dms/ahaguide.html Guidance for industry on
labeling for topically applied
cosmetic products containing
alpha hydroxy acids as
ingredients
www.fda.gov/fdac/special/newdrug/ndd_toc.html FDA consumer: From test tube
to patient (1995) (A more recent
edition available by mail)
www.fda.gov/cder/ob/default.htm The Orange Book – Approved
drug products with therapeutic
equivalence evaluations
www.fda.gov/ola/2003/generic0617.html Statement of Daniel E. Troy,
Chief Counsel U.S. Food And
Drug Administration before the
Committee on the Judiciary,
United States Senate (Jun 17,
2003)
www.fda.gov/oc/pdma/report2001/default.htm PDMA report to Congress, a
full review (Jun 2001)
www.fda.gov/cber/pdma.htm Prescription Drug Marketing Act
www.hc-sc.gc.ca/cosmetics Canada, Cosmetics
www.hc-sc.gc.ca/hpb-dgps/therapeut/htmleng/ Canada, Drugs
http://pharmacos.eudra.org/ European Union, cosmetic
regulations
www.pharmasys.gr.jp Japan, cosmetic regulations
http://vm.cfsan.fda.gov/~dms/cos-toc.html United States, cosmetic
regulations
Hatch-Waxman: Hatch-Waxman provides innovator drug products protection

against the approval of generic applications until their patent terms have expired.
It provides for up to five years of patent term restoration to compensate sponsors
of innovator products for part of the time lost in clinical trials and in the FDA
484
approval process. It also provides up to five years of marketing exclusivity for the
first approval of a new chemical entity regardless of patent status and up to three
years of exclusivity for the first approval of a new dosage form or new use.
Once the innovator’s patent terms and exclusivity have expired, Hatch-Waxman
allows FDA to approve abbreviated new drug applications (ANDAs) for generic
versions without the requirement of reproving the safety and efficacy of the active
ingredient. ANDA applicants simply show that their generic versions get the ac-
tive ingredients into the blood stream at the same rate and to the same extent as
the innovator version.
Hatch-Waxman requires sponsors of innovator drug products to submit, as
part of a New Drug Application (NDA) or supplement, information on any patent
that 1) claims the pending or approved drug or a method of using the approved
drug, and 2) for which a claim of patent infringement could reasonably be asserted
against an unauthorized party. Patents that may be submitted are drug substance
(active ingredient) patents, drug product (formulation and composition) patents,
and method of use patents. Process (or manufacturing) patents may not be submit-
ted to FDA. FDA publishes patent information on approved drug products in the
Orange Book, available electronically on the FDA web site. A generic manufacturer
that successfully challenges the validity of a listed patent and then wins approval
for an ANDA receives 180 days of marketing exclusivity against other generic
manufacturers. Hatch-Waxman also provides for a 30 month stay on generic drug
approvals while certain patent challenges are litigated.
Both Hatch-Waxman and subsequent amendments are intended to balance
two important public policy goals: meaningful market protection incentives to
encourage the development of valuable new drugs and early public access to
generic products once patent protection and marketing exclusivity have expired.
Under Hatch-Waxman, more than 10,000 generic drugs have entered the market
since 1984.7
Prescription Drug Marketing Act: The Prescription Drug Marketing Act
(PDMA) was enacted to ensure that prescription drug products would be safe and
effective by avoiding unacceptable risks that counterfeit, adulterated, misbranded,
subpotent or expired drugs can enter the marketplace. PDMA requires state li-
censing of wholesale distributors, requires wholesale distributors not authorized
by the manufacturer to provide purchasers a statement identifying each prior sale
and prohibits sale of drug samples. See the PDMA Report to Congress for a full
review.8
Transition from cosmetic to drug: Some cosmetics have successfully made
the scientific transition from cosmetic to prescription or over-the-counter drug
products. Earlier I noted that some cosmetic manufacturers might benefit by de-
veloping the product as a drug with an intended use. In some cases a product may
have two intended uses—one as a cosmetic and the other as a drug. For example,
a shampoo can be a cosmetic because the intended use is to cleanse the hair. This
same shampoo can be a drug because it is intended—based on scientific data—to
treat dandruff.
485
A question industry often asks is how far can I go with a claim? The answer is
in the reading of the definition of a cosmetic versus a drug. The line is set some-
where between “articles intended to be applied to the human body for cleansing,
beautifying, promoting attractiveness, or altering the appearance without affecting
the body’s structure or function” and “articles used for diagnosis, cure, mitigation,
treatment or prevention of disease or articles intended to affect the structure or
any function of the body of man or other animals.” The claim for the shampoo
above was to cleanse the hair as a cosmetic and treat dandruff as a drug. The sex
cosmetics mentioned earlier must stay within this paradigm.
Summary
Aging consumers cherish each new product that reverses the ravages of life.
These consumers are looking for the magic genie in a bottle. If that bottle is to
be marketed as a cosmetic, it cannot promise more than to cleanse, beautify or
promote attractiveness.
Published April 2006 Cosmetics & Toiletries magazine.
References
1. FD&C Act, Sec 201(g)(1)
2. Cosmetic safety: More complex than at first blush, FDA Consumer (Nov 1991)
3. 21 CFR 740.10
4. 40 FR 8917 (Mar 3, 1975)
5. http://vm.cfsan.fda.gov/~dms/cos-ch00.html
6. 21 CFR 207
7. DE Troy, Statement of Chief Counsel US Food and Drug Administration before The
Committee on the Judiciary United States Senate (Jun 17, 2003) http://www/fda.gov/
ola/2003/generic0617.html
8. PDMA Report to Congress June 2001, http://www.fda.gov/oc/pdma/report2001/
default.htm
9. CTFA to seek clarity on wrinkle product regulatory status, BSE rule, The Rose Sheet 7
(Feb 16, 2004)
Chapter 50
Correlating Porosity
and Tensile Strength of
Chemically Modified Hair
This study validates the porosity method against the widely
accepted method of tensile strength for determining the hair
damage imparted to hair due to cosmetic treatments.
key words: hair porosity, hair tensile strength, hair damage,

permanent hair colors, avid permanent waves, hair relaxers,
hair bleaches
O ver the years, many individual studies have been conducted regarding the
extent of damage imparted to hair. These studies deal with the damaging
effects of various chemical processes such as permanent waves, permanent colors
and hair bleaches.1–8
The most commonly employed method to quantify this damage is the measure-
ment of change in tensile properties of the hair. This method takes two to three days
in the preparation of samples of hair fibers. It also requires a minimum of 30–40
fibers for statistical analysis. Therefore, there is a need for other simpler methods
that are equally valid and less time-consuming.
One such method could be the determination of hair porosity or water uptake of
hair fibers as described by Valko et al.9 and by Menkart et al.1 However, to the best
of our knowledge, no study so far has correlated the tensile strength method with
the water uptake (swelling/porosity) method following chemical treatments such as
permanent waves, permanent colors, hair bleach, and permanent hair relaxers.
Therefore, we have conducted a study whose purpose was to validate the po-
rosity method against the tensile strength method. Another purpose of this study
was to use these two methods to compare the magnitude of hair damage between
permanent waving, permanent coloring, hair bleaching, and permanent straighten-
ing processes. Finally, this study ranked the various chemical processes in terms of
their hair damage potential. We believe this is the first comparative damage ranking
for various chemical processes in the hair care field.
Swelling or Porosity of Hair

Professionals who are involved in the art of styling hair define the porosity of
hair as the capacity of hair to absorb liquids. Hair that absorbs a larger quantity
487
488
Correlating Porosity and Tensile Strength Beginning Cosmetic Chemistry
of liquid is said to be more porous than hair that absorbs less liquid. Hair stylists
associate higher porosity of hair with higher degree of damage.10
Water is able to penetrate into hair after a sufficient contact time. As explained by
Feughelman, the absorption of water takes place initially onto the hydrophilic sites
of the globular protein matrix and on the surface of the microfibrils. After the initial
absorption, more sorption of water builds up on water molecules already attached to
the protein structure.11 According to Chamberlain and Speakman, the total uptake
of water is 31.18% at 100% humidity.12 The uptake of water or swelling of hair can
be measured by two methods: the volume method or the weight method.
Volume method: Shansky, in 1963, was the first person to measure the change
in the diameter of the individual hair fibers using a microscope.13 In 1990, Nothen
et al. devised a more accurate instrument utilizing an optical unit for sensing the
diameter of a single fiber, and an online analyzer for displaying the data in real
time.14 In 1998, Syed et al. measured real time swelling of individual fibers using a
laser micrometer that measured the major and minor axis of the fiber simultane-
ously during the immersion of the fiber in an appropriate solution.15
In each of these volume methods, the selection of the fibers takes a long time
and then swelling of each fiber has to be measured over a 20–30 minute period.
Also many individual fibers have to be used in order to get statistically significant
results. Additionally, this method may not be appropriate for measuring the change
in diameter of African-descent fibers where the inherent variation in diameter is
significant within a single fiber along the hair shaft.16
Weight method: The weight method is much less tedious and has the ability
to study the swelling or water uptake of hair fibers using a centrifuge. With this
method, a single operator can conduct more than 50 measurements a day.17 The
weight method is also known as the liquid retention or porosity test. Valko and Bar-
nett have defined porosity as the capacity of hair fibers to absorb water.9 Chemically
damaged fibers are considered hydrophilic or porous and therefore would more
readily pick up moisture and retain water than the untreated or unmodified hair.
Valko and Barnett believed that the greater the porosity of hair, the greater was the
damage to the hair fiber. They found the uptake of water for unmodified or normal
hair to be 31.10%. Therefore, the porosity technique may become a primary method
for determining hair damage due to cosmetic treatments if it correlates with most
widely accepted methods for measuring hair damage. One of those methods is the
measurement of tensile strength.
Tensile Strength of Hair

The tensile properties of hair fibers play an important role in determining the
efficacy of hair treatments such as permanent waves, permanent hair colors, bleaches
and permanent hair straighteners. The influence of various hair treatments on the
tensile properties of hair can be measured using tensile meters such as Instrona
and Dia-Stronb.18
One commonly used method to determine if hair fibers have been altered by
treatment with cosmetic products is to extend the fibers to 20% of their length
before and after treatment and determine the so-called F20 Index. A single fiber
489
is stretched to 20% strain or elongation at a specified constant rate (elongation per

minute). The area under the curve (Energy) required to stretch the fiber to 20%
strain is used to assess the condition of the fiber. The index values (After/Before
Treatment) are calculated and used to assess the extent of hair damage. An Index
of less than 1.0 indicates damage to the hair fiber produced by the chemical hair
product. This method was first developed by Speakman in 1947 in order to study
the effects of physical and chemical processes on keratin properties. Speakman used
a percentage to express the changes in the stress for a fixed strain of fibers.18
Sookne and Harris coined the term 30% index as the ratio of extension values.19
This test is similar to the F20 test except that the single fiber is stretched to 30%
strain or elongation.
Over the last 50 years, it has become a standard practice to ascertain the F20
Index of the fibers before and after the given treatment in order to determine the
positive or negative effect of the treatment on the fibers. In 1966, Menkart et al.
compared the F20 Index of hair and wool and found hair to have slightly higher
F20 Index than wool.1
In addition, many published studies have examined the changes in the tensile
strength of cosmetically modified hair in the area of permanent hair colors, per-
manent hair waves, and hair bleaches.2-8 The field of permanent hair relaxers is
not well researched, although Syed et al. have compared the tensile strength of
Caucasian hair against African-American hair using the methods of Speakman18
and Menkart et al.1
Therefore, in order to verify the reliability of the porosity/weight method, we
designed a study to correlate the porosity of hair fibers at 100% humidity with the
tensile strength of hair fibers at 100% humidity. We hypothesized that a negative
correlation would exist between porosity and tensile strength. Additionally, we
asserted that if the coefficient of determination (r2) is at 0.95 or higher, then the
porosity/weight method would be considered correlated and thereby established
as a reliable method for future use in the laboratory.
This method will enable the hair researcher to obtain results that are both faster
and reliable. This method will also allow the hair chemist to compare the degree
of damage imparted during various cosmetic treatments.
Experimental
Treating the hair: For the porosity testing, all hair used was Caucasian hair 8
inches long, assembled into six tresses of equal weight. The tresses were accurately
weighed on an analytical balance at 4.0 g ±0.1 mg.
For testing the tensile strength of the hair, dark brown European-descent fibers
(Level 2) of 80–90 microns were obtainedc and separated into six different groups.
Of the six weighed tresses, one was left untreated as a control, and each of the
other tresses was subjected to one of the following cosmetic treatments: permanent
hair color, acid wave, permanent hair relaxer (sodium hydroxide), permanent hair
relaxer (guanidine hydroxide) and hair bleach. Details of these treatments are
presented in Table 50.1. The method of treatment employed in each case was
the same as practiced in the market place.
490
Table 50.1. Hair treatments by commercial cosmetic products prior to

determination of porosity and tensile strength of treated hair fibers
Treatment
Treatment contact
Hair Treatment quantity time
Treatment mixture applied with hair Rinsea Shampoo Rinseb
Hair color 28 g Logice AN 45 min ANc 3 min
Permanent Color TRP NCS
Blond-12G
38 g Logic Color
Developer
(30 vol H2O2)
Acid wave 77 g Syntonicsf AN 20 min 2.5 min 5 min 2.5 min

