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(11) EP 2 694 834 B1


(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:


of the grant of the patent: A61K 8/36 (2006.01) A61K 8/44 (2006.01)
17.07.2019 Bulletin 2019/29 A61K 8/46 (2006.01) A61K 8/49 (2006.01)
A61K 8/55 (2006.01) A61Q 5/04 (2006.01)
(21) Application number: 12754671.1 A61K 8/65 (2006.01) A61K 8/67 (2006.01)
A61K 8/20 (2006.01) A45D 7/06 (2006.01)
A45D 7/04 (2006.01) A45D 2/00 (2006.01)
(22) Date of filing: 09.03.2012
(86) International application number:
PCT/US2012/028444

(87) International publication number:


WO 2012/122457 (13.09.2012 Gazette 2012/37)

(54) KERATIN-BASED HAIR STRAIGHTENING FORMULATIONS, METHODS AND SYSTEMS


HAARGLÄTTUNGSFORMULIERUNGEN AUF KERATINBASIS SOWIE VERFAHREN DAFÜR UND
SYSTEME DAMIT
PRÉPARATIONS, PROCÉDÉS ET SYSTÈMES DE DÉFRISAGE DES CHEVEUX À BASE DE
KÉRATINE

(84) Designated Contracting States: (74) Representative: Bradley, Adrian et al


AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Cleveland LLP
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO 10 Fetter Lane
PL PT RO RS SE SI SK SM TR London EC4A 1BR (GB)

(30) Priority: 09.03.2011 US 201161464683 P (56) References cited:


US-A1- 2006 024 257 US-A1- 2007 028 938
(43) Date of publication of application: US-A1- 2009 165 812 US-A1- 2009 211 593
12.02.2014 Bulletin 2014/07 US-B1- 6 488 920 US-B1- 6 984 250

(73) Proprietors: • HALL K E ET AL: "APPLICATION OF THE


• Baum, Marc Michael THEORY OF HYDROPHOBIC BONDS TO HAIR
Pasadena, California 91107 (US) TREATMENTS", JOURNAL OF THE SOCIETY
• Baum, Janelle Marie COSMETIC CHEMISTS, SOCIETY OF COSMETIC
Pasadena, California 91107 (US) CHEMISTS, US, vol. 28, no. 5, 1 May 1977
(1977-05-01), pages 231-241, XP000603880, ISSN:
(72) Inventors: 0037-9832
• Baum, Marc Michael • DATABASE GNPD [Online] MINTEL; 1 April 2010
Pasadena, California 91107 (US) (2010-04-01), "Straight Hair Essence", Database
• Baum, Janelle Marie accession no. 1334679
Pasadena, California 91107 (US)
EP 2 694 834 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)


