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Development Team

Principal Investigator Prof. Farhan J Ahmad


Jamia Hamdard, New Delhi
Dr. Vijaya Khader
Former Dean, Acharya N G Ranga Agricultural University
Dr. Javed Ali
Paper Coordinator
Jamia Hamdard, New Delhi

Content Writer Dr. Javed Ali


Jamia Hamdard, New Delhi

Dr. Pratibha Nand


Content Reviewer Principal, South Point College, Haryana

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CONTENTS:

 Introduction to basic thermodynamics

 Theory of emulsions

 Fragrance selection, stability and testing

 Environmental safety and industrial network

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Introduction to basic thermodynamics

The term “thermodynamics” was coined by William Thompson (Lord Kelvin) in year

1749.Itcomes from the Greek words: thermo (heat) and dynamics (power).The name heat-power

is appropriate because thermodynamics explains the conversion of heat into power by steam

engines. Thermodynamics in context of cosmetics reflect the stability and elegance of the

formulation. Thermodynamically stable cosmetic preparations show better stability in storage

conditions. There are some basic laws of thermodynamics which are described as:

Zeroth law of thermodynamics

If two systems are in thermal equilibrium with a third one, they are also in thermal equilibrium

with each other. Systems are assumed to be in thermal equilibrium with each other if

spontaneous molecular thermal energy exchanges between them do not lead to a net exchange of

energy. This law is assumed in every measurement of temperature.

First law of thermodynamics

This is the fundamental laws of nature and is based on the principle of conservation of energy.

The first law of thermodynamics states that during an interaction, energy can only change from

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one form to another, neither created nor destroyed but the total amount of energy remains

constant.

Second law of thermodynamics

Energy has quality as well as quantity, and actualprocesses occur in the direction of decreasing

quality of energy.Whenever there is an interaction between energy and matter, thermodynamics

isinvolved. The thermodynamically stable cosmetic preparations are considered to be the stable

ones. It is discussed below in reference to the emulsion because various cosmeceuticals are

prepared through emulsification processes.

Theory of emulsion

In ancient time, there was a paradox as “water and oil can’t mix” but the concept of emulsion

demonstrated that these two phases- aqueous and oily, can be mixed very well to form stable

formulation. It has been known for many centuries that emulsion was used for cosmetics

purpose. Nowadays there is an enormous scope of emulsion technology in cosmetics, toiletries

and health-care markets. The reasons for popularity of emulsion include incorporation of both

polar and non-polar materials in the same formulation. Earlier, emulsion technology has been

associated with skin care products, but now the application of emulsion has become much wider.

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Currently, hair conditioners, antiperspirants, color cosmetics and cleansing products are also

based on latest emulsion technology.

Emulsion can be defined as mixture of two or more immiscible liquidsor it can also be

defined as a two phase system which is consisting of two immiscible or partially miscible liquids

in which one is dispersed in another as very fine droplets. These two phases are oil and aqueous

system. The term emulsion was coined from Latin word for “to milk” as milk is an emulsion of

fat and water with many more ingredients. Emulsion is mainly categorized in two categories

namely; oil in water type and water in oil type.

Oil in water type: In which discrete droplets of oil are dispersed in water.

Water in oil type: In which discrete droplets of water are dispersed in oil.

In addition to these two classes of simple emulsion, some more complex systems are also there

such as three phase complex emulsions- oil-in-water-in-oil (O/W/O) or water-in-oil-in-water

(W/O/W). These newer classes offer greater degree of formulation flexibility with more

efficacious and pleasant cosmetic products. As emulsions are thermodynamically unstable, the

emulsifier is added to stabilize the emulsion system. Emulsifier stabilizes the system by forming

a thin filmaround the globules of dispersed phase.

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Of late, there are advanced classes of emulsion namely microemulsion and nanoemulsion with

droplets size of less than 200 nm.

Many theories have been given to explain the stabilization of emulsion by the emulsifier. At

present, there is no single theory that can be applied universally to all emulsions. Rather, there

are different theories namely electric double layer theory, phase volume theory, hydration theory

of emulsions, oriented wedge theory, adsorbed film and interfacial tension theory to justify the

stabilization of emulsion via emulsifier.