Multiplex Acid TRP CNS
Wave Lotion
18.5 g Syntonics
Waving activator
Relaxer SHj Affirmg No-Base 12 g 18 min 3 min 2 min 1 min

Relaxer 2x NCNS
Relaxer GHk 139 g Affirm 12 g 18 min 3 min 2 min 1 min

No-Lye No-Base 2x NCNS
Relaxerh
37 g Affirm Liquid
Activator
Hair bleachl 7.5 g Logic ANd 45 min 3 min 1 min 1 min

Powder Bleach TRPH NCS
9.0 g Logic Color
Generator (30 vol)
a
Rinsed with warm running tap water
b
Rinsed with running tap water
c
Rinsed until all excessive Color was gone
d
Applied by brush to cover entire tress
e
Logic products are manufactured by Matrix, a part of L’Oréal, France.
f
Syntonics is a trademark of Syntonics International, Summit, Illinois USA.
g
Affirm is a trademark of Avlon Industries Inc, Bedford Park, Illinois USA.
h
Affirm Sensitive Scalp No-Lye No-Base Relaxer Normal Strength
j
Permanent hair relaxer containing sodium hydroxide
k
Permanent hair relaxer containing guanidine hydroxide
l
Permanent hair bleach
AN = as needed
NCS = non-conditioning shampoo
CNS = conditioning neutralizing shampoo
NCNS = non-conditioning neutralizing shampoo
TRP = tress wrapped in plastic
TRPH = tress wrapped in plastic and placed under overhead dryer at 55°C
491
The six sized groups were processed in the same way as the weighed tresses,
again according to the details presented in Table 50.1.
Determining hair porosity: The porosity of the hair was determined utilizing
the centrifuge method of Valko and Barnett.9 Each of the six tresses was divided
into eight samples weighing 0.5 gram each. All samples were equilibrated at 65%
relative humidity and 21°C for 2 weeks prior to using.
To begin the porosity measurements, each sample was weighed at 65% R.H.
using a microbalanced. The samples were immersed in 100 ml of deionized water
for 30 minutes, removed with stainless steel forceps, and placed into polystyrene
centrifuge tubes (28 ml) containing a mesh at the bottom of the tubes to keep the
hair separate from the drained water. The tubes were capped and centrifugede at
7,000 rpm for 10 minutes. After centrifuging, the samples were removed and weighed
again on the microbalance. This method produced repeatable results for each of
the treatments. The porosity of hair was calculated as shown in Figure 50.1.
Figure 50.1. Calculation of porosity
Determining fiber tensile strength: The untreated fibers and fibers of chemi-
cally treated tresses were crimped at 30 mm length from the root tip and then
immersed in deionized water at 21°C for 30 minutes. Then the amount of work
required to extend the wet fibers by 20% of their original length was determined
on the automated tensile testerf (Phase 1 = 20%; Maximum Force = 200 gmf;
Number of cycles = 1; Gauge = 1).
Results and Discussion

It is apparent from Table 50.2 that untreated hair has the lowest amount of
water uptake (31.15±0.63%, N=6) that is very close to the value of 31.18% found by
Chamberlain and Speakman.12 Our value of 31.15% is also very close to the value of
31.10±1.00% found by Valko and Barnett.9 Therefore, our method of determining
water uptake is in agreement with both of those studies.
The cosmetic treatments such as permanent hair color, acid wave, permanent
hair relaxers and hair bleach impart increasingly higher water in that order, as
shown in Table 50.2. It is clear that permanent hair relaxing and hair bleaching
are more damaging than processes such as permanent hair colors and acid per-
manent waves.
492
Table 50.2. Porosity of treated hair
Average porosity
Treatment type* (%)
Untreated 31.15 ±0.63 N=6
Hair color with 30 vol developer 32.01 ±0.12 N=8
Acid wave 35.32 ±0.29 N=8
Hair relaxer (NaOH) 36.15 ±1.26 N=8
Hair relaxer (guanidine) 38.00 ±1.17 N=7
Hair bleach with 30 vol developer 54.57 ±2.48 N=5
N = Number of samples
*See Table 50.1 for specific products tested.
As shown in Table 50.3, untreated hair had the highest average tensile strength
(1.210±0.180 mJ, N=60). On the other hand, cosmetic treatments such as permanent
hair color, acid wave, permanent hair relaxers and hair bleach produced increas-
ingly greater reductions in tensile strength (to a low of 0.480±0.080 mJ, N=51). The
order of damage in terms of tensile strength for each of the cosmetic treatments is
shown in Table 50.3 and it is similar to the order of water uptake for each of the
cosmetic treatments in Table 50.2.
Table 50.3. Tensile strength of treated hair
Average tensile
Treatment type* strength (mJ)
Untreated 1.210 ±0.18 N=60
Hair color with 30 vol developer 1.138 ±0.20 N=41
Acid wave 0.991 ±0.12 N=55
Hair relaxer (NaOH) 0.776 ±0.11 N=53
Hair relaxer (guanidine) 0.698 ±0.11 N=57
Hair bleach with 30 vol developer 0.480 ±0.08 N=51
N= Number of samples
* See Table 50.1 for specific products tested.
Using a statistical packageg, we correlated the porosity data from Table 50.2
and tensile strength data from Table 50.3. The coefficient of determination (r2)
was found to be 0.9607 (Figure 50.2), which is statistically significant. Therefore,
the water uptake method or porosity method and the tensile strength method are
highly correlated.
493
Figure 50.2. Correlation between porosity and tensile strength of hair treated by
selected cosmetic products (see Table 50.1 for details on the products tested)
As shown in Tables 50.2 and 50.3, the order of damage caused by the cos-
metic treatments is as follows: Untreated hair < Permanent Hair Color (Golden
Blonde-Level 12) < Permanent Wave (Acid Wave) < Hair Relaxer containing sodium
hydroxide < Hair Relaxer containing guanidine hydroxide < Hair Bleach.
Conclusion
It is clear from this study that Valko and Barnett’s weight method (water uptake)
or porosity of hair is significantly correlated (r2 = 0.9607) to tensile strength of hair
when hair fibers are chemically treated with various cosmetic treatments.
This study also compares the damage imparted to hair fibers from various
chemical cosmetic treatments such as permanent hair colors, acid permanent
waves, hair relaxers and hair bleaches. The order of magnitude of hair damage is
also determined and it is found that permanent hair colors are least damaging fol-
lowed by acid permanent waves and hair relaxers, whereas the bleaching of hair is
the most damaging cosmetic treatment.
The weight method or porosity of hair is a less tedious and less time-consuming
method for cosmetic chemists. It can be used instead of the tensile strength method
to determine the degree of damage.
The porosity method would seem to be especially convenient to use on exces-
sively curly hair in which the Young’s modulus varies significantly within a single hair
fiber due to its ever-changing diameter along the hair shaft. The Young’s modulus
is equal to the stress/strain, where strain is the deformation expressed in length,
while stress is equal to the force divided by the cross-sectional area of the fiber.
The modulus is usually obtained in the Hookean region (less than 2% strain) where
the fiber can be stretched repeatedly without undergoing permanent deformation
or damage from extesion.
494
This study needs to be expanded to many different hair shades in permanent

hair colors; this study was limited to only one hair color and only a 30 volume de-
veloper. Similarly, this study needs to be expanded to various types of permanent
waves, such as alkaline permanent waves.
Published November 2002 Cosmetics & Toiletries magazine
References
1. J Menkart, LJ Wolfram and I Mao, Caucasian hair, Negro hair, and wool: Similarities
and differences, J Soc Cosmet Chem 17 769–787 (1966)
2. CE Reese and H Eyring, Mechnical properties and the structure of hair, Textile Res J
20 743–750 (1950)
3. YK Kamath, SB Hornby and HD Weigman, Mechanical and fractographic behavior of
Negroid hair, J Soc Cosmet Chem 35 21–43 (1984)
4. R Wickett, Kinetic studies of hair reduction using a single fiber technique, J Soc
Cosmet Chem 34 301–316 (1983)
5. EG Bendit, There is no Hookean region in the stress-strain curve of keratin,
J Macromol Sci-Phys B17(1) 129–140 (1980)
6. W Edman and M Marti, Properties of peroxide-bleached hair, J Soc Cosmet Chem 12
133 (1961)
7. L Wolfram, The reactivity of human hair: A review, in Hair Research, Springer-Verlag,
New York 497(1981)
8. TA Evans, TN Ventura and AB Wayne, The kinetics of hair reduction, J Soc Cosmet
Chem 45 279–298 (1994)
9. EI Valko and G Barnett, A study of the swelling of hair in mixed aqueous solvents,
J Soc Cosmet Chem 3 108-117 (1952)
10. Milady’s Standard Text Book of Cosmetology, Thomson Learning, Albany, New York
233 (2000)
11. M Feughelman, Physical properties of hair, in Hair and Hair Care, DH Johnson, ed,
Marcel Dekker, New York 17 (1997)
12. NH Chamberlain and JB Speakman, Z Electrochemie 37 374 (1931)
13. A Shansky, The osmotic behavior of hair during the permanent waving process as
explained by swelling measurements, J Soc Cosmet Chem 14 427–432 (1963)
14. J Nothen, V Bollert, G Blankenburg and H Hocker, The influence of the cosmetic
swelling behavior on the quality of the permanent wave, Proceedings of the 16th
IFSCC Conference, New York, October 8-11, 1990, vol 1 315–324 (1990)
15. A Syed, H Ayoub and A Kuhajda, Recent advances in treating excessively curly hair,
Cosmet Toil 113(9) 47–55 (1998)
16. A Syed, A Kuhajda, H Ayoub and K Ahmad, African-American Hair: Its physical
properties and differences relative to Caucasian hair, Cosmet Toil 110(10) 39–47 (1995)
17. DH Powers and G Barnett, A study of swelling of hair in thioglycolate solutions and its
reswelling, J Soc Cosmet Chem 92–100 (1953)
18. JB Speakman, Mechano-chemical methods for use with animal fibers, J Text Inst 38(2)
T 102–126 (1947)
19. A Sookne and M Harris, J Res Natl Bur Stand 19 535 (1937)
a
Instron, Instron Corporation, Canton, Massachusetts
b
Dia-Stron, Dia-Stron Ltd, Broomall, Pennsylvania
Chapter 51
In Vivo Quantitative
Evaluation of Gloss
A real time polarization analysis technique is described that
differentiates components of scattered light in video images and
enables in vivo quantitative evaluation of gloss from hair and
skin during quality control and claims substantiation.
key words: Gloss, shine, skin, hair, light scattering,

polarization, imaging
C osmetic manufacturers need to quantify the visual appearance of their products

objectively and accurately to study skin and hair, to improve the performance,
quality and the reproducibility of cosmetic products, and to substantiate their claims.
In vivo non-contact testing provides the most meaningful results since it is carried
out in realistic conditions directly on a model. For this chapter, in vivo gloss mea-
surements were conducted on commercially available hair and skin products.
Color and Gloss