1 EP 2 694 834 B1 2

Description wavy hair leading to a straighter form without the use of


harsh chemicals has grown in recent years. The popular
FIELD OF INVENTION temporary hair straightening process known as escova
progressiva was pioneered in Brazil. Known in the United
[0001] The present invention relates to keratin-based 5 States as "Brazilian hair straightening" or "keratin
hair straightening formulations, methods and systems. straightening," this process can provide results lasting
up to 5 months and uses high temperatures (typically
BACKGROUND 230° C, 450° F), keratin lysate, and elevated levels
(1-5%) of formaldehyde as its primary components. The
[0002] The following description includes information 10 highly toxic nature of formaldehyde, a proven human car-
that may be useful in understanding the present inven- cinogen, and the high temperatures used in the process
tion. It is not an admission that any of the information raise legitimate concerns regarding its safety for stylists
provided herein is prior art or relevant to the presently and clients. Other, similar treatments have emerged that
claimed invention, or that any publication specifically or replace the toxic formaldehyde with chemicals such as
implicitly referenced is prior art. 15 glyoxal. For example, Resnick et al. disclose a formula-
[0003] Hair is a filamentous biomaterial that grows from tion and method relying on keratin lysate, a crosslinking
follicles found in the dermis. Human hair has many tex- agent such as a polyfunctional aldehyde, and styling with
tures, from fine to coarse, and from straight to curly. The a flat iron to achieve curl minimization (1). This treatment,
outermost layer of the hair filament is called the cuticle however, has the disadvantage of requiring high levels
and consists of translucent scales that cover the shaft. 20 of heat (typically > 200°C) to be effective, and these high
The cuticle protects the shaft from environmental dam- temperatures often cause an undesirable change in color
age. It is also sensitive to pH changes: at high pH the of the processed hair (e.g., orange coloring). Syed et al.
scales open, leaving the cortex exposed to environmen- also discloses a curl minimizing composition based on
tal conditions. This is commonly exploited in hair process- keratin lysate, a crosslinking agent, and heat to achieve
ing, from straightening to coloring. Hair is composed pri- 25 temporary hair straightening (2). However, that treat-
marily (around 88%) of keratin, a protein made up of ment, as described, is unlikely to achieve sustained hair
chains of polypeptide helix coils. The polypeptides have straightening lasting in excess of several months with
a high cystine content that leads to extensive crosslinking repeated hair washing. Considering the practical limita-
via the disulfide linkage. The bonds are perpendicular to tions and safety concerns relating to existing hair straight-
the helix coils, with one bond for every four turns of the 30 ening treatments and methods, there is clearly a need in
helix. It is the crosslinking that gives hair its toughness the art for a more effective and non-toxic means of hair
and abrasion resistance, as well as defining its shape. straightening.
[0004] Curly hair is made of hair strands with irregular
surfaces that mesh and tangle to make combing and BRIEF DESCRIPTION OF PRIOR ART
management more challenging than with straight hair. It 35
therefore has become popular among many individuals [0007] US2009/165812 discloses a hair straightening
to relax or straighten hair in order to increase managea- formulation comprising one or more keratin hydrolysates
bility and ease of styling. and an aldehyde.
[0005] The oldest form of hair straightening involves [0008] US6488920 is directed to a hair relaxation com-
the use of strongly alkaline agents, at pH 12-14, to per- 40 position consisting essentially of an activator containing
manently convert the crosslinking disulfide bonds in cys- a thiosulfate compound, an acidifier, and a catalyst, hav-
tine to lanthionine. During this harsh chemical treatment, ing a pH in a range of about 3.0 to 4.5.
the hair is mechanically maintained in a straight confor-
mation. In a milder, alternative hair relaxation process, SUMMARY OF THE INVENTION
the cystine disulfide bonds are chemically reduced to pro- 45
duce temporary cysteine residues. Common reducing [0009] In some embodiments, the invention teaches a
agents used in these processes include thioglycolic acid, hair straightening composition, having a pH of from 3.0
ammonium thioglycolate, and bisulfite. These are typi- to 4.5, comprising an organic acid; one or more reducing
cally used at high pH (e.g., 9.5). A neutralizer/fixative is agents capable of breaking at least a portion of the S-S
applied in the second stage of the treatment, along with 50 bonds in human hair when applied to said human hair
mechanical straightening and flat-ironing at 200°C wherein said reducing agents are compatible with a pH
(400°F), to restore the pH balance to the hair and to re- of from 3.0 to 4.5, wherein said reducing agents are se-
form the disulfide crosslinks in their new positions. This lected from the group consisting of naturally-occurring
process produces permanent straightening, is damaging amino acids, non-naturally occurring amino acids, mem-
to the hair, and takes a relatively long time (4-6 hours) 55 bers of the thiazoline family, members of the 2-mercapto-
to perform. ethane family, dithiothreitol, tris(2-carboxyethyl)phos-
[0006] The demand for temporary (1-6 months) hair phine, tris(2-carboxyethyl phosphine-HCl, sulfamic acid,
straightening systems that remove the frizz from curly or sulfamates, FeCl2, and combinations thereof; a keratin