Electric double layer (EDL) or double layer (DL) theory:

The first theory for the electrical double layer was given by Gouy and Chapman. DL is a

structure which appears onto surface of an object when it is exposed to a fluid. It refers to the

parallel layers of charge surrounding object. The first layer is of surface charge(positive/

negative), comprises of ions adsorbed onto the object due to chemical interactions. Second layer

is made up of ions that are attracted to the surface charge via the Coulomb force. The second

layer is associated with object. It is composed of free ions which move in fluid with the influence

of electric attraction and thermal motion. It is therefore called as "diffuse layer”.Themagnitudeof

these forces increases with increase in surface charge density (or the electrical surface

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potential).For unequally charged objects and eventually at shorter distances, these forces may

also be attractive. The theory ofDerjaguin, Landau, Verwey, and Overbeek (DLVO) combines

such double layer forces together with Van der Waals forces in order to estimate the actual

interaction potential between colloidal particles.

According to this theory there is an interaction between infinite homogenously charged wall

(described by surface charge density σ) and infinite electrolyte solution extending on one side of

the wall. Ions of the electrolyte are described by point-like charges of both signs in water

medium (which is defined by the permittivity constant ε). According to this model the electric

potential function and the corresponding average charge distribution are computed in the

neighborhood of the charged surface. The layers of two oppositely charged ions, known as

Helmholtz double layer, are not confined just to emulsions but to all boundary. The electric

charge is a key factor to be considered for the stability of emulsions which is stabilized with

emulsifying agents.

The phase-volume theory

If spheres of the same diameter are packed as close as possible, one sphere will touch 12 others

and the volume that spheres occupy is about 74% of the total volume. Thus if the spheres or

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drops of the dispersed phase remain rigid it is possible to disperse 74 parts of the dispersed phase

in the continuous phase, but if the dispersed phase is increased to more than 74 parts of the total

volume, a reversal of the emulsion will occur. However, the dispersed phase does not remain

rigid in shape but the drops flatten out when they come in contact with each other. Moreover, all

the dispersed particles are not of the same size; therefore, it is possible for the dispersed phase to

be consisted of 1 to 99% of the emulsion.

Hydration theory of emulsions

Fischer and Hooker stated that hydrated colloids make the best emulsifiers. Fischer stated that

emulsifying agent, by which a permanent emulsion is obtained, invariably "proves to be a

hydrophilic colloid when water and oil emulsions are concerned. Put another way, oil cannot

permanently be beaten into water, but only into a colloid hydrate."

Oriented wedge theory

This theory has been given from the work of Langmuir and Harkinsfor the manner in which

emulsions are stabilized. It is based upon the concept that the molecules of the emulsifier orient

themselves at the interface between the dispersed and continuous phases, forming a wedge like

structure, the curvature of which determines the size of the dispersed phase. It explains the

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emulsion formation on the basis of selective solubility of surfactant. Surfactant possesses a polar

and non-polar group. It orients itself in such a way that the polar group faces water and non-

polar group faces the oils, e.g., Soap.

Adsorbed film and interfacial tension theory

It is probably the most universally accepted theory for the formation of emulsions. This theory

has been developed or rather extended from earlier theories. According to this theory,

emulsification is influenced by the mass of the emulsifying agent, the ease with which this agent

is adsorbed at the interfacial separating surface, and the nature of the ions adsorbed by the

resultant film.

Plastic film theory (Interfacial film theory)

According to this theory, the emulsifier is deposited upon the surface of the droplets of the

dispersed phase in the form of plastic monomolecular film. This film prevents contact and

coalescence of the dispersed liquid. Actionof the emulsifier is purely mechanical and does not

depend upon surface tension.

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Fragrance selection

Selection of a suitable fragrance/perfume is a tedious task. A product which is intended to be

applied to a person’s body to make the person more attractive is defined as a cosmetic under the

law. Some examples of fragrance products that are regulated as cosmetics include Perfume,

Cologne and Aftershave.