Color and gloss are two important parameters that define the visual appearance
of an object. To simply explain the physics of the light-scattering phenomena, let’s
consider the case of a planar object illuminated by an incident light coming from
one direction (see Figure 51.1). The outgoing scattered light can be divided into
different categories.1-3
Figure 51.1.
495
496
In Vivo Quantitative Evaluation of Gloss Beginning Cosmetic Chemistry
Mirror-like reflected light or specular reflection: A portion of light is

optically reflected by the surface of the object at a symmetrical angle (mirror-like
reflection at specular angle) just like a bouncing ball. Specular light does not usually
penetrate the object, so in most cases it does not carry any information related to
the color pigment. Thus, the color of the specular light is related to the color of the
illumination. Indeed, one can easily observe a white reflection when looking at an
object from the specular angle. Artists call it a highlight,3 to scientists it’s a specular
reflection or surface scattering, and cosmeticians term it gloss, shine or luster.
Volume scattering: A portion of light penetrates inside the object and is scat-
tered/absorbed by the color pigments. The volume-scattered light that is not fully
absorbed leaves the object carrying the color information of the pigments. Indeed,
when viewing an object from an angle other than the specular angle, one can observe
the color of the object. Volume-scattered light is also called diffused light.
Surface scattering: Finally, a portion of light is scattered at the surface of the
object because of the presence of surface defects. The surface-scattered light carries
the information of surface quality and surface defects. It is of particular importance
for the analysis of metallic surfaces, when there is no volume-scattered light.
Degrees of Gloss: Gd and Gd*

Based on the above parameters, we can define two gloss degrees (abbreviated
Gd and Gd*):
• Gd, ranging from 0% (low gloss) to 100% (high gloss), is the percentage of
specular light in the total amount of reflected light.
• Gd*, ranging from 0 (low gloss) to ∞ (high gloss), is the ratio of specular
light divided by the volume-scattered light in the direction of observation.
Gd* allows the classification of high gloss objects.
Both Gd and Gd* cover a large range of glosses and allow the evaluation and
classification of cosmetics products. Furthermore, because they take into account
the total reflectivity of the object, they are correlated to the visual assessment car-
ried out by the human eye. Dark objects, for example, appear glossier (because of
their low reflectivity) than light objects (high reflectivity).
Operating Principle
Our evaluation technique is based on differentiating and measuring the types
of scattering events. Depending on its origin, the light scattered exhibits various
polarization signatures.1,2,4 Specular light, for example, has the property of preserv-
ing the original polarization state whereas diffused light is fully depolarized. We
use an innovative real time polarization analysis5,6 technique (see the Polarization
Analysis sidebar) to quantify the scattering events described above.
By using a polarimetric camera with a high polarization contrast parameter
value (>100) at a fast video rate (15-30 frames/sec), one can now measure the
following scattering parameters—1,2,4 specular light, surface-scattered light, and
volume-scattered light, all in black and white— or if needed, in the red, green
and blue colorimetric space. Figure 51.2 presents three images delivered by this
imaging systema.
497
Figure 51.2.
Polarization Analysis
Using a polarized illumination, specular and diffused components of
light can be retrieved by measuring parallel and crossed polarizations. This
separation has already been used and explained in past literature for hair
luster analysis.7
Thanks to recent advancements in electro-optics technology, a fast polari-
metric video camera with a high polarization contrast (>100) was developed
in order to perform real-time analysis. The polarization contrast is actually a
parameter that quantifies how well the technique can break the scattered light
into its components. The higher the polarization contrast of the system used,
the better the analysis and the separation of the components. It is critical to
use a high polarization contrast (>100) technique in order to well separate
the components and carry out accurate gloss measurements.
The classical image is the real image delivered by a usual camera. It presents
both color and gloss information. It contains the information of totally reflected light
and is the sum of the parallel polarization (P) and the crossed polarization (C).
In the case of skin, the surface image does not provide any color information
and is black and white. It shows the distribution of the surface scattered light on the
complex shape of the face, highlighting the surface imperfections (pores, wrinkles).
In addition, it extracts and displays the specularly reflected light. Mathematically,
it is the exact difference between the P and the C image.
The volume-scattering image presents no specular light and shows the diffused
light and the true colors of the skin. It was calculated by multiplying by two the
crossed polarization image C.
Using the definitions previously given, the images are then processed and com-
bined to provide accurate and consistent gloss values Gd and Gd* on areas of the
object specifically chosen by the user. The primary innovation of this technique is
that it allows for the gloss characterization of curved and highly textured surfaces
which, until now, was not possible with classical gloss meters.
498
Experimentation
The experimental set-up for gloss measurement includes: a polarimetric imaging
sensor; a polarized illumination system; and a computer with software dedicated
to fast polarization image acquisition, processing and display of results (Figure
51.3).
Figure 51.3.
The illumination can be based on fluorescent lights (cool white) or white Light
Emitting Diodes (LEDs), which make it compact, cold and easily controllable. The
software was developed to provide calibration, acquisition of polarization images,
gloss measurement, real-time analysis, display and recording of various images. A
chin rest or a head rest is also used to control the position of the face for optimum
repeatability.
Results
In vivo gloss measurement of foundation: Foundations presenting various
levels of gloss were tested with the system. A Region of Interest (ROI) in the “T”
area of the face was chosen for the measurement. The gloss degree was measured
on each pixel in the entire ROI; then the average of all the values was calculated.
Results of eight commercially available foundations are shown in Figure 51.4.
The gloss results correlate to visual observation and confirm the matte/glossy
nature of each foundation. The glosses ranged from 19% to 45% on the Gd scale,
which demonstrates large differences between commercially available products.
The accuracy of our measurement was better than 0.5 gloss unit on the Gd scale
without using any additional time averaging with the video imaging sensor.
Efficiency testing of hair product: We also quantified the evolution of hair
shine in the following five different conditions: uncombed; combed; combed with a
reference conditioner; combed with a shine improvement conditioner; and combed
with a shine improvement conditioner plus a liquid polish. Since hair is a highly
reflective object with low diffusion (Gd>70%), we chose to plot the results on a
Gd* scale as shown in Figure 51.5.
499
Figure 51.4.
Figure 51.5.
The results show a large range of Gd* values depending on hair conditions and
the products that were applied. Combing drastically increases the reflected light by
50% and makes hair shinier. A classical conditioner increased the shine of combed
hair by another 10% while a second conditioner, claiming to improve the shine,
increased it by 40%. By adding a liquid polish, we could further increase the shine
of combed hair by 60% reaching a Gd* value of 7.85. The total uncertainty of the
measurement was 0.3 on the Gd* scale.
The Gd* measurements obtained correlate to the visual assessment and depend
on the hair color of the model. The present measurements were carried out on light
brown hair. Higher values of Gd* as well as larger gloss effects due to the applica-
tion of the products are expected in the case of dark brown or black hair.
Gloss distribution: We calculated the Gloss Degree (percentage of specular light
in the total amount of reflected light), pixel by pixel, in order to instantly represent
the spatial distribution of the gloss of a complex 3D surface such as a human face
using the formula Gd = (P – C)/(P+C). The color of the images of Figure 51.6 was
encoded by the Gloss Degree using the color scale shown in each image. This “gloss
mapping mode” allows the user to visualize immediately the gloss distribution and
efficiently communicate the differences between two products. Figure 51.6 shows
500
two examples of a model face with a matte and a glossy foundation. Here, the red
color corresponds to a gloss of 50% while blue corresponds to 0%.The right image
(glossy foundation) shows that Gd is larger in specific areas where specular light
can be observed by the camera: tip of nose, T area, eye lids. A matte foundation
presents a more uniform, low Gd on the face.
Figure 51.6.
Advantages to Gloss Measurement

Gloss measurement is a perfectly standardized procedure in the industry. Clas-
sical gloss meters are already widely used in the textile industry, paint industry, etc.
and measure the intensity of light reflected from the object in the specular direction.
However, they use single detectors and work only on flat surfaces8 with low texture.
They cannot quantify accurately the gloss of complex 3D surfaces.
Thanks to the scattering/polarization analysis it offers, the described imaging
technique is well adapted to cosmeticians and provides an objective, accurate as-
sessment of skin optical properties independently of the object shape. In addition,
the scattering analysis technique offers non-contact in vivo measurement indepen-
dent of texture and shape as well as fast analysis with 5–25 Hz real time operating
speed for simultaneous display and calculation of polarization images and results.
The speed of the system developed provides the user with optimum experimental
conditions and allows real time measurements. The measurements presented in
this chapter correlated to human eye assessment. High accuracy (0.3% on Gd
scale) and high consistency (0.3%) is obtained, depending on the application. The
technique leads to other light scattering characterizations such as the measurement
of whitening powers, radiance, soft focus power and calibrated color measurement
of scattered light.
The main limitation of the technique remains in the repositioning of the object.
Indeed, between treatments or applications of new makeup or products, the object
(human face, nails) should be repositioned at the same location with the same
orientation. Therefore, for face measurements for example, accurate mechanical
positioning systems such as chinrests and headrests are being used to maximize
the accuracy of the technique.
501
Conclusion
The described imaging technique opens the possibility of measuring objectively
the gloss of textured, complex 3D objects. The examples presented in this chapter
demonstrate the efficacy of the technique for crucial applications such as the in vivo
gloss measurement of skin and hair. The technique is well adapted for the cosmetic
industry to formulate, evaluate products and substantiate claims.
References
1. S Breugnot, L Le Hors, D Dolfi and P Hartemann, Phenomenological Model of Paints
for Multispectral Polarimetric Imaging, Aerosense, Orlando, Florida (2001)
2. HC Van De Hulst, Light Scattering by Small Particles, Dover, New York (1981)
3. The Munsell Book of Color, Munsell Color Company, Baltimore, MD (1976)
4. E Collett, Polarized Light, M Dekker, Inc New York (1993)
5. M Rowe, EN Pugh Jr, JS Tyo and N Engheta, Polarization difference imaging: A
biologically inspired technique for observation through scattering media, Optics
Letters 20(6), 608–610 (Mar 15, 1995)
6. S Breugnot and P Cl menceau, Modeling of a polarization active imager at λ =806 nm,
Optical Engineering 39(10) 2677–2680 (Oct 2000)
7. R McMullen, J Jachowicz, Optical properties of hair: Effect of treatments on luster as
quantified by image analysis, J Cosmet Sci 54 335–351 (July/Aug 2003)
8. R Korichi, Video imaging in the measurement of makeup efficacy and performance,
Cosmet Toil 117(10) 39–48 (2002)
Chapter 52
Evaluating Shampoo Foam

Although the foaming properties of a shampoo has little to do
with it’s actual performance (aka cleansing), thick rich foam has
become associated with quality in the minds of consumers.
key words: viscosity, foaming, lubricity
T here is probably no personal care category that is more competitive than sham-
poos. With this in mind, formulators of shampoos are asked by marketing to
develop products to both appeal to consumers and perform (whatever “perform”
means).
Performance
Speaking about performance, I scanned the shampoo products available on www.
drugstore.com and quickly was able to come with a list of claims (see the Shampoo
Label Claims Found in a Quick Search of Drugtore.com sidebar). I stopped
looking at the claims after reviewing the labels of approximately 25 shampoos of
the more than 300 they sell!
We have come to expect these outrageous claims, as have consumers. A con-
sumer may indeed purchase the shampoo based on one or more of these claims,
but the four attributes that come into play only during use, and that are rarely
mentioned (and are most valued by consumers), are: cleansing, fragrance, viscos-
ity and foaming.
Cleansing: Cleansing is taken for granted by consumers. In fact, while market-
ing people may be concerned that the shampoo being developed by R&D cleans
adequately, in reality all shampoos contain several times the amount of surfactant
needed to clean even the most soiled hair! It would be almost impossible to make
a shampoo using today’s anionic surfactants that didn’t clean the hair.
Fragrance: Fragrance is one of the most important reasons a person buys a
shampoo. Have you ever seen a shampoo that was fragrance-free? I think not!
Viscosity: To a purchaser, a shampoo that is thick implies it must be “rich”
(whatever that means) and will certainly perform. It is silly, but who am I to argue
with consumers?
Foaming: The consumer, standing in the shower with eyes closed and wet hair,
applies the shampoo, rubs, feels the foam/lather and quickly makes a judgment as
to the performance of the shampoo. If it does not provide a copious, lubricious,
dense foam quickly (that also smells pleasant) the consumer will have a rather
negative impression of the shampoo that will be difficult to overcome even if it
503
504
Evaluating Shampoo Foam Beginning Cosmetic Chemistry
does a great job in providing hair conditioning. Let’s spend a few minutes talking
about foam evaluation.
Shampoo Label Claims Found in a Quick Search of Drugstore.Com