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3 EP 2 694 834 B1 4

protein fraction; a crosslinking agent comprising a non- acids, mono-epoxy compounds, poly-epoxy compounds,
formaldehyde aldehyde; and optionally a Lewis acid cat- carbonates, imidoesters, carbodiimides, hexamethylene
alyst. diisocyanate, N-hydroxysuccinimide esters, haloacetyls,
[0010] In some embodiments, the invention teaches a pyridyl disulfide, hydrazides, aryl azides, and combina-
method for straightening a quantity of hair, the method 5 tions thereof.
comprising: providing a composition having a pH of from [0012] In some embodiments, the invention teaches a
3.0 to 4.5, the composition comprising one or more re- kit for straightening a quantity of hair, including: a hair
ducing agents capable of breaking at least a portion of straightening composition described herein; and instruc-
the S-S bonds in human hair when applied to said human tions for the use thereof for straightening the quantity of
hair wherein said reducing agents are compatible with a 10 hair. In some embodiments, the kit further includes a
pH of from 3.0 to 4.5, and said reducing agents are se- shampoo, a conditioner, a flat iron, a hair dryer, one or
lected from the group consisting of naturally-occurring more disposable gloves, a brush, and/or a comb.
amino acids, non-naturally occurring amino acids, mem-
bers of the thiazoline family, members of the 2-mercapto- DESCRIPTION OF THE INVENTION
ethane family, dithiothreitol, tris(2-carboxyethyl)phos- 15
phine, tris(2-carboxyethyl phosphine-HCl, sulfamic acid, [0013] Unless defined otherwise, technical and scien-
sulfamates, FeCl2, and combinations thereof, and one tific terms used herein have the same meaning as com-
or more keratin protein fractions, one or more pH lowering monly understood by one of ordinary skill in the art to
agents, and one or more crosslinking agents, and apply- which this invention belongs. March, Advanced Organic
ing the composition to the quantity of hair. In some em- 20 Chemistry Reactions, Mechanisms and Structure. 5th
bodiments, the method further includes applying to the ed., J. Wiley & Sons (New York, NY 2001); International
quantity of hair one or more substances selected from Cosmetic Ingredient Dictionary and Handbook. 9th ed.;
the group consisting of amino acids, botanicals, sur- Cosmetic, Toiletry, and Fragrance Association: Wash-
factants, emollients, emulsifiers, skin-cleaning agents, ington DC, 2002; Vol. 1-3; 2001 McCutcheon’s Directo-
preservatives, fragrances, pre-conditioners, thermal pro- 25 ries. McCutcheon’s Division, The Manufacturing Confec-
tectants, and aqueous-based diluents. In some embod- tioner Publishing Co.: Glen Rock, NJ, 2001; Vol. 1-2; and
iments, the quantity of hair is substantially dry when the DiBerardino, L., CBR Cosmetic Bench Reference - Di-
one or more pH lowering agents, reducing agents, rectory of Cosmetic Ingredients 2005. Cosmetics and
crosslinking agents and keratin protein fractions are ap- Toiletries, Allured Publishing Corporation: Carol Stream,
plied to the quantity of hair. In some embodiments, the 30 IL, 2005, together provide one skilled in the art with a
quantity of hair is wet when the one or more pH lowering general guide to many of the terms used in the present
agents, reducing agents, crosslinking agents and keratin application.
protein fractions are applied to the quantity of hair. In [0014] One skilled in the art will recognize many meth-
some embodiments, the method further includes wash- ods and materials similar or equivalent to those described
ing the quantity of hair with a shampoo no more than 35 herein, which could be used in the practice of the present
three hours prior to applying the one or more pH lowering invention. Indeed, the present invention is in no way lim-
agents and reducing agents. In some embodiments, the ited to the methods and materials described. For the pur-
method further includes applying a straightening iron to poses of the present invention, the following terms are
the quantity of hair. defined below.
[0011] In some embodiments, the composition further 40 [0015] As used herein, the terms "solution," "prepara-
includes one or more substances selected from the group tion," "composition" and "formulation" can be used inter-
consisting of amino acids, botanicals, surfactants, emol- changeably. The terms "modulates hair frizz," "defrizzes
lients, emulsifiers, skin-cleaning agents, preservatives, hair" and "curl minimizing" are used interchangeably. As
fragrances, pre-conditioners, thermal protectants, and defined herein, "modulates" hair frizz means that it either
aqueous-based diluents. In some embodiments, the or- 45 reduces or prevents hair frizz. The term "curl minimizing
ganic acid is a naturally-occurring organic acid. In certain agent," as used herein, refers to compounds disclosed
embodiments, the organic acid is an aliphatic or aromatic herein capable of forming a covalent bond or crosslink
mono-carboxylic acid or a poly-carboxylic acid. In certain with a protein end group in human hair keratin, when
embodiments, the organic acid is selected from the group applied thereto by an aqueous vehicle. The term "heat-
consisting of formic acid, acetic acid, propionic acid, tar- 50 assisted," as used herein, refers to the use of a frizz min-
taric acid, adipic acid, succinic acid, ascorbic acid, malon- imizing composition of the present invention in conjunc-
ic acid, oxalic acid, pyruvic acid, picolinic acid, dipicolinic tion with a heating device, such as an electrically heated
acid, citric acid, and combinations thereof. In some em- flat hair iron or hair dryer, at some point in the process.
bodiments, one or more of the crosslinking agents in- [0016] Hand-held hair dryers are conventionally used
cludes one or more substances selected from the group 55 to "blow dry" hair, preferably using an ambient heat set-
consisting of monofunctional aldehydes, polyfunctional ting temperature in the range of about 100°C to about
aldehydes, ketones, hydroxyketones, ketoaldehydes, 108°C, more preferably in the range of about 105°C to
activated olefin-containing compounds, polycarboxylic about 106°C. Commercial electric flat hair irons are avail-