Fragrance ingredients are also commonly used in other products, such as shampoos, shower gels,

shaving creams, and body lotions etc. Even some products labeled “unscented” may contain

fragrance ingredients which might react with active ingredients. This is because the manufacturer

may add just enough fragrance to mask the unpleasant smell of other ingredients, without giving

the product a noticeable scent. Some fragrance products that are applied to the body are intended

for therapeutic uses, such as treating or preventing disease, or affecting the structure or function

of the body. Products intended for this type of use are treated as drugs under the law, or

sometimes as both cosmetics and drugs.

Fragrances are classified into various olfactory families or groups.

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Aromatic scents: It consists of fragrances from aromatic plants. They are widely used in

aromatherapy and herbal medicine and currently their popularity in high-end perfumery has been

increased as well. These days, perfumes rarely belong to a single olfactory group.

Aldehydic perfumes: They contain chemicals belonging to the aldehyde group.

Aromatic perfumes: These are made up of various herbs, e.g. rosemary, basil or thyme.

Example: Aqua allegoriaherbafresca (Guerlain)

Aquatic perfumes: They have a base of synthetic ingredients that evoke the sea, mountain air or

fresh linen. Example: L'Eaud'Issey" (Issey Miyake)

Citrus/fruity perfumes: This includes bergamot, grapefruit, lemon, mandarin, sweet orange and

fruits such as peach, red berries, watermelon, etc. Example: Dior Addict 2.

Floral perfumes: They contain flower extracts, such as rose, lily or jasmine. Example: Pure

Poison (Dior).

Green perfumes: This is formerly known as chypre, are made of bergamot, labdanum, patchouli

and oakmoss. Example: Coco mademoiselle (Chanel).

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Gourmand perfumes: They consist of vanilla and tonka bean, chocolate or caramel. Example:

Delices (Cartier).

Oriental perfumes: These have a base of amber, musks, vanilla and other exotic plants.

Example: Dior addict (Dior)

Woody perfumes: These are made of woods such as cedar, patchouli, sandalwood and vetiver.

Example: Mediterranean (Elizabeth Arden)

Stability testing of cosmetics

The prime purpose of testingcosmetic products is to ensure a new or tailored product meets the

proposed physical, chemical and microbiological quality standards and aesthetics when stored at

suitable conditions. Development of cosmetic products is comparatively short, and testing

activity should not become economically disproportionate. Every year, each manufacturer may

have their disposal tests that are adapted according to their activity. Each manufacturer must

design their stability testing program such as it should be reasonable and efficiently addresses the

testingrequired. In other words “Stability testing is an experiment in which the samples of

cosmetics preparation is put at different environmental conditions for a set period of time. These

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conditions vary in temperature and light levels and are meant to simulate what will happen to the

product during its life cycle”.

Good Manufacturing practice as described in 21 CFR part 211 is applicable to all over the

counter (OTC) and prescription drug products and can be applied to cosmetics, in some ways,

and has been applied to nutritional supplements also.

Testing protocol

At selected intervals, evaluation of samples is required for various physical, chemical and

performance characteristics to see how they have changed. If the changes are found minimal

according to standards, then it is said to have “passed” stability testing. This means that the

cosmetic preparation has good stability and it will be stable for the duration of testing period.

The underlying assumption in stability testing is that increasing storage temperature speeds up

the aging reactions. A simple handy thumb rule is that a sample stored at 45 ºC for 8 weeks is

equivalent to one that is stored at room temperature for a year. This isn’t an exact predictor, but

is good enough for the purposes of cosmetic products.

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Due to extensive variety of cosmetics and their inherent complexity, “standard” stability tests

may not be prescribed. Manufacturers, who have depth knowledge of their products and

packages, need to modify testing protocols and to make a sound scientific basis to assess product

stability. Specific tests should be performed in order to predict possible alterations in the product,

to be at par with new/unusual technologies, and to be able to provide extended shelf lives to the

product.

New prototypes: Whenever we make a new formula and are satisfied with the way it performs,

we want to assess its stability.

New raw materials: Whenever we have to change the fragrance, color, or other raw material in

a formula, we have to assess its stability to make sure there aren’t any unacceptable changes.

Also, when we have a new raw material source (or supplier), stability testing is required.

New manufacturing procedure: Manufacturing is focused on finding faster ways to make

formulas. This often means to change some order of addition or shorten mixing time. Whenever

changes like this happen, it could affect the formulation time. This further requires to run a

stability test to see if the change is acceptable.