Volumizer Thickens
100% vegan DEA free
Sulfate free Mild
Purifies Balances
Conditions pH balanced
Maximizes bounce 50% organic ingredients
Shiny hair Detangles
Healthy hair Softer hair
Hydrating Ultra-hydrating
Clarifies and absolves impurities Rejuvenates
Adds vibrancy Provides weightless moisturizing
Foam Evaluation
Without question the best method to evaluate the foaming ability of the sham-
poo is consumer testing, most often done in a salon setup. However, it is costly and
very time consuming. Just imagine, you have just finished preparing a shampoo
formulation using a new conditioning polymer and you have to wait several days
(at best) before you will know if it negatively affects the foam attributes. This situ-
ation is intolerable.
Foam evaluation has been going on for many years. Following is a brief descrip-
tion of the most popular methods employed by chemists. In each of these methods
the temperature of the water and water hardness may be varied. Additionally, a
synthetic sebum may be added to simulate the presence of “soil,” i.e., dirty hair.
Ross Miles: This method is the oldest standardized method, dating back to
1941. A dilute solution is dropped from a fixed height into a pool of the same dilute
solution and the foam volume is measured. This test produces an airy foam that
in no way approximates foam produced in actual use by the consumer. These days
it is only used by suppliers of surfactants. It doesn’t give an accurate reading on
foam volume, foam density or foam longevity. In my opinion, it shouldn’t be used
by anyone.
Cylinder shake: Also developed in 1941 (Stiepel), the cylinder shake method
is, by far, the most widely used foam evaluation test method.
A fixed amount of dilute shampoo is poured into a graduated cylinder. A stop-
per is placed onto the cylinder and it is inverted for a fixed number of times. The
foam volume is then measured.
While is very easy and quick to run, the data generated, just like the foam, is
very inconsistent. It is very operator dependent. Even the same operator has dif-
ficulty in reproducing data. A standard shampoo should always be used to try to
insure reproducibility.
505
Many people have tried to reduce operator dependence of this test. One such
modification (Beh-James) uses 300 ml of a dilute shampoo solution in a 1000 ml
graduated cylinder. The cylinder is subjected to rotation on a vertical plane perpen-
dicular to the axis of a motor (attached to the cylinder). It is rotated for 2 minutes at
36 rpm. The foam height reading is taken 30 seconds after rotation has finished.
Perforated disk: This foam evaluation method was developed in 1958 (Bar-
nett & Powers). A sample of 200 grams of shampoo solution is placed into a glass
cylinder (6.3 cm in diameter and 30 cm in length). A perforated disk (6 cm in
diameter) is moved up and down in the tube (26.5 cm) at a speed of 30 strokes per
minute. The foam height is measured after 30 strokes. This method is fairly good
in its consistency, but the foam it produces is loose and airy.
Moldovanyi-Hungerbuhler: A 500 ml shampoo solution is prepared and poured
into a flask. The flask has an input tube to permit nitrogen gas to flow into the solu-
tion (from the bottom) at a rate of 17 liters/minute. The time needed to produce
2 liters of foam is measured. The liquid is drained off and the flask is weighed. We
now have a measure of the foam density. If we wait a fixed period of time and then
drain off additional liquid, we have an indication of foam stability.
This method is a bit cumbersome and like the other methods discussed, pro-
duces a loose, airy foam.
Hart-deGeorge blender method: This foam evaluation method was the first
to incorporate a blender to generate the foam. The foam produced is thick and
creamy and very similar to the foam seen is actual use tests.
A 200 ml shampoo solution is agitated in a blender (1 liter vessel size) for one
minute. The foam is then poured into a funnel placed on a sieve with a mesh of
0.5 mm. The funnel measures 182 mm (top) to 23 mm (bottom). A gauging wire
is placed 80 mm from the bottom of the funnel. The time for the level of foam to
reach the wire (seconds) is recorded; the higher the number, the better the foam.
This is an excellent method for assessing foam.
Blender Foam Volume/Drainage: For this method (1981- Henkel Corp.), a
10% solution of shampoo is prepared. Four grams of this solution are added to 146
grams of water (50 ppm hardness) at 29°C. The solution is agitated for 10 seconds
at a medium speed in a blender. The foam is poured into a 1000 ml graduated
cylinder and the volume is measured. After 3.5 minutes the position of the foam
water interface is recorded (drainage). The evaluator may add 0.5 grams of synthetic
sebum (or castor oil) to determine its effect. Additionally, the time of agitation may
be decreased to 5 seconds to determine flash foam. This method is, in this author’s
opinion, the best technique (aside from salon testing) currently available.
Blender-Foam Density/Stability/Lubricity: In this method (1967-Unilever)
a 10% solution of the shampoo is prepared. Four grams of this solution are added
to 146 grams of water (50 ppm hardness) at 29°C. The solution is agitated for 10
seconds at a medium speed in a blender. The foam is poured into a 100 ml gradu-
ated cylinder to overflowing. A rubber stopper is gently dropped into the foam.
This stopper has been shaved so that it is slightly smaller in diameter than the
inside diameter of the graduated cylinder. The time for the rubber stopper to pass
between two points (80–40 ml) is measured. A longer time indicates a denser and
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Evaluating Shampoo Foam Beginning Cosmetic Chemistry
more stable foam. The rate at which the stopper falls is dependent on the upward
pressure. This upward pressure is inversely proportional to the size of the bubbles.
Thus, a more dense foam will cause the rubber stopper to fall more slowly. This
test is very good test method as it closely approximates consumer perception of
foam “quality.”
While none of these tests is without drawbacks, by using the last two (Blender
Foam Volume/Drainage and Blender-Foam Density/Stability/Lubricity), the
formulator can quickly get a very good reading on how consumers will judge the
foaming of the tested shampoo.

Chapter 53
What You Should

Know About Testing
on Human Hair
This chapter discusses the importance of hair quality in tress
testing. The source of hair as well as how these tresses are
processed is included.
key words: tress testing, hair sources
O ne of the most important attributes of a haircare product is its ability to improve

the combing properties of hair. Testing on hair tresses readily provides data
that match consumer perception of these properties. The detangling and combing
capabilities of shampoos and conditioners are especially well suited to tress evalua-
tion. In addition, tress testing allows repetition of experimental observations without
introducing a variable such as different hair types. The success of such testing,
however, is dependent upon the reliability of the equipment (the consistent quality
of the tresses and the apparatus and combs used) and the methodology to evaluate
the tresses. This chapter describes the type of hair used in tresses and outlines a
procedure for evaluating hair formulations on tresses.
Sourcing human hair

Many new chemists are surprised to find that human hair can be purchased for
testing purposes. In fact, human hair is available in many colors and lengths from
a number of vendors. Not all hair is created equal however, and it’s good for the
chemist to have an understanding of the type of hair used for testing purposes.
The supply and sale of human hair to the laboratory has changed significantly
over the past 20 years. Originally, human hair for laboratory research was provided
primarily by wig manufacturers or the companies that sold hair to wig makers.
Today, laboratories are aware of the need to buy hair that is specifically geared
to their needs. The hair must be natural, untouched by chemicals, washed in a
solution without additives and properly aligned. The need for laboratory quality
hair that is most closely associated with hair off of the human head is what is now
required and demanded.
The only way to make sure that the substrate that is bought for the lab is in
fact laboratory quality is to buy the hair from a source that maintains a controlled
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What You Should Know About Testing on Human Hair Beginning Cosmetic Chemistry
hair purchase and preparation procedure throughout their entire system. It is not
enough for the supplier to buy high quality natural hair but also to maintain a system
where the hair is sorted, washed, dried, worked and stored properly.
Buying natural, raw, untreated hair, in and of itself is a difficult task. Getting
the wrong kind of hair can cause many problems. For example, imagine that you
need hair of a certain natural color for testing. One unscrupulous company has been
known to create “gray” by mixing bleached and pigmented hair together to create
a salt and pepper color. Another supplier fulfilled an order for natural red hair by
dying the tresses! And yet another provided what was supposedly kinky African hair
but was actually Chinese hair that had been crimped to resemble it.
One can imagine the waste of time and effort these examples must have caused.
These examples clearly point out the importance of understanding the origin of
the hair you use.
Sourcing of hair, original sources of hair

When developing and testing products for a specific region, you should be sure
that your test hair is sourced from that region. You would not want to use Asian
hair for a predominantly European market, and vice versa. Reputable global hair
suppliers source from all over the world including Africa, the Caribbean, South
America, Asia and Europe.
• Basic hair types
• European
• Asian
• African
• Yak
Specifically it is yak belly hair. A yak is a bull-like creature that is found in certain
areas of China and especially Tibet. Two types of yak exist, white haired and black
haired. Of course for color testing, the white haired yak is used but only a certain
part of this animal’s hair should be used for testing. This hair is found on the area
around the center portion of the belly.
You may ask why from only the area around the belly and that would be a good
question. The answer is that the hair from the center area of the belly is much softer
and finer than the tail and general body hair. Therefore it is more close to that of
human hair than the rest of the animal’s hair which is generally much thicker and
much coarser. Also, since it is fairly white, especially after be cleaned properly, it
easily shows the difference in color when you are doing color uptake testing.
Preparation of hair for testing

Another important consideration is how the test hair has been cleaned and
prepped. Thought was never given to the type of cleaning product that was used
to wash hair years ago. As a matter of fact certain suppliers used extremely harsh
soaps to wash certain types of hair simply to make the process quicker and easier
but after this harsh soap application the damage to the hair was much higher than
“normal washing” by an individual. The products they used could literally burn
your scalp. So you can imagine what it did to the cuticle.
509
Something else that was used in washing years ago was conditioner in the water
to make the hair softer and shinier. Now for an individual or for someone who is
using this hair to make a wig that is perfectly acceptable. However, that result is
definitely not something a chemist wants to have on the hair that he is about to
use for testing!
The hair must be cleaned thoroughly but not by anything that has any kind of
fragrance or additive, such as a color or conditioner, then rinsed thoroughly. You
want the hair to be as natural in your lab as that of clean natural hair on a person’s
head.
The hair is then dried in a natural environment before processing. NOTHING
about the hair is altered unless of course the order is for bleached or dried hair.
When this hair is processed in some way (either by dyeing or damaging) it is done
in such a way to ensure that the process is highly reproducible so the next time you
order the same hair it has the same properties. It is essential that the substrates you
use are uniform and have a consistent and a standard level of damage is maintained
through out. And not only does the hair have to be processed in the same way, but
the size and weight and consistency of the tress need to be the same across a large
number of swatches.
Common hair treatments
• Virgin
• Bleached
• Permed
• Dyed
“Old timers” in this industry will recall a time, prior to 1993, when tresses
were required to be made by hand. In fact, the first edition of Beginning Cosmetic
Chemisty included a chapter that described how to make your own tresses. Prior
the early 1990s, almost all of the hair care work was based on ordering hair that
came in bundles of string tied hair. Whether the hair was six inches long or 14 inches
long overall, the chemist or lab technician would order the required substrate and
the hair would come in bundles so described and he needed to somehow get the
hair into a configuration that was practical for a lab environment. These bundles,
(for about 6 inch hair), were around 2.5 ounces each and almost unusable in their
delivered state and they were proportionately heavier if the hair was longer hair.
The chemist opened the bundle, pulled off and weighed out the desired amount
of hair, say for example 5 grams, tried to keep the hair even at the root and tip end
and then some how bound the root end so the hair didn’t fall all over the laboratory
counter, which happened in any case every now and then. Or, if the lab was large
enough, some companies would hire some one to come in and make the pieces,
which still was not very accurate as the binding agent was not always the best and
in rare cases an outside agency might be hired to make the pieces off site which
brought about extra time delays.
Thankfully, tress-making is no longer a skill that chemists are required to have
because advances in technology have made uniform hair tresses widely commercially
available. The first innovation of hair preparation for the laboratory, hair swatching
by International Hair Importers (IHIP), allowed the chemist to now order the hair
510
in a preformed fashion, held at the root end so that when the technician or chemist
opened the box of pre-weighed, sewn and swatched hair, he or she would simply
have to cut off the section of hair they wanted to use and begin their testing.
This particular advancement along with the specific, consistent quality of labo-
ratory grade hair now gave laboratories a new and quicker way to get the testing
done. There was now no worrying about the origin or quality of the substrate and
no need to spend hours trying to prepare the hair to be used in the testing.
With the increased level of testing and further advanced equipment such as
computer enhanced robotic systems that were not only able to repeatedly soil, wash,
condition, rinse and dry hair swatches, the demand for newer ways of delivering
the hair brought greater demands for the suppliers of hair.
It is now possible to by tresses in almost any configuration imaginable, from a
.25 gram, 2 inch overall swatch to a 30 gram, 14 inch swatch using various binding
materials and parts. The possibilities are almost endless.
Tress Studies
A wide spectrum of information can be attained by evaluating formulations on
tresses (see Table 53.1).
Table 53.1. Shampoo or conditioner properties for tress studies
Wet tresses
Application properties (how the product spreads through the hair)
Lathering properties (speed of foaming, volume of lather, richness, creaminess
of foam)
Rinsability
Detangling properties
Wet combing properties
Tactile properties (leaves the hair feeling clean, smooth, silky)
Dry tresses
Drying properties
Dry combing properties
Tactile properties (silky/smooth feel)
Tactile properties (leaves the hair feeling clean, smooth, silky)
Antistatic properties
Volumizing properties (leaves hair with body and fullness)
Styling properties (ease of curling)
Overall appearance
Such varied product properties as application feel, rinsability, and the wet and dry
feeling products impart to the hair are all readily observable on swatches. However,
511
tress testing is most useful for evaluating the combing properties of shampoos and
conditioners. Naturally, the design of each study will depend on the specific goals
of the product being tested and so each study will vary somewhat. However, in the
most general terms, every tress study should adhere to the following guidelines.
Questionnaire design: A range of critical attributes should be explored with
each study. Avoid focusing solely on the most important qualities, as this may tend
to bias the panelists. The best data is obtained when the focus of the questionnaire
is not too narrow. Keep in mind that if a questionnaire is too lengthy, the impact
of each point may be diluted. Use your best judgment when determining which
questions to ask. Refer to Table 53.2 for an example of a questionnaire used in
an Ease of Combing Study.
Pay special attention to the questionnaire’s rating scale when considering how
panelists will rank the designated attributes. The scale in Table 53.2 assigned values
weighted by descriptive terms. The result is a 100-point scale which attempts to
assign some objective basis for gauging subjective sensory perceptions. This scale
can be adapted as necessary for individual tests, but some version of a weighted
scale should be maintained.
Table 53.2. Sample panelist questionnaire
Study # ______
Panelist Name________________________
Date _________
Title: New Conditioning Shampoo Study
Attribute: Ease of Combing
Tress Code_______
100 Severe Drag—uncombable; comb will not pass through tress without extreme
force
75 Heavy Drag—comb passes but only with some snagging or catching; tress
feels very rough against comb
50 Moderate Drag—comb passes through tress without snagging, but tress feels
rough; rasping sound and friction are obvious
25 Slight Drag—combs easily but some dragging is readily perceived
10 Very Slight Drag—comb glides through tress with some friction barely
perceived
0 No Drag—comb passes through tress without apparent friction
Calibration of panelists: Panelists often consist of coworkers willing to spend