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5 EP 2 694 834 B1 6

able having variable heat settings, and preferably are that the numerical ranges and parameters setting forth
ceramic, heated to platen temperatures in the range of the broad scope of some embodiments of the application
about 100°C to about 240°C, more preferably in the range are approximations, the numerical values set forth in the
of about 150°C to about 235°C. specific examples are reported as precisely as practica-
[0017] The term "temporary straightening" means that 5 ble.
the frizz modulating effect resists reversion to the natural [0019] Keratin-protectant, curl minimizing composi-
curl configuration on being subjected to more than one tions and processes of the present invention avoid the
washing, preferably at least four washings, and more deleterious action that can be caused by conventional
preferably at least eight washings, or the effect lasts until highly alkaline lanthionization chemical hair relaxer proc-
the scalp hair grows sufficiently to visibly warrant another 10 esses, manifested as measurable changes in the phys-
frizz reducing procedure. The terms "washed" and ical, chemical, and mechanical integrity of the keratin fib-
"washing" include rinsing with water, shampooing or a ers. Measurable changes in the integrity of the hair in-
combination of rinsing with water and shampooing. The clude changes in tensile strength properties, elasticity,
terms "precondition," "preconditioning," and grammatical porosity, cuticle erosion, fiber breakage, wet and dry
variations thereof, as used herein, refer to compositions 15 combing force and the like, as well as changes in dis-
containing conditioners that are applied to the hair in a cernible subjective properties, i.e., tactile feel, and visible
first step of a multi-step curl minimizing process, and to sheen or appearance.
hair that has been so conditioned. As defined herein, [0020] Hard keratin fibers, such as human hair and
"leave-in" conditioner is a conditioner that is applied to wool, have a complex morphological structure and are
hair and is not removed by rinsing. The terms "keratin- 20 predominantly proteinaceous. The proteins in human
protectant" and "hair protectant" are used interchangea- hair, for example, are polymers made up of a number of
bly as applied to a curl minimizing composition of the amino acids, and the linkages of the amino acids and
present invention and refer to allowing for the retention peptide bonds are responsible for the strength of the pro-
of at least one discernible desirable characteristic, such tein backbone. Hair fibers are quite strong, and strength
as strength, sheen, smooth tactile character, and reten- 25 is conferred on the fiber by the inner cortex and protective
tion of original, natural hair color or tone, and the like, outer cuticle sheath. The main bulk of the fiber, the cortex,
that is conventionally associated with the physical, me- consists essentially of long coiled peptide chains joined
chanical integrity of natural hair keratin before receiving in one plane by salt and sulfur linkages, and in the other
a curl minimizing procedure with the composition, and, plane by hydrogen bonds. The chemical structure of hair
in particular, before receiving a heat-assisted, curl mini- 30 keratin makes it susceptible to attack by chemical rea-
mizing procedure of this invention. The term "isoelectric gents. Hair keratin is more susceptible to alkaline hydrol-
point" is defined as the pH at which a particular molecule, ysis than to acid hydrolysis (3).
polymer, or surface carries no net electrical charge. The [0021] Naturally occurring covalent crosslinks in hair
term "reducing agent" is used herein to refer to any chem- keratin contribute to the physical stability and mechanical
ical agent that, under the conditions described herein, 35 strength of the fibers. Some naturally occurring covalent
can chemically reduce the S-S bond in cystine residues crosslinks in the hair include: disulfide (cystine) bonds
inherent in the proteins contained in human hair. The formed between two cysteine residues in either the same
term "crosslinker" is defined as one or more chemical protein chain or adjacent protein chains; isopeptide
agents that can forms crosslinks with at least one protein bonds formed as amide crosslinks in the follicle; and pep-
end group in hard keratin, such as human hair keratin or 40 tide bonds existing between the amino groups of lysine
wool. For example, formaldehyde can form crosslinks and the carboxyl groups of aspartic acid or glutamic acid
between NH, OH, and SH groups in such proteins. The in portions of the same polypeptide chain or between
term "polyfunctional aldehyde" means more than one al- different polypeptide chains. The tensile properties of wet
dehyde is present in the compound, such as a dialde- keratin fibers are related to the presence of disulfide
hyde, a trialdehyde, and the like. 45 bonds and the tensile properties of dry keratin are influ-
[0018] In some embodiments, the numbers expressing enced by the peptide bonds. The presence of crosslinks
quantities of ingredients, properties such as molecular in human hair introduced by chemical reagents has been
weight, reaction conditions, and so forth, used to describe measured in the art directly by analytical techniques, and
and claim certain embodiments of the application are to indirectly, based on changes in the mechanical strength
be understood as being modified in some instances by 50 and/or physical stability of the fiber measured instrumen-
the term "about." Accordingly, in some embodiments, the tally or quantitatively from such fiber properties as swell-
numerical parameters set forth in the written description ing, sorption, super contraction, setting, tensile strength,
and attached claims are approximations that can vary weight gain, alkali solubility and the like.
depending upon the desired properties sought to be ob- [0022] The reaction between hair and chemical rea-
tained by a particular embodiment. In some embodi- 55 gents is generally complex and more than one type of
ments, the numerical parameters should be construed in linkage is affected. Naturally-occurring sites and linkages
light of the number of reported significant digits and by that are susceptible to reaction with simple chemical re-
applying ordinary rounding techniques. Notwithstanding agents, for example, include hydrogen bonds and van