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New packaging: Cosmetic products require diversified types of packaging and their materials.

Paper, glass, metal and plastic material are generally used for cosmetics packagingand the global

market basically utilizes bottles, tubes, jars, containers, sticks, pumps, dispensers, roller balls,

caps and closures etc. for packaging purpose. Whenever the package is new, then it has to be

checked that the formulation is compatible with the container. Stability testing further ensure the

parameters.

How do we test stability of a cosmetic?

There are no set rules on how to conduct a stability test for cosmetic products. Of course, for

cosmetic OTC products like sunscreens, or dandruff shampoos, FDA has specific stability test

requirements that have to be followed. Some basic procedures are described that can be followed

for conducting a cosmetic formula stability test.

 A cosmetic preparation batch is designed. Then the amount of formulation is calculated

based on the number of samples that will be used for the stability testing. Usually, it’s a

good idea to make 30-40% more than we think we will need.

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 The glass jars are filled with the product along with the finished package. In stability

testing, both glass and packaging are subjected to testing if possible. The number of

samples depends on how much testing is to be done but at minimum we should have 2

samples for each storage condition.

 Initial readings are noted. Once we have a sample filled, it is tested for all the

characteristics we are going to evaluate later. The exact tests depend on the particular

product but minimally physical characteristics such as appearance, color and fragrance

are recorded. The viscosity and pH measurements are also performed. For aerosol

products, spray patterns are tested.

 Samples are put in different conditions. Stability testing requires different temperature

and light conditions. Some standard temperatures include 50 ºC, 45 ºC, 37 ºC, 25 ºC,

(RT), and 4 ºC. A freeze/thaw stability test is also conducted which involves cycling

ofproduct through 24 hours of freezing then 24 hours of thawing. Different lightening

conditions involve a fluorescent light box and a natural light box (to simulate sunlight).

 The product is evaluated. Samples should be evaluated at the following intervals of 2, 4,

8, 12 , and 52 weeks. Only the RT, 37 ºC and 4 ºC samples will be evaluated after one

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year. The highest temperature samples and the light exposed samples need to be

evaluated for the first three test intervals. The evaluation tests should be the same ones

we conducted when taking the initial readings.

 Lastly, stability is determined. After 8 weeks we can confidently decide whether the formula is

stable or not.

There are three forms of stability tests:

I. Physical and chemical integrity tests which evaluate color, odor/fragrance, pH value,

texture,viscosity, flow, and emulsion stability (signs of separation).

II. Microbiological stability tests which evaluate the degree of contamination with bacteria,

yeast and mold.

III. Packaging stability tests which evaluate the packaging of the product.

Physical/Chemical Stability Tests

Various approaches are described to predict how cosmetics will resist common stresses as higher

temperature and light. Generally manufacturers determine whether to perform such testing based

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on vulnerabilities of cosmetics product and its predictable shipping, storage display and use

conditions. Common test procedures include:

Temperature Variations: High temperature is now commonly used as a predictor of long-term

stability. Various companies conduct their high temperature testing at 37 ºC (98 ºF) and 45 ºC

(113 ºF). If a product is stored at 45 ºC for three months (and exhibits acceptable stability) then it

should be stable at room temperature for two years. Evidently, the product must be stored at 25

ºC (77 ºF) for a period of one year.

Cycle Testing: The product should pass three cycles of temperature testing from -10ºC (14ºF) to

25 ºC (77ºF). The product is placed at -10 ºC for 24 hours and at room temperature (25 ºC) for 24

hours. This comprise of one complete cycle. If the product passes three such cycles then it can be

said that the product has a good degree of confidence in the stability. An even more rigorous test

is a -10 ºC to 45 ºC five-cycle test. This puts emulsions under a remarkable stress and, if it passes

the test, it indicates that the emulsion exhibits very high stability.

Centrifuge Testing: The dispersed phase (of an oil-in-water emulsion) has a tendency to

separate and rise to top of the emulsion as oil droplets. This phenomenon is called creaming.

Creaming is one of the first signs of impending emulsion instability and this should be taken

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seriously. Centrifugation is a good test method to predict creaming of emulsion. Wherein, the

emulsion are heated to 50 ºC and then centrifuged for 30 minutes at 3000 rpm. After

centrifugation, the resultant product is inspected for creaming. This test is necessary for the

products which contain any kind of powders such as liquid/cream make-up.