a few minutes of their time participating in the test and filling out the question-
naire. For any scale to be effective, all the panelists must use it in a consistent
fashion. Prior to testing, instruct or “calibrate” the panelists on the rating scale to
ensure uniformity when scoring various properties. This procedure may be done
by first evaluating their results on a series of control swatches for consistency in
their readings.
512
Testing procedure: The mechanics of any given test vary from study to study,
but it can be assumed that the greater number of tresses and panelists, the better
the data. As a general recommendation, use a minimum of five pairs of tresses
evaluated by at least three panelists. Such a study should indicate large differences
in functionality. If more subtle differences are to be detected, a larger data base is
required. The key to obtaining good tress data is to treat all tresses as identically
as possible. Tresses used in a given test should be from the same lot of hair and, if
possible, should have been damaged at the same time.
Before beginning the study, tresses should be given a final wash with detergent
and, if necessary, air dried. While the tresses are drying, determine the code numbers
or symbols to be used on each tress and prepare 2x2 inch squares of index cards
marked with the appropriate code. These tags may be inserted into the top of the
plastic mounting card either prior to or immediately after product application.
Once all preparations are completed, the test can be initiated. Apply the test
and control products to the appropriate tresses following the product use direc-
tions. Each test may require a different protocol, but typically, the test would use
a 1 min application period followed by a 30 sec rinse with tap water at a specified
temperature. Transfer the tresses (with code tags in place) to a tress bracket ap-
paratus, which supports the tresses during combing. Slide the plastic mounting
card into the clamp on the end of the bracket. Insert the card, as far as possible, to
keep it from bending and causing the tress to move during combing. Tighten the
wing nut to hold the tress securely.
Evaluation of tresses: Once the tresses are in place, they are evaluated by
individual panelists. Using the specified combs, each panelist evaluates the tresses
according to the questionnaire. Each tress should be evaluated with one comb only,
to avoid contaminating the combs with residue from treated tresses. When several
panelists are conducting evaluations, it may be necessary to rewet the tresses to
ensure the evaluation of “wet combing.”
Treatment of data: Average the scores for the tresses and apply statistical
analysis as appropriate.
Tress testing is an important tool for determining how formulations may need
readjustment to achieve the desired performance for the marketplace.
Published in Beginning Cosmetic Chemistry, Second Edition
Suggested Reading
G Scottand and W Waggoner, Instrumental Method for the Determination of
Hair Raspiness, JSCC 17 171–179 (1966)
Y Kamath and H Weigmann, Measurement of Combing Forces, JSCC 37
111–124 (1986)
J Prall and D Wedderburn, Hair Product Evaluation: From Laboratory Bench
to Consumer and Back Again, JSCC 24 561–576 (1973)
C Robbins and G Scott, Effects of Surfactant Solutions on Hair Fiber Friction,
JSCC 31 179–200 (1980)
Y Kamath, et al, Wettability of Keratin Fiber Surfaces, JSCC 28 273–284
(1977)
Chapter 54
Evaluating Shine on Hair

This chapter defines shine in the context of hair care and
discusses ways to measure it.
key words: hair shine, cuticle, shampoos, conditioners
W ebster’s Third New International Dictionary tells us that shine means “to be
bright with the reflection of light, to gleam or glisten.” But what Webster
doesn’t tell us is that shine is one of the most sought after, yet most elusive, of all
hair care benefits.
What Makes Hair Shine?

Physical structure of hair: To understand what makes hair shine we must
first understand its physical structure. The cuticle (the shingle-like outer layer of
the hair) is primarily responsible for shine. In virgin hair these overlapping scales
are undisturbed and are stacked tightly one on top of another approximately five to
10 layers deep. In this configuration they form a very flat surface that is relatively
reflective. They are held tightly in place by intercellular lipids, including ceramides,
and they are protected by a fatty layer consisting of materials such as 18-methyl
eicosanoic acid. These materials naturally protect hair from surface damage.
As hair ages it is exposed to a variety of damaging effects from sunlight, physical
abrasion, repeated washing and drying, and chemical treatments such as perms and
coloring. These physical and chemical intrusions can gradually strip away the hair’s
natural protection. Once the cuticle is no longer cemented in place, the individual
scales loosen and begin to lift away from the surface. This lifting process makes
the hair more irregular and initiates an inevitable downward spiral of damage. As
the cuticular plates begin to lift, it becomes easier for them to be torn away by
combing and brushing. And as each successive layer of cuticle is stripped away, the
layer beneath is exposed to more damaging effects, which in turn cause them to
be loosened and stripped away. Left untreated, this process will continue to strip
away the cuticular layers, making the surface increasingly irregular.
Optical properties of hair: The regularity of the hair’s surface helps determine
how reflective it is. When a beam of light strikes a perfectly smooth surface, such as
a mirror, the angle of the incident light exactly matches the angle at which the light
is reflected. This type of reflection is known as spectacular reflectance and it does
occur on hair to some degree. However, since hair is not as smooth as a mirror, it
interacts with light in other ways as well. Some portion of this light bounces off hair
at a different angle than the incident beam. This type of reflectance is called diffuse
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Evaluating Shine on Hair Beginning Cosmetic Chemistry
reflectance. Some of the light passes through the cuticle, which is transparent, and
is reflected off the back wall of the hair. In light scattering analysis, this “back wall”
reflection is seen as a second peak. This secondary peak has greater intensity for
blonde hair but less for dark hair, because the melanin pigment present in darker
shades tends to absorb more light. Using a polarized illumination with a polarization
analysis makes it possible to differentiate between the specular and the diffused
light. The specular reflection gives information about how smooth and glossy or
conversely, how rough, the hair is. The diffused light provides information about
the color of the hair.
The physical construction of the hair and the optics involved in reflection are
only part of the story. To understand how complex the phenomena of hair shine
is, consider that hair consists of over 150,000 discrete fibers that can move inde-
pendently. Every movement of the body, every turn of the head can cause the hair
to cascade in new patterns that affect the continuity of its surface. Unlike hard
surfaces, hair is not continuous and is never completely at rest. The discontinuous
nature of hair makes an accurate assessment of shine very difficult.
Consumer expectations: To complicate matters even further, the formula-
tor must take into consideration the consumer’s mind set regarding hair shine. A
brief review of the claims made by today’s hair care products shows that shine is a
nearly ubiquitous benefit promised to some degree by almost every shampoo and
conditioner.
For the majority of products, shine is simply mentioned along with the other
conditioning benefits. But for some products shine is a pre-eminent claim. Take,
for example, Procter & Gamble’s Pantene Pro V. Throughout the 1990s Pantene’s
advertising proclaimed they would give you “hair so healthy it shines.” According
to data from Information Resources Inc., a Chicago-based market research orga-
nization, P&G spends somewhere in the neighborhood of $40 million on Pantene
advertising each year. Therefore, it is reasonable to assume they’ve spent close
to hundreds of millions over the past 10 years to convince women that their hair
should be shiny. Although P&G has since discontinued this campaign, shine remains
strongly associated with healthy hair in the minds of many consumers.
Another example of a product line in which shine is the key benefit is Advanced
Research Laboratories’ Citre Shine. The Citre Shine line consists entirely of treatment
products focused on making hair shiny. While not as influential in terms of advertis-
ing as Pantene, Citre Shine continues to be successful in the market place.
The net effect of brands like Pantene and Citre Shine has been to raise consumer
awareness and expectations regarding shine even though it is difficult for women to
ascertain when it is being delivered. Therefore, formulators must understand that
hair care products can affect shine both positively and negatively. The remainder of
this article is designed to give the cosmetic scientist a fundamental understanding of
how hair care products affect shine and how changes in shine can be measured.
The Role of Hair Care Products

The basic approach to increasing shine involves smoothing the hair’s surface.
When the aforementioned cuticular layers lay flat on hair the light is reflected more
515
uniformly. Some improvement can be made just by lubricating the hair so the cu-
ticles are not disturbed during grooming. Smoothness can be further increased by
coating the hair with materials that are reflective themselves. Certain silicone- and
hydrocarbon-derived materials will form reflective films on hair. Similarly, shiny
particles like titanated mica can give hair a glitter effect.
However, the drawback is that in both these cases the process requires that a
substantial amount of material be left behind on the hair. Here we encounter one
of the most dreaded of all hair care sins—weighing down the hair. According to
a 1999–2000 Gallup study of female hair-care practices, nearly 15% of all women
are concerned specifically about hair shine. But, 28% percent of women are wor-
ried about their hair becoming limp and weighed down. For this reason, merely
coating the hair with a shiny layer is not a solution that will be acceptable to all
consumers.
Not only is it difficult to increase shine, but many hair care products can actually
decrease it. Even the hair’s own natural sebum can make its surface look dull. Rob-
bins cites a study by Scherbece that shows the natural oils on the hair can indeed
negatively impact shine. Similarly, soaps that can leave a hard water residue on hair
also diminish shine. This effect occurs because fatty anions in the soap combine
with metallic cations in the water and form an insoluble complex that deposits on
the hair. This problem is less common today since true soaps are very rarely found
in shampoo products.
This same type of dulling effect has also been shown to occur in some shampoo
formulations that contain cationic polymers. These polymers do not deposit uni-
formly on the hair and may therefore increase light scattering. Studies have shown
that hairsprays can also dull hair, once again presumably because deposition of the
resin reduces uniform reflectance. Not surprisingly, hair treatments, which chemi-
cally degrade the hair, such as permanent waves and oxidative colors, also reduced
shine. This effect is presumed to be due to the the weakening of the cuticle.
It is important for formulators to be aware of the potential dulling effects that
these products may have. They should not assume their product will increase shine
just because it provides conditioning benefits. If hair shine is a desired benefit, each
product should be evaluated on hair tresses and on panelists to ensure it is having
a positive effect on light reflection.
Hair Shine Testing Methods