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7 EP 2 694 834 B1 8

der Waals forces between adjacent peptide chains and its greatest insolubility and greatest ionic stability against
side chains of the alpha-keratin-fibers, and salt linkages chemical reactions. Hair treated at its isoelectric point
that can be reversibly fissioned by acids or short time pH, so that its protein can acquire an uncharged neutral
exposure to base. Temporary hair styles that rely on state, is likely rendered stronger than hair treated at other
bonding through salt linkages and hydrogen bonds typ- 5 pHs. Accordingly, the curl minimizing preparation of the
ically are broken by exposure to water and humidity re- present invention preferably contains at least one buffer
sulting in loss of temporary hair set, typically seen as substance or a buffer system, which has buffer capacity
reversion of a hair style set to its natural configuration, in a range of about pH 2.0 to 7.0, and especially includes
i.e., revert to a curly state (rekink or frizz) or uncurl to a the isoelectric point of human hair, as described herein.
naturally straight state. 10 [0028] In various embodiments of the present inven-
[0023] Bearing in mind all of the above-described prop- tion, one or more substances are used to lower the pH
erties of hair, and its responses to various chemical treat- to approximately the above-referenced range. In some
ments, the inventors developed new and improved for- embodiments, one or more of the substances used to
mulations, systems and methods for straightening hair. lower the pH of the formulation to the above-referenced
[0024] The present invention teaches a novel ap- 15 range are selected from the group consisting of: formic
proach to keratin-based hair straightening based upon acid, acetic acid, propionic acid, other aliphatic or aro-
the integration of three key synergistic components, in- matic mono- or poly-carboxylic acids, and combinations
cluding: (1) adjusting the pH of hair to a value close to thereof. In the present invention, one or more organic
its isoelectric point; (2) chemically reducing the disulfide acids are used to lower the pH of the formulations dis-
bonds in the keratin proteins making up hair fibers; and 20 closed herein to 3.0-4.5. In certain embodiments, one or
(3) chemically crosslinking reactive groups in the keratin more of the organic acids are selected from the group
proteins making up hair fibers as well as between reactive consisting of: tartaric acid, adipic acid, succinic acid,
groups in the keratin proteins making up the hair fibers ascorbic acid, malonic acid, oxalic acid, pyruvic acid, pi-
and proteins in the keratin lysate included in the formu- colinic acid, dipicolinic acid, citric acid, and combinations
lations disclosed herein. 25 thereof. In certain embodiments, a plurality of acids is
[0025] The novel approach set forth herein results in used as a mixture.
the following significant advantages, among others: (1)
efficient curl-minimization with reduced frizz for periods Reducing Agents
lasting up to five months or longer; (2) avoidance of highly
toxic formaldehyde, or formaldehyde precursors, in the 30 [0029] Reducing agents used in various embodiments
crosslinking step; and (3) lowering of the processing tem- of the present invention must be compatible with the
perature to below the 232°C (450°F) typically used in above-described pH range, which excludes those in the
other keratin curl-minimizing treatments, resulting in less thioglycolate family typically used in the art for this pur-
damage to the hair. pose.
[0026] Formulations, methods, and systems based on 35 [0030] In certain embodiments, one or more of the re-
the approach described above are disclosed in detail be- ducing agents include natural and/or non-natural amino
low. acids that are sufficiently electrochemically reducing un-
der the conditions of the curl minimizing treatment de-
Isoelectric Point Adjusting Agents scribed herein to break the S-S bonds in human hair. In
40 certain embodiments, the amino acids are selected from
[0027] Hair comprises proteins and proteins are char- the group consisting of: cysteine, cysteine-HCl, methio-
acterized, among other things, by an isoionic point and nine, methionine-HCl, and combinations thereof. In cer-
an isoelectric point (4). The isoionic point is the pH value tain embodiments, the reducing agents are members of
at which the number of total positive charges on a protein the thiazoline family. In some embodiments, the mem-
is equal to the number of total negative charges. The 45 bers of the thiazoline family used herein are selected
isoionic point of hair is about equal to pH 6.0. The isoe- from the group consisting of: thiazoline, thiazolidine car-
lectric point is a surface property of solid proteins and is boxylic acid, and combinations thereof. In various em-
that pH value at which the number of positive charges bodiments of the present invention, the reducing agent
on the surface of the protein equals the number of neg- is a member of the 2-mercapto-embodiments of the
ative charges. The isoelectric point of human hair nor- 50 present invention, the reducing agent is selected from
mally is about pH 3.7. The exact value for individual hair the group consisting of: tris(2-carboxyethyl)phosphine
can vary slightly from this value, and investigators differ (TCEP) and tris(2-carboxyethyl)phosphine-HCl (TCEP-
on the range of isoelectric point pH values; pH 3.3 to 4.5 HCl). In certain embodiments, one or more of the reduc-
and more recently pH 2.45 to 3.17 (5, 6). In any case, at ing agents consists of sulfamic acid. In certain embodi-
the isoelectric point, protein carries a neutral charge. An 55 ments, one or more of the one or more reducing agents
advantage is gained from inducing hair protein keratin to is a sulfamate. In certain embodiments, the sulfamate is
gather a neutral ionic charge, that is, to treat hair at its selected from the group consisting of: O-substituted-, N-
isoelectric point. At its isoelectric point, a protein displays substituted-, and di-/tri-substituted derivatives of sulfam-