Light Exposure Testing: Both formulas and packaging can be sensitive to the UV radiation. All

products must be placed in glass and the actual package, in the window and if its available a light

box that has a broad-spectrum output. Another glass jar totally covered with aluminum foil is

placed in the window to serve as control. Frequently, we will see significant discoloration of the

product and sometimes of the package also. This discoloration might be due to fragrance or some

other sensitive ingredient. Usually all that is needed is the addition of a UV absorber (e.g. 0.1%

of benzophenone).

Mechanical Shock Testing: In order to determine shipping damage of the cosmetic and its

packaging, mechanical shock testing is often conducted. Vibrational testing (e.g. on a pallet

shaker) may help in determination of de-mixing (separation) of powders or granular products.

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Monitoring: For all of the above mentioned tests, the color, odor / fragrance, viscosity, pH

value, and, if available, particle size uniformity and/or particle agglomeration should be

monitored under the microscope.

Microbiological Stability Tests

Microbial contaminants generally come from two different ways, firstly during production and

filling and secondly through the use of the cosmetics by consumers. From initial, the cosmetic

unit is opened by the consumer, a permanent microbial contamination to cosmetic is introduced

due to contact with the consumer’s hands and body.

Microbial preservation is essential to make sure microbial safety of cosmetics for consumers,

maintain the quality of the product, and confirms hygienic and high-quality handling.Therefore,

it is necessary to carry out routine microbiological analysis of each batch of the finished product.

Pseudomonas aeruginosa, Staphylococcus aureus and Candida albicans are considered as the

main potential pathogens in cosmetic products. These specific potential pathogens must not be

detectable in 0.1 g or 0.1 ml of a cosmetic product. The parameters examined, the criteria and

methods used, and the results obtained per batch should be well documented.

Screening Tests: There are various simple testing kits available in the market (e.g. dip-slides or

plate counts) which provide quick and semi-quantitative results whether a cosmetic product is

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significantly contaminated or not. Sampling and evaluation of the results is simple and can be

performed by personnel without any microbiological training.

Quantitative Tests: Quantitative tests determine the actual count level of bacteria, mold and

yeast. These tests are very sophisticated and laborious and can be performed only by qualified

personnel in professional microbiological testing laboratories. Methods of isolation for

microorganisms from cosmetic products comprise direct colony counts and enrichment culturing.

Packaging Stability Tests: Packaging may directly affect finished product stability because of

interactions which may occur between product, the packages and external surroundings. For

example, product constituents may be absorbed into the container or may chemically react with

the container. In addition, the container may not fully protect the product from adverse effects of

atmospheric oxygen and/or moisture or volatile product constituents (e.g. fragrances) may

evaporate through the container.

 Glass Tests: Glass is the most inert material and does not react with a cosmetic product in any

way. For this reason all testing should be done in glass and the actual packaging. In this way it

can be determined that whether the cause of product failure is the formula or the package.

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 Weight Loss Tests: To determine evaporation (water loss through the container wall or closure

gaps) weight loss evaluation is one of the most important tests that must be conducted. This

testing (performed in the actual package with the cap torqued to 100% of target torque) is done at

room temperature and at 45 ºC for a period of three months. The weight loss should not exceed

1% per month for the package to be considered acceptable.

 Leaking Tests: It is desirable to test the finished packaged product in different orientations

(upright, inverted, on its side, etc.) to determine whether the packaging may leak (especially

during transport).

Environmental safety and industrial network

Cosmetics are the products which are applied to human body for cleansing, beautifying, and

making the skin more attractive and pleasing. The purpose of using cosmetic products is to

maintain the body in a good condition, protect it from the effects of the environment and aging

processes, alteration in appearance, and to improve the body smell. Cosmetic products are widely

used by every socioeconomic class of human beings to cleanse, perfume, protect, and change the

appearanceof skin. Consumer’sassumption is that the cosmetic products are safer and pose no

risk to the human health, but the actual scene is different. A number of complaints have been

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filed and various regulatory bodies have found that sometimes the ingredients which are used to

make formulations were not safe. A number of chemicals are usually added to cosmetics

preparations as preservatives and fragrances, lots of them are found toxic and prohibited from

usage as ingredients becausetheycan cause cancer, mutation, reproductive toxicity, and endocrine

disruption. Studies conducted by the Environmental Defense in Canada revealed that heavy

metals such as lead,arsenic, and antimony were found as ingredients which were not listed on the

product label. These ingredients may be from raw materials and/or from processing methods.