Formulating products that increase hair shine is challenging because the subtle,
incremental increases that are invariably obtained can be difficult to perceive. They
can be even harder to quantify. None the less, a variety of methods have been de-
veloped for measuring hair shine and the effect that cosmetic products have on it.
These can be conveniently classified as instrumental and subjective methods.
Instrumental evaluations: Instrumental tests should theoretically provide the
most consistent and controlled results for shine evaluations. In the best instrumental
tests, the data obtained is highly-repeatable, has a low standard deviation and cor-
responds with subjective evaluations. They also do not suffer from the uncontrolled
variability of subjective evaluations.
516
Gloss meter: One of the earliest methods of instrumental shine determination

was using a gloss meter. The gloss meter is a device that was developed for the
coatings industry. It consists of a light source and a photoreceiver. Light is shone
on the test surface at a specific angle and the photoreceiver captures the reflected
light at the corresponding angle. The device then outputs a specular gloss value
based on the intensity of light reflected. Unfortunately, this device was designed for
a flat, regular surface, which hair is not. Hair is more of a cylinder shape and when
light is shone on it, it reflects at multiple angles. Since the perceived hair shine is
dependent on much of the light reflecting at different angles, the gloss meter does
not detect a large portion of this light. Consequently, the gloss meter is of limited
value for determining hair shine.
Goniophotometer: A better device for measuring hair shine is a goniophotom-
eter (or photogoniometer). This device has a moving detector which measures the
reflected light over a range of angles. Light is shone on a hair fiber and the detector
moves along a set path to measure the reflected light intensity over a range. In this
way a more complete picture of the hair’s light reflection is obtained. In a typical
study, a number of hair fibers are taken from numerous tresses and tested on the
goniophotometer. The results are recorded as the initial values before treatment.
The tresses are then treated with the shine-enhancing product, such as a shampoo,
conditioner or styling formula. Fibers are then removed and run on the goniopho-
tometer. If the product increased shine, an increase will be found in the amount of
reflected light across the detected limits. This increase can provide the basis for a
shine-enhancing claim. Typically, an untreated control sample is run for comparison.
It is worthwhile to note that damaged hair reflects less light than non-damaged hair.
This fact should be considered when testing shine-enhancing products.
At the time of this writing, the state of the art method for instrumentally evaluat-
ing hair shine is a device known as the SAMBA Hair System available from Bossa
Nova Tech. This device combines polarization and color analysis to separate and
measure independently the angular distributions of all three light components.
In other words, the SAMBA system not only measures shine but also provides
information on the color of the hair.
While instrumental tests can provide excellent data, they suffer from certain
drawbacks for formulators. First, the instruments themselves can be expensive, so
they are not generally available. Testing of just a few samples can be cost prohibi-
tive. This reduces the usefulness during the formulation phase. Also, instrumental
improvements in hair shine often correlate with consumer perceptions, but not
always. Sometimes the instruments show differences that can not be noticed by
product users. These drawbacks demonstrate that subjective testing is useful during
both the formulating and finished-product development phase.
Subjective shine testing: If an instrumental test method demonstrates that a
product makes hair 50% shinier but consumers cannot tell a difference, the formu-
lation may not satisfy its intended market. On the other hand, if the product does
not show any instrumental difference but consumers believe it improves shine,
then the product should meet consumer expectations. Subjective tests using real
517
people will get closer to finding out how well consumers will perceive increases in
hair shine. This testing can be done on both hair tresses and in a salon.
Tress analysis: One of the simplest types of subjective analysis for hair shine
is performed using hair tresses. In these studies, human evaluators rate multiple
hair tresses before and after treatment with a product. The most important factors
to control in these studies are the characteristics of the hair tresses and the way
they are displayed. The type of tress used can significantly affect the results from
subjective evaluations. For shine studies, darker hair generally works better than
lighter hair because the contrast with reflected light is greater. The tresses should
be of identical length and type. It has been suggested that six to nine tresses are
the most that should be used for any single test. Any more can lead to evaluator
burn out.
Since hair shine is dependent on how a tress is displayed, care should be taken
to reduce variations. When having tresses evaluated, the alignment of hair fibers
should be consistent and parallel. It is advisable to get a shine box for displaying
tresses. A shine box is an all black box equipped with uniform lighting and mount-
ing devices. Tresses in a shine box can be viewed in a consistent manner which
helps reduce variability. To reduce positional bias, tresses should be rearranged
between evaluations.
Whenever subjective analyses are done, the question arises as to whether to
use trained or untrained evaluators. Which evaluators to use depends on the type
of data desired. Trained evaluators are taught to consistently give shine ratings in
line with a controlled scale. They are shown tresses with different levels of shine
intensity and told the shine rating. They are then tested on a blind basis to see
how well their blinded rating matches the given rating. They will provide tighter
and “theoretically” more objective data that will be useful during the formulation
stage. Untrained evaluators are given no initial testing prior to evaluation. In this
way different evaluators may give entirely different relative shine ratings. However,
untrained evaluators may better reflect the perception of the consumers. Therefore,
it may be better to use untrained evaluators after instrumental testing has shown that
a formulation improves hair shine and before performing a consumer use study.
To get repeatable data, 15–20 evaluators should be used. This number should
provide adequately precise data so a study is repeatable. In a typical study, tresses
are treated with a product, allowed to dry and displayed in a shine box. The evalu-
ators score each of the tresses on a set scale and then rank the tresses in order of
shine intensity. Reliable and consistent data can be obtained by using the optimum
number of tresses and evaluators.
Tress testing is a convenient method for evaluating shine, making it useful during
the formulation process. It does have certain drawbacks, however. For example,
the differences in hair shine are typically subtle. Tress testing typically will find
only big differences, missing smaller, subtle changes. Also, tresses only simulate
real life, which means they do not show exactly how a product will perform on a
consumer’s head.
Salon evaluations: Another useful type of testing for hair shine is salon test-
ing. In these tests, professional salon technicians apply the product in a half-head
518
manner. One is the test side and the other is the control. The products are applied
in a blinded manner and the hair is rated after treatment. These tests are much
like tress tests although they are even more indicative of a real-life situation. For
best results, 20 or more test subjects should be used along with multiple salon
evaluators.
Salon tests suffer from the same drawbacks as tress tests in that they can only
show large differences and may miss small, subtle differences. However, salon
tests use human volunteers so they require significantly more resources than lab
instrumental or tress tests. This makes them more difficult to use for directing
formulation and evaluating raw materials. They are better for comparing different
finished products.
Consumer-use studies: Consumer perception is the ultimate judge as to whether
a product increases shine, so a consumer-use study is an appropriate way to measure
it. A general plan for conducting a consumer-use study is to have panelists rate the
level of hair shine before and after product use. The increase (or decrease) in shine
is determined by the difference between the initial and final ratings.
It is important that subjects are chosen thoughtfully for these types of studies
to be most effective. First, the panelists should be selected to reflect the demo-
graphics of the consumers who would use a shine product. They should also be
prescreened and only those who would find benefit from a hair-shine product should
be used. Factors such as hair type, color and condition should all be recorded and
controlled. A significantly large number of panelists (30) should be used to get
reliable, repeatable data.
The initial phase of a consumer-use test would be to develop a questionnaire.
It should minimally ask the panelists to rate their hair shine using, for example, a
10-point scale. Prior to testing, it is legitimate to require a minimum shine rating for
any panelist who will be included in the study. This ensures that only people who
would measurably benefit from using a hair shine enhancing product are tested.
At least two questionnaires are given during the study. The initial questionnaire
should be designed to collect all the appropriate ancillary data such as hair type,
color and condition. Subsequent questionnaires should repeat the questions from
the initial survey excluding the background information.
Depending on the desired information, panelists can be instructed to use the
product once or repeatedly over the course of a few weeks. Certain products such
as shine sprays, gels or hair sprays are better for single use tests. Other products
such as shampoos and conditioners are better tested over the course of a few days
or weeks.
The test can be monadic or comparative. A monadic test involves having pan-
elists use the product for a certain length of time and rating their hair before and
after. This type of test works well for claim substantiation. A comparative study is
more useful for product development. In this type of study, the group of panelists
is segmented into control and test groups. The average initial hair shine rating
should be the same for both groups. One group is given the test prototype and the
other is given a control product. The control product should be one that gives a
519
known shine value or one that would not be expected to impart hair shine such as
a normal shampoo.
Another possible test design is to have both test groups try each product sequen-
tially. That is, one group tries the control product first and then the test product. The
other group tries the test product first and then the control product. The benefit
to conducting this type of study is that each panelist tries both products so a more
direct comparison is possible. The drawback is that the effects of one product may
be influenced by the other product. For example, if a shampoo that relies on coat-
ing the hair is being evaluated, the panelists who use the control product second
may have artificially high scores.
Rating scores obtained from these types of consumer use tests can be converted
into a percentage increase or decrease in shine. The changes can be quite large and
impressive. It should be noted, however, that to some extent these types of tests are
affected by the halo effect. If a consumer likes the product because of how it smells
or how easy it makes hair to comb, he or she may give higher ratings for hair shine
even though no shine improvement was present. Another drawback to this type of
testing is that unless a large number of test panelists are used, small differences
between how two products affect hair shine may not be found.
The ideal testing situation for any hair product is a combination of both instru-
mental and consumer tests. The instrumental tests provide a scientific rationale for
consumer perception. They also provide a good screening tool that can be used to
guide formulation. The consumer tests tell the formulator how well consumers will
like the product and their perceptions of how well the product works.
The authors would like to thank Philippe Clemenceau of Bossa Nova Technologies for his help in
researching this article.
For Further Reading

M Reiger, ed., Harry’s Cosmetology 8th Ed., Chemical Publishing Co., NY
(2001)
CR Robbins, Chemical and Physical Behavior of Human Hair, 2nd ed, Springer-
verlag NY (1988)
R Schueller and P Romanowski, Hair tress testing, Cosm Toil vol. 114, #11
47–52 (Nov. 1999)
C Reich and C and R Robbins, Light scattering and shine measurements of
human hair: A sensitive probe of the hair surface, JSCC 44 221–34 (July/
Aug 1993)
W Czepluch et al., Gloss of hair surfaces: Problems of visual evaluation and
possibilities for goniophotometric measurements of treated strands, JSCC,
44 299–318,(Nov/Dec 1993)
520
K Keis and K.R. Ramaprasad, Studies of light scattering from ethnic hair fibers,
J Cosm. Sci 55 49–63 (Jan/Feb 2004)
R McMullen and J Jachowicz, Optical properties of hair: effects of treatments
on luster as quantified by image analysis, J Cosm. Sci 54 335–51 (July/Aug
2003)
Index
A fragrances, 283, 287

regulations, 399
ACGIH (American Conference of
Association of Analytical Communities
Governmental Industrial Hygienists), 59
(AOAC), 444. See also preservatives,
ACS (American Chemical Society), 16
PET (preservative efficacy testing)
ADC (accelerated double challenge) test,
ASTM (American Standards of Testing
448–450
Materials), 16, 444
applications, 444
requirements, 445
versus USP (United States B
Pharmacopeia) testing, 450–453 bath/shower products
aerosols, 12, 259–260 fragrances, 283, 284, 286
alternatives, 269–270 gels, 253
disadvantages, 265 botanicals, INCI differences, US and EU,
expelled aerosol forms, 267–268 43, 45
fragrances, 283, 287
manufacturing, 268–269 C
packaging, 260–264
product concentrate chemistry, careers in cosmetic science
264–266 company types in industry, 4
propellants, 266–267 industry organizations, 16
QC/QA, 269 ingredients suppliers, 9–10
regulators, 260 perfumery, 10
sun care, 378–379 process engineering, 9
American Conference of Governmental product development, 3–5
Industrial Hygienists (ACGIH), 59 programs available, 5–7
American Standards of Testing Materials QC/QA (quality control/quality
(ASTM), 16, 444 assurance), 7–8
anitperspirants. See APDs (antiperspirant/ regulatory specialty, 9
deodorants) CAS (Chemical Abstracts Service), 59
AOAC (Association of Analytical CDER regulations, 26
Communities), 444. See also CER (Cohesive Energy Ratio) system, 135
preservatives, PET (preservative efficacy CERCLA (Comprehensive environmental
testing) Response, Compensation, and Liability
APDs (antiperspirant/deodorants). See Act), 59
also sweat glands/sweating CFC (chlorofluorocarbon), 13
antiperspirants, 398, 400 CFR (Code of Federal Regulations), 18
versus deodorants, 397–398 MSDSs, 59
efficacy, 400 recalls, 23
cosmetic sticks, 255 warnings, 23
521
522
Index Beginning Cosmetic Chemistry
Chemical Abstracts Service (CAS), 59 Engelhard borosilicate Reflecks,