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9 EP 2 694 834 B1 10

ic acid. a total composition weight basis. In some preferred em-


[0031] In certain embodiments of the present inven- bodiments, these crosslinking agents are in the range of
tion, one or more of the reducing agents is organic and about 0.15-2.0% on a total composition weight basis. In
has antioxidant properties. In certain embodiments, the other preferred embodiments, these crosslinking agents
reducing agent with antioxidant properties is ascorbic ac- 5 are in the range of about 0.2-0.5%, on a total composition
id.This embodiment does not form part of the appended weight basis.
claims but is retained for information purposes. [0039] In certain embodiments, one or more of the one
[0032] In some embodiments of the present invention, or more aldehydes are dialdehydes. In some embodi-
one or more of the reducing agents used consists of an ments, the dialdehydes are selected from the group con-
inorganic salt. In certain embodiments, the inorganic salt 10 sisting of: glutaraldehyde, glyoxal, glycolaldehyde dimer,
is iron (II) chloride (FeCl2). and adipaldehyde. In some embodiments, these
[0033] In some embodiments, one or more of the re- crosslinking agents are about 0.1-3.0% on a total com-
ducing agents used herein also lower the pH of the for- position weight basis. In some preferred embodiments,
mulation. In some embodiments, these reducing agents these crosslinking agents are in the range of about
are selected from the group consisting of: cysteine-HCl, 15 0.15-2.0% on a total composition weight basis. In other
2-mercaptoethylamine-HCl, sulfamic acid, FeCl2, and preferred embodiments, these crosslinking agents are in
combinations thereof. the range of about 0.2-0.5%, on a total composition
[0034] As disclosed above, in various embodiments a weight basis.
plurality of reducing agents are used as a mixture. [0040] While not wishing to be bound by any one par-
20 ticular theory, it is very likely that one or both functional
Crosslinking Agents groups of dialdehydes can react with protein end groups
to advantageously produce a more complex, more
[0035] The keratin-protectant, curl minimizing compo- crosslinked protein-aldehyde product with a higher mo-
sitions of the present invention employ one or more curl lecular weight that is more stable (i.e., less readily hy-
minimizing agents that can form crosslinks with protein 25 drolyzed) than complexes formed by the monofunctional
end groups in naturally curly keratin to achieve hair styles aldehyde formaldehyde.
having a decreased bulk in hair volume by loosening or [0041] In certain embodiments, glutaraldehyde is used
straightening fiber alignment. The Keratin-protectant, in combination with hydrolyzed polyvinyl alcohol (PVA).
curl minimizing compositions of the present invention While not wishing to be bound by any one particular the-
contain an effective quantity of at least one physiologi- 30 ory, PVA reportedly reacts with glutaraldehyde by ace-
cally tolerable curl minimizing agent that is capable of talization to form a bulky pentane dilated PVA having
forming crosslinks with at least one protein end group in highly reactive aldehyde, hemiacetal, and acetal groups
hard keratin. In some embodiments, the hard keratin is available for reaction with the amino acids of hair con-
selected from the group consisting of: human hair keratin, taining OH groups, such as serine, tyrosine and threo-
animal hair keratin, and wool. Certain embodiments de- 35 nine, to form a crosslinking network. The reported per-
scribed herein are for use on human hair keratin. centage of serine in hair is relatively high (11.5%) and
[0036] The highly toxic aldehyde, formaldehyde, or hence serine can be easily targeted for crosslinking. In
chemicals that release formaldehyde upon heating such these embodiments, any free PVA present in the hair
as paraformaldehyde are expressly excluded from cer- which has not reacted with the dialdehyde can remain in
tain embodiments of the present invention. In other em- 40 the matrix of the fiber and further help in straightening
bodiments, the formulations disclosed herein are sub- due to its high molecular weight. Furthermore, free glu-
stantially free of formaldehyde. taraldehyde left after the acetalization reaction is also
[0037] The highly toxic aldehyde, formaldehyde, or available to crosslink the hair.
chemicals that release formaldehyde upon heating such [0042] In certain embodiments, one or more of the one
as paraformaldehyde are expressly excluded from cer- 45 or more crosslinkers is a ketone. In certain embodiments,
tain embodiments of the present invention. In other em- the crosslinkers include hydroxyketones and/or ketoal-
bodiments, the formulations disclosed herein are sub- dehydes. In certain embodiments, one or more of the one
stantially free of formaldehyde. or more crosslinkers are selected from the group con-
[0038] In certain embodiments of the present inven- sisting of: hydroxyacetone, pyruvaldehyde, pyruvic acid,
tion, one or more of the one or more crosslinking agents 50 combinations thereof and the like.
include one or more monofunctional non-formaldehyde [0043] In some embodiments, the present invention
aldehydes. In various embodiments, the crosslinking teaches combinations of one or more of the crosslinkers
agents are selected from the group consisting of: ben- with a Lewis acid catalyst. In some embodiments, the
zaldehyde, butanal, propanal, cinnamaldehyde, and sal- Lewis acid catalyst is selected from the group consisting
icylaldehyde. Other embodiments include chemicals se- 55 of: zinc nitrate (Zn(NO3)2), magnesium chloride (MgCl2),
lected from vanillin, glyceraldehyde and the like, present iron chloride (FeCl2 or FeCl3), and the like. Polyfunctional
in physiologically tolerable amounts. In some embodi- aldehydes can react with hydroxyl groups to form a
ments, these crosslinking agents are about 0.1-3.0% on hemiacetal, which can be catalyzed by a Lewis acid to