Similarly,high levels of mercury in cosmetics creams and endocrine-disrupting chemicals were

also foundincosmetic products. Astudy from Nigeria also indicated an elevated level of lead in

facial talcum powders and othermetals in personal care products.

After these findings many countries have taken steps towards regulations of cosmetic products

and a committee has been coined to see the cosmetics product for its toxicity. All this led to

“Campaign for Safe Cosmetics”. It was the result of sincere efforts of educational, religious,

labor, women's, environmental and consumer groups with a goal to protect the health of

consumers and workers. It propels the health and beauty industry to make clear the use of

chemicals which are linked to cancer, birth defects and other health related problems and

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substitute them with suitable alternatives. It was started in 2002 with the release of a report, "Not

Too Pretty: Phthalates, Beauty Products and the FDA".

In this context, environmental and public health groups contacted with a laboratory to test 72

brand, off-the-shelf beauty products for the presence of phthalates and the laboratory testing

found the presence of phthalates in nearly¾th of the cosmetic products tested. Furthermore, the

chemicals that were used in these formulations were not listed on any of the labels. A second

report, "Pretty Nasty", documented similar product test results in Europe.

In February 2003, the European Union passed a new amendment to their Cosmetics Directive

that prohibits the use of known or suspected carcinogens, mutagens and reproductive toxins

(CMRs) from cosmetics. This amendment came into force in September 2004.

In 2004, members of the Campaign for Safe Cosmetics and more than 50 other organizations

signed a letter asking cosmetics companies and personal care product companies to sign the

Campaign for Safe Cosmetics (Campaign for the Global Production of Safer Health and Beauty

Products), a pledge to remove toxic chemicals and replace them with safer alternatives in every

market they serve.

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Safe Cosmetics and Personal Care Products Act of 2013

The purpose of this act was to ensure, all personal care products should be free from harmful

ingredients. Because existing laws, which were not been significantly updated since 1938, had

many loopholes, and allow use of chemicals linked to cancer, birth defects, learning disabilities

and other health related problems.The cosmetics industry was facing serious problems because

beauty products, shampoos, and lotions etc. were contaminated with toxic chemicals like cancer-

causing formaldehyde in baby shampoos, lead in lipsticks and mercury in skin creams. The Safe

Cosmetics and Personal Care Products Act of 2013 gave the beauty industry a much-needed

make-over.

Safe Cosmetics and Personal Care Products Act of 2013 proposed the following:

 To substitute ingredients that are linked to cancer, birth defects and others developmental

harm.

 To make health-based safety standards those includeespecially protections for children,

elderly, workers and other vulnerable populations.

 To close labeling loopholes by providing full ingredient list on labels and company

websites also.

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 To provide access to information about unsafe ingredients in cosmetics.

 To share the data for avoidance of duplicative testing and promote the other alternatives

to animal testing.

 To provide sufficient funding for the FDA Office of Cosmetics and Colors so that it has

the resources thatreport error of the cosmetics industry.

Industrial network

Voluntary self-regulation by the U.S. cosmetic industry is considered by many to be both a

regulatory anomaly and an excellent success.No industry in the history of the United States has

ever made a greater assurance to self-regulation or has been more successful in achieving it than

the U.S. cosmetic industry. Protecting industry image entails the maintenance of favorable

consumer perceptions of safety levels in order to achieve steady retail sales. The cosmetic

industry is sensitive to the image of an uncontrolled market where anything goes. They counter

this image with well-established self-regulation programs. Protecting industry independence

entails ensuring adequate industry safety levels in order to avoid the need for increased federal

regulation which would externally impose more stringent requirements upon the industry. Thus,

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the cosmetic industry since the 1960s or so has relied on self-regulation, particularly in times of

problems, to convince Congress not to enact new, more intrusive legislation.

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