chemical feedstock, 14 163–164
chlorofluorocarbon. See CFC inorganic, 149–153
CIR (cosmetic ingredient review), 18 inorganic, versus organic, 154
Expert Panel, 46 market demand, 159–161
PCPC, 30 QC/QA, 156
Code of Federal Regulations (CFR), 18 selection process, 151–153
MSDSs, 59 Comprehensive environmental Response,
recalls, 23 Compensation, and Liability Act
warnings, 23 (CERCLA), 59
Cohesive Energy Ratio (CER) system, 135 Consumer Commitment Code, PCPC
COLIPA (European Cosmetic, Toiletry (Personal Care Products Council
and Perfumery Association), 16 (formerly CTFA), 29
INCI ingredient nomenclature Consumer Federation of America, 30
conventions, 30–38 consumer perceptions, 17, 26
information sources in US and EU, Consumer Federation of America, 30
42 cortex (hair), 13, 76–77
labeling, 41 cosmeceuticals, 26
name assignment procedures, 41 regulations, 466
sources, 38–39 cosmetic industry
systems, 39–41 nanotechnology, 431
Color Additives Amendments of 1960, nanomaterials, 432–433
FD&C (Food, Drug and Cosmetic safety, 433–434
Classification) Act, 23 RFID (radio frequency identification)
colorants, 14 tags, 427–431
batching process, 155–156 terminology, 12
chemical classification, 148–150 Cosmetic Ingredient Dictionary, 461–462
hues, 150 cosmetic ingredient review. See CIR
shades, 154–155 cosmetic products
dyes, 148, 149 claims, 464–465, 469–471
emulsions, 240 body and mind connection,
hair, oxidative, 173–175 471–477
history, 147–148 supporting, 9, 18
INCI differences, US and EU, 43–45 definition
International Color Handbook (CTFA), FD&C, 25, 479–480
147, 149 Federal Registry, 18
nomenclature systems, 39–40, 151 general development, process, 232–233
Japan, 149 constraint workarounds, 233–234
US and EU, 148–149 initial concepts, 231–232
outlook, 157 regulations, 234
pigments, 148, 149 terminology, 12–13
versus colorants, 159 cosmetic science careers
Eckart Visionaire metallic effect, company types in industry, 4
162–163 industry organizations, 16
effects, 161 ingredients suppliers, 9–10
EMD Chemicals Timiron Splendid, perfumery, 10
164–165 process engineering, 9
523
Beginning Cosmetic Chemistry Index
product development, 3–5 E

programs available, 5–7
ELNs (electronic lab notebooks),
QC/QA (quality control/quality
209–212, 221–222
assurance), 7–8
emollients, 14
regulatory specialty, 9
emulsions, 239
cosmetic sticks, 254
hair conditioners, 99–100
APDs (antiperspirant/deodorants), 255
emulsions/emulsion systems, 12, 237–238
chemistry, 255
aerosols, 268
lipsticks/lip moisturizers, 255
CER (Cohesive Energy Ratio) system,
manufacturing, 256–257
135
skin applications, 255–256
emulsifiers, 14, 130–131, 239
sun care, 378
polymeric, in creams, 241–242
Cosmetics Directive, EU, 46–47
formulation process, 133–135
CPSA (Consumer Products Safety
polymer-stabilized creams, 242–243
Administration), aerosols, 260
fragrances, 292–295
creams/lotions, rheological studies,
HLB (hydrophilic/lipophilic balance)
241–244
system, 134–135
results, 244–249
hydrophilic, 129
CSPA (Consumer Specialty Products
hydrophobic, 129
Association), aerosols, 260
multiple emulsions, 130
C&T magazine, 468
o/w (oil/water) emulsions, 129, 238–240
CTFA (Cosmetic Toiletry and Fragrance
phases
Association), 16, 444. See also PCPC
aqueous, 130
(Personal Care Products Council)
oil, 15, 130
regulations, 457
PIT (Phase Inversion Temperature)
international regulations, 462–463
system, 135
from TGA, 461
stability, 131
CTPA (Cosmetic, Toiletry and Perfumery
destabilization, 131–133
Association), UK, 16
structures, 131
sun care, 377–378
D surfactant properties, 113–114
Delany Clause, FDA (Food and Drug w/o (water/oil) emulsions, 129
Administration), 18 environmental concerns, regulations, 465
denatured alcohol, INCI differences, US EPA (Environmental Protection Agency),
and EU, 43, 45 aerosols, 260
deodorants. See APDs (antiperspirant/ EP/BP (European Pharmacopoeia/
deodorants) British Pharmacopoeia), 444. See also
dimethicone, hair conditioners, 101 preservatives, PET (preservative efficacy
DOT (Department of Transportation), 16 testing)
aerosols, 260 European Pharmacopoeia/British
MSDSs, 59 Pharmacopoeia (EP/BP), 444. See also
drugs, definitions preservatives, PET (preservative efficacy
FD&C, 19 testing)
Federal Registry, 19
524
F formulation process, 181–182, 193, 282

polarity, 295–297
Fair Packaging and Labeling Act. See
solubility, 283–285, 295–296
FPLA
stability issue, 182–183
FDA (Food and Drug Administration), 16
water/octanol partitions coefficients,
cosmetic industry role, 21–28
296–297
Delany Clause, 18
INCI nomenclature, 43, 46
regulations, 22–23
odor profiles, 285–287
Voluntary Cosmetic Registration
purchasing influences of, 188–189
Program, 28
raw materials, 291–292
FD&C (Food, Drug and Cosmetic
natural, 180, 190–192
Classification) Act, 14, 23
odor changes to, 187–188
Color Additives Amendments of 1960,
synthetic, 192
147, 149
safety and regulations, 183–186,
cosmetics or drugs, determination, 25
195–196
recalls, 23
allergens, 184, 195
Federal Food, Drug & Cosmetic Act. See
in surfactant systems, 297–299
FFDCA
terminology, 178
Federal Registry
testing, 193–194
cosmetics, definition, 18
FTC (Federal Trade Commission), 16
drugs, definition, 19
Federal Trade Commission. See FTC
(Federal Trade Commission) G
FFDCA (Federal Food, Drug & Cosmetic gels/mousses, 12
Act), 19 aerosols, 268
Food, Drug and Cosmetic classification. body care, 253
See FD&C clarity, 252
Food and Drug Act of 1906, 147 facial care, 253
Food and Drug Administration. See FDA gelling agents, 14
(Food and Drug Administration) hair care, 252, 307, 309
FPLA (Fair Packaging and Labeling Act), hair styling, 330
19, 23 manufacturing, 254
fragrance houses, 4, 12, 177 oral care, 253–254
in development process, 181 shear thinning, 251–252
in formulation process, 182, 183 sun care, 378
fragrances, 14 GMPs (good manufacturing practices), 28
creation process, 177, 188, 292 good manufacturing practices. See GMPs
bases, 179–180, 183 green cosmetics, 12
fragrance briefs, 177, 178–179, creams, polymer-stabilized, 242
189–190 environmental regulations, 465
development process, 181
checklist, 290 H
in emulsions/emulsion systems, 240,
292–295 hair
environmental issues, 287–289 color and gloss, 495–500
cortex, 13, 76–77
cuticle, 13, 74–76
525
lipids in hair shaft, 77–78 I

optical properties, 513–514
ICMAD (Independent Cosmetic
physical structure, 513
Manufacturers and Distributors), 16
hair care products. See also gels/mousses;
IFRA (International Fragrance
hair conditioners; hair styling; shampoos/
Association), 178
conditioning shampoos
IFSCC (International Federation Societies
chemically modified
of Cosmetic Chemists), 16
experiments, 489–493
INCI (International Nomenclature of
porosity, 487–488
Cosmetic Ingredients) nomenclature, 19
tensile strength, 488–489
colorants, 151
curl retention testing, 17
conventions, 30–38
hair bleaching, 172–173
EU
hair coloring, 311
colorants, 148–149
oxidative, 173–175
differences with US, 43–46
hair relaxers, 170–172, 310
information sources in, 42
permanent waving, 168–170, 309–310
polymers, 307–308
Japan
shine evaluations, 513–515
colorants, 149
testing methods, 515–519
solvents, 308
labeling, 41
tress testing, 507–512
MSDSs, 59
hair conditioners, 14
name assignment procedures, 41
dimethicone, 101
sources, 38–39
emollients, 99–100, 306
systems, 39–41
emulsifiers, 307
US
fragrances, 383, 386
colorants, 148–149
humectants, 100–101, 306–307
differences with EU, 43–46
petrolatum, 101
information sources in, 42
polymers, cationic, 98–99, 306
quats, 97–98
International Fragrance Association
surfactants
(IFRA), 178
cationic, 13, 97–98, 305–306
properties, 114, 304
hair styling J–K
aerosols, 329–330 Japanese Pharmacopoeia (JP), 444. See
gels/mousses, 330 also preservatives, PET (preservative
hair dressings, 330 efficacy testing)
hair sprays, 307, 309 JCIA (Japanese Cosmetic Industry
history, 325–327 Association), 16
packaging, 331 JP (Japanese Pharmacopoeia), 444. See
pomades, 330 also preservatives, PET (preservative
VOCs (volatile organic compounds), efficacy testing)
326–328, 331
HLB (Hydrophile/Lipophile Balance)
system, 16, 134–135
526
L microencapsulation–microcapsules/
millicapsules
lab notebooks
fragrance management, 273–276
example, 218–220
performance enhancement, 277–279
formats
technology, 271–273
books, 212, 217–218, 220–221
microorganisms, personal care products
electronic, 209–212, 221–222
contamination of products, 198–199
pages, 212–213
bacteria, 197–198
information to include, 209, 217
molds, 198
patent issues, 211
yeasts, 198
regulations, 211
growth/infections, 198
storage/preservation, 209, 210,
tracking/controlling, 199
216–217, 221–222
preservatives, 199–200
value, 207–208, 215–216
alcohols, 202
labeling
diols with higher molecular weight,
FDA, 22–23
203
INCI nomenclature, 41
formaldehyde, 201
regulations, 458, 465–466, 480–482
organic compounds, 202–203
requirements, 28
parabens, 200
LAST (lactic acid sting test), 82–83
phenol derivatives, 201–202
quaternary compounds, 202
M Ministry of Health, Labor and Welfare,
manufacturing Japan, 47–48
aerosols, 268–269 MPA (Manufacturing Perfumersí
contract manufacturers, 4, 12 Association), 457
cosmetic sticks, 256–257 MSDSs (Material Safety Data Sheets), 19,
FDA 57–58. See also regulations; safety
inspections, 16 critical sections, 58–60
registering with FDA, 25 requirements
finished goods manufacturers, 12 international, 60
gels, 254 preparing MSDSs, 60–61
gels/mousses, 254
GMPs (good manufacturing practices), N
28
NAD (National Advertising Division of the
ingredient supplier careers, 9
Council of Better Business Bureaus), 16
laboratory batching
nanotechnology, 431
considerations, 227–229
nanomaterials, 432–433
preparations, 225–227
nanoparticle regulations, 467
product storage, 229–230
safety, 433–434
procedures, 16
National Fire Protection Association
Manufacturing Perfumersí Association
(NFPA), 59
(MPA), 457
Natural Movement. See green
Material Safety Data Sheets. See MSDSs
natural oils
methyl esters, natural oils, 125–126
classification, 121–123
cosmetic applications, 123–124
methyl esters, 125–126
527
preparation process, 119–121 PCPC (Personal Care Products Council