6
11 EP 2 694 834 B1 12

form a stabilized acetal. selected from the group consisting of: oxalic acid, malon-
[0044] Because the crosslinking effect is mediated by ic acid, tartaric acid, dipicolinic acid, 1,2,3,4-butanetet-
the Maillard Reaction and cross-linking of the keratin fib- racarboxylic acid (BTCA), 1,2,3,4-cyclopentanetetracar-
ers, in some embodiments, other Maillard reactants and boxylic (CPTA), citric acid, polyacrylic acid, and the like.
cross-linking agents are substituted for the above alde- 5 In certain embodiments, the invention discloses a com-
hydes. In some embodiments, the chemical cross-linking bination of a polycarboxylic acid and cyclodextrin. In
effect involves sugars, including dihydroxyacetone, ac- some embodiments, the invention discloses the combi-
etones and ethers that undergo the Maillard reaction. nation of BTCA and cyclodextrin. Advantageously, this
[0045] In some embodiments, the invention discloses combination reportedly forms a copolymer that can
an activated olefin-containing substance having at least 10 crosslink through amide groups, based on studies with
one double bond bearing at least one electron withdraw- wool. In some embodiments, the invention discloses the
ing substituent, such as, without limitation, a carboxylic use of esters of one or more of the above polycarboxylic
acid, an ester, an amide, an imide, a nitrile, or an anhy- acids. In some embodiments, the esters include dimethyl
dride. In some embodiments, the physiologically tolera- oxalate and dimethyl malonate. In certain embodiments,
ble, activated olefin-containing substance is substantially 15 these crosslinkers are used in a range of about 1.0-25.0%
non-irritating to human skin; substantially chemically sta- on a total composition weight basis. In preferred embod-
ble in the composition medium; and does not itself impart, iments, these crosslinkers are used in a range of about
or contribute to, any visibly undesirable coloration on the 5.0-20.0% on a total composition weight basis.
hair or skin. In some embodiments disclosed herein, ac- [0049] In certain embodiments of the present inven-
tivated olefin-containing substances include one or more 20 tion, one or more epoxy-type crosslinkers are used. In
chemicals selected from the group consisting of: maleic some embodiments, the epoxy-type crosslinkers include
acid, esters of maleic acid, maleimides, N-substituted de- styrene oxide and/or epihalohydrins. In some embodi-
rivatives of maleimides, maleamic acid, N-substituted de- ments, the epoxy-type crosslinkers include epichlorohy-
rivatives of maleamic acid, maleic anhydride, and com- drin and/or epibromohydrin. In a preferred embodiment
binations thereof. Preferred N-substituents are 25 the epoxy crosslinker is epichlorohydrin. In some embod-
N-(C1-C20)-alkyl, N-aryl, and N-haloaryl. In certain em- iments, the invention discloses the use of diepoxides as
bodiments, maleic acid derivatives are used. In some crosslinkers. In some embodiments, the crosslinkers are
embodiments, the maleic acid derivatives are maleim- 1,4-butanediol- diglycidyl ethers. In some embodiments,
ides. Advantageously, maleimides are known to undergo the one or more crosslinkers are precursors of epihalo-
nucleophilic addition reactions with thiol groups in wool, 30 hydrins and diepoxides. In certain embodiments, the pre-
and also crosslink amine, hydroxyl, and amide groups. cursors are selected from the group consisting of: 1,3-
[0046] In some embodiments, the present invention dichloropropanol-2 and 1,4- dichloro-2,3-dihydroxybu-
teaches the use of mono-esters of maleic acid. In some tane.