selection guidelines, 117–118 (formerly CTFA), 16, 19
surfactant transformation, 126–128 aerosols, 260
titer points, 119 CIR (cosmetic ingredient review), 30
triglycerides, 118–119 Consumer Commitment Code, 29
classification, 121 cosmetic industry role, 29–30
wax esters, 124–125 INCI ingredient nomenclature
NDA (New Drug Application), 19 conventions, 30–38
approval requirements, 27–28 information sources in US and EU,
New Drug Application. See NDA 42
NFPA (National Fire Protection labeling, 41
Association), 59 name assignment procedures, 41
notebooks. See lab notebooks sources, 38–39
systems, 39–41
O pearlizing agents, 15
PEL (Permissible Exposure Limit), 59
Occupational Safety and Health
perfumery. See also fragrances
Administration. See OSHA
careers, 10
(Occupational Safety and Health
Permissible Exposure Limit (PEL), 59
Administration)
perspiration. See sweat glands/sweating
oral care products, gels, 253–254
PET (preservative efficacy testing),
OSHA (Occupational Safety and Health
443–444
Administration), 16
methodologies, in-house, 446–447
MSDS, 57
methodologies, standard, 444–446
MSDSs, 59
objectives, 447
OTC (over-the-counter) drugs, 19
Pharmaceutical Affairs Law, Japan, 47–48
compliance, 27–28
Phase Inversion Temperature (PIT)
monographs, 19
system, 135
pigments
P colorants, 148, 149
PABA (para-amino benzoic acid), 375 effects, 161
packaging, 18, 419 inorganic, 149–153
aerosols, 260–264 inorganic, versus organic, 154
container types, 419–421 versus pigments, 159
closures, 421–422 Eckart Visionaire metallic effect,
engineerís role, 425–426 162–163
FPLA (Fair Packaging and Labeling EMD Chemicals Timiron Splendid,
Act), 19 164–165
hair styling, 331 Engelhard borosilicate Reflecks,
materials 163–164
glass, 423 market demand, 159–161
metals, 423 PIT (Phase Inversion Temperature)
plastics, 422–423 system, 135
selection process, 423–425 preservatives, 15
Patent and Trademark Office, laboratory accelerated testing, issues, 447–448
notebooks, 211, 215–216, 218 ADC (accelerated double challenge)
test, 448–450
528
applications, 444 regulations, 464–465. See also MSDSs;

requirements, 445 safety; testing
versus USP (United States additives
Pharmacopeia) testing, 450–453 bleaching agents, teeth, 465
ASTM (American Standards of Testing color, 460, 463–464
Materials), 444 food, 460
CTFA (Cosmetic Toiletry and methylene chloride, 464
Fragrance Association), 444 APDs (antiperspirant/deodorants), 399
PET (preservative efficacy testing), batch certification, 459
443–444 bovine scare, 467
methodologies, in-house, 446–447 careers, 9
methodologies, standard, 444–446 CDER, 26
objectives, 447 Color Additive Amendment, 460–461
process engineering communication with public, 460
careers, 9 cosmeceuticals, 466
terminology cosmetic products, 439
marketing, 18 claims, 9, 464–465
process, 15–17 versus drugs, 482–485
product development, 3–5. See also CTFA, 457
specific products international regulations, 462–463
analytical methods development, 8 from TGA, 461
intended use, 26 deceptive products, 459
terminology Eagleton Bill, 462
industry, 12 environmental concerns, 465
product types, 12–13 FDA, 22–23
scientific, 13 ingredients, 458
testing, 17–18 labeling, 458, 465–466, 480–482
MPA, 457
Q nanoparticles, 467
phthalates, 467
QC/QA (quality control/quality assurance)
regulatory career specialty, 9
aerosols, 269
self-regulation, 461
analytical methods development, 8
sun care products, 466–467
careers, 7–8, 17
terminology, 18–19
colorants, 156
Cosmetic Ingredient Dictionary,
461–462
quats/quaternary compounds, 15
C&T magazine, 468
hair conditioners, 97–98
marketing, 18
preservatives, 202
product testing, 17–18, 463
TGA, 459
R to CTFA, 461
radio frequency identification (RFID) warnings, 23, 481
tags, 427–431 Web sites, 483
record keeping. See lab notebooks Relative Polarity Index (RPI), 347–354
Registry of Toxic Effects of Chemical repeat insult patch testing. See RIPT
Substances (RTECS), 59 RFID (radio frequency identification)
tags, 427–431
529
rheological additives, 15 skin. See also skin delivery

RIPT (repeat insult patch testing), 17 color and gloss, 495–500
Risk and Safety Statements, EU, 60 facial care
RPI (Relative Polarity Index), 347–354 conspicuous pores, structure,
RTECS (Registry of Toxic Effects of 403–404
Chemical Substances), 59 conspicuous pores, treatment,
407–408
S nucleated cells, 404
sebum component effects, 404–406
safety. See also MSDSs; regulations
unsaturated fatty acid effects,
career specialties, 9
406–407
FDA, 22–23
fragrances
nanotechnology, 433–434
lotions/creams, 283, 286
PCPC, 29–30
powders/talcs, 283, 287
SARA (Search and Rescue Aid), 59
makeup formulations
SCC (Society of Cosmetic Chemists), 16
materials, 409–413
SCCP (Scientific Committee on
optical effects, measuring, 413–415
Consumer Products), EU, 46
testing, 415–417
fragrance regulations, 183–184
sensitive skin, 81–84, 357–358
SCS (Society of Cosmetic Scientists), UK,
allergic reactions, 334
16
barrier functions, 359
Search and Rescue Aid (SARA), 59
formulations, 336–338, 366–367
shampoos/conditioning shampoos, 303
harsh ingredients, 335
conditioning agents, 304
harsh products, 335
foaming, 503–506
hypoallergenicity, 336
formulations, 313–315
ICD and ACD, 334
fragrances, 283, 285, 286
identifying risks, 364–366
surfactants, 304
immune responsiveness, 359
thickeners
LAST (lactic acid sting test), 82–83
acrylics, acid-based, 321
neurosensory input, 358
alkanolamides, 317–318
physiology, 358
cellulose, 320–321
SC (stratum corneum), 83–84
gums and clays, 321–322
sensitization, 334–335
polyethylene glyccol, 318–320
testing, 338–340
salts, 316–317
testing, in vitro, 363–364
silicones, 15, 137–139
testing, in vivo, 363
compounds, silicone-modified versus
testing, measuring skin response,
hydrocarbon, 144
362–363
emulsions, 240
testing methods, 82–83, 359–360
hair conditioners, 99
testing panels, 361–362
nomenclature systems, 39
skin delivery, 344–345
quartz to silicon, 137
formulations, influence on, 346
structure
RPI (Relative Polarity Index), 347–354
construction, 139–141
SPF (sun protection factor), 19
derivitization, 143–145
DHA effect, 389
functionalization, 142–143
ratings, sun care products, 379–380
530
sun protection factor. See SPF properties, 111–115

sunscreens/sun care products solutions, 105–106
chemical absorbers, 374–376 structure/function chart, 110
formulations, 376–379 sweat glands/sweating, 87–88. See also
outlook, 379 APDs (antiperspirant/deodorants); skin
self-tanners, 381–382 axilla microbiology, 92–93
quantification, 387–388 bad order precursors, 90–92
self-tanners, DHA (dihydroxyacetone) odor controls, 397
chemistry, 384 odor formation biochemistry, 93–94,
discovery/acceptance, 382 396–397
formulations, 385–386, 388–392 odor perception, 94–95
ingredients, 386–387 sweating process, 88–90, 395–396
structure, 382–383 T
SPF ratings, 379–380
testing. See product development, testing
DHA effect, 389
cosmetic products, 234–235
testing, 379
functionality tests, 439, 440–441
UV (ultraviolet) light effects
physiochemical tests, 437–439
hair, 374
regulations, 439
regulations, 466
preservatives
skin, 373–374
accelerated testing, 447–448
suppliers, 12
ADC (accelerated double
careers, 9–10
challenge) test, 444, 445, 448–453
and chemists, 68–69
ASTM (American Standards of
idea/trend generation, 68–69
Testing Materials), 444
new ingredients, 65–66
CTFA (Cosmetic Toiletry and
samples, evaluating, 66–67
Fragrance Association), 444
samples, requesting, 66
PET (preservative efficacy testing),
cosmetics industry role, 63
443–447
vendor view, 64–65
product development
working relationships, 70
laboratories, 4
and purchasing departments, 69–70
raw materials, 4
TEWL (transepidermal water loss) testing,
specifications, 68
18
sales calls, 65
TGA (Toilet Goods Association), 459
technical support, 67
to CTFA, 461
technical testing, 68
Threshold Limit Value (TLV), 59
surfactants, 15
TLV (Threshold Limit Value), 59
amphoteric, 107, 109, 111
Toilet Goods Association (TGA), 459
anionic, 107, 109
Toxic Substances Control Act (TSCA), 59
cationic, 107, 108 111
toxicology, career specialties, 9
fragrances, 297–299
transepidermal water loss. See TEWL
natural oils, 126–128
trivial names, INCI differences, US and
nonionic, 107, 108, 111
EU, 43, 45–46
physical chemistry, 103–105
TSCA (Toxic Substances Control Act), 59
531
U–Z
United States
Consumer Products Safety
Administration (See CPSA
(Consumer Products Safety
Administration))
Department of Transportation
(See DOT (Department of
Transportation))
Environmental Protection Agency
(See EPA (Environmental Protection
Agency))
Federal Registry (See Federal Registry)
Federal Trade Commission (See FTC
(Federal Trade Commission))
Food and Drug Administration
(See FDA (Food and Drug
Administration))
Occupational Safety and Health
Administration (See OSHA
(Occupational Safety and Health
Administration))
Patent and Trademark Office (See
Patent and Trademark Office)
VCRP (Voluntary Cosmetic Registration

Program), 28
VOCs (volatile organic compounds), 15
WHMIS (Workplace Hazardous Materials

Information System), 60

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Beginning Cosmetic Chemistry

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Beginning Cosmetic Chemistry Third Edition

■ Perry Romanowski, Randy Schueller

Practical Knowledge for the

Allured Business Media

Copyright 2009, by Allured Publishing Corporation. All Rights Reserved.

Allured Business Media

2. Your Primer of Technical Terms and Chemical Jargon

3. Cosmetic Ingredient Nomenclature

4. INCI Names: International Harmonization

5. Material Safety Data Sheets

6. Building Effective Supplier Relationships

Section II: Basic Cosmetic Science: Biology of hair and skin;

8. New Directions for Sensitive Skin Research

9. Axillary Odor: Its Physiology, Microbiology and Chemistry

10. Conditioning Agents for Hair and Skin

11. Surfactant Science

12. Oils of Nature

13. Understanding Emulsions

14. Silicone Chemistry

15. Creating Colorful Cosmetics

16. Pigments: Achieving the Effect

17. The Science of Reactive Hair Care Products

18. The Essence of Fragrance

19. Common Scents

20. Microorganisms and Personal Care Products

Section III: Product Development: From Beaker to Bottle

22. Laboratory Notebooks: Valuable Indicators of Intellectual

23. Laboratory Batching of Cosmetic Products

24. Successful Product Development

25. Formulating Cosmetic Emulsions: A Beginner’s Guide

26. The Aging of Polymer-Stabilized Creams:

27. Gels and sticks

28. Aerosols for Apprentices

29. Encapsulation Technologies: Tailored Solutions for Delivery

30. What Every Formulator Needs to Know about Fragrance

31. Fragrance in Emulsion and Surfactant Systems

32. Fundamentals of Formulating Hair Care Products

33. Introduction to Shampoo Thickening

34. Innovations in Hair Styling Technology

35. Understanding “Mild” Cosmetic Products

36. Formulating for Efficacy

37. Formulating for Sensitive Skin

38. The ABCs of SPF

39. Self-Tanners: Formulating with Dihydroxyacetone

40. The Dry Facts About Wet Perspiration

41. Improving the Appearance of Facial Pores

42. A Light-Diffusing Concept for Antiaging Effects in Makeup

43. Cosmetic Product Packaging

44. Emerging Technologies and the Future of Cosmetic Science

Section IV: Does It Work: Product Testing, Regulatory

46. Preservative Efficacy Testing: Accelerating the Process

47. The Century of Progressive Regulation

48. Mind Over Matter: Cosmetic Claim Substantiation Issues

49. The Regulatory Interface: When is it a Cosmetic and

50. Correlating Porosity and Tensile Strength of Chemically

51. In Vivo Quantitative Evaluation of Gloss

52. Evaluating Shampoo Foam

53. What You Should Know About Testing on Human Hair

54. Evaluating Shine on Hair

Your Career in Cosmetic

key words: careers, contract manufacturers, testing laboratories,

Industry Overview Sidebar

degrees in biology or related science. A few US colleges offer specialized cosmetic

Table 1.1. Cosmetic science programs in the United States

22. Laboratory Notebooks: Valuable Indicators of Intellectual

26. The Aging of Polymer-Stabilized Creams:

42. A Light-Diffusing Concept for Antiaging Effects in Makeup

48. Mind Over Matter: Cosmetic Claim Substantiation Issues

49. The Regulatory Interface: When is it a Cosmetic and

50. Correlating Porosity and Tensile Strength of Chemically

Table 3.3. Inventory of Ingredients—Nomenclature Conventions

istribution of components due to their natural source (e.g., coconut) are