embodiments, mono-ester is a poly(C2-C4)-alkylene gly- [0050] In some embodiments, the present invention
col ester. In certain embodiments, the polyalkylene glycol 35 discloses the use of polyepoxy compounds that are
ester is selected from the group consisting of: polyethyl- sometimes used as collagen crosslinking agents (7-8).
ene glycol esters, polypropylene glycol esters, polybuty- At least some of these known polyepoxy fixatives are
lene glycol esters, and combinations thereof. In preferred commercially available under the trademark Denaco™
embodiments, the polyethylene glycol ester is a poly- from Nagase Chemicals, Ltd., Osaka, Japan. In particu-
alkylene glycol bis-maleinate, sold commercially as a wa- 40 lar, one difunctional epoxy compound which has been
ter miscible, medium-viscosity, liquid under the trade used as a collagen crosslinking agent is an ethylene gly-
name MIRALANTM HTP, by Ciba Specialty Chemicals col diglycidyl ether based compound commercially avail-
Corporation. According to the supplier’s data sheets, MI- able from Nagase Chemicals, Ltd. of Osaka, Japan under
RALANTM HTP contains about 65 to about 75% by the designation Denacol Ex-810. Other epoxy com-
weight poly(oxy-1,2-ethanediyl)-alpha-hydro-omega-hy- 45 pounds used in the present invention that have been pre-
droxy, (2Z)-2-butenedioate corresponds to CAS Number viously disclosed for use as collagen crosslinking agents
37310-95-5, has a pH in the range of about pH 2 (5% include commercially available substances such as De-
solution) to about pH 2.7 (1 gram/liter), and is reportedly nacol Ex-313 and Dencacol Ex-314 from Nagase Chem-
anionic in character. icals, Ltd. of Osaka, Japan (8).
[0047] In certain embodiments, N-substituted maleim- 50 [0051] In some embodiments, one or more of the
ide derivatives are used in the present invention. In some crosslinkers used in the present invention are imi-
embodiments, the N-substituted maleimide derivative is doesters. In some embodiments, the imidoesters are se-
N-naphthylmaleimide or N-trifluorophenylmaleimide. An lected from the group consisting of: dimethyl adipimidate-
exemplary N-substituted maleamic acid derivative is N- HCl (DMA), dimethyl pimelimidate-HCl (DMP), dimethyl
trifluorophenylmaleamic acid. 55 suberimidate-HCl (DMS), and dimethyl 3,3’-dithiobispro-
[0048] In certain embodiments, a polycarboxylic acid pionimidate-HCl (DTBP). In some embodiments, one or
is used as one or more of the crosslinkers. In some em- more of the one or more crosslinkers disclosed herein
bodiments, one or more of the polycarboxylic acids are are carbodiimides. In some embodiments, the carbodi-

7
13 EP 2 694 834 B1 14

imides are N,N’-dicyclohexylcarbodiimide (DCC) or N-(3- but not limited to, one or more of the 20 natural alpha-
dimethylaminopropyl)-N’-ethylcarbodiimide hydrochlo- amino acids, beta- or gamma-amino acids, or any unnat-
ride (EDC). In some embodiments, the chemical com- ural amino acids. In some embodiments, the amino acids
pounds that are used as fixatives for cross-linking keratin are derived from silk fibers.
and/or collagen are selected from the group consisting 5
of: hexamethylene diisocyanate, polyepoxy compounds, Cosmetic Ingredients
N-hydroxysuccinimide esters, haloacetyls, pyridyl di-
sulfides, hydrazides, carbonates, and aryl azides. [0057] In certain embodiments, the hair-protectant,
[0052] The above keratin crosslinking agent(s) are curl minimizing compositions of the present invention in-
present in an amount of about 0.05%-10.0% by weight 10 clude curl minimizing agent in a cosmetically acceptable
In a preferred embodiment, the cross-linking agent(s) are aqueous vehicle suitable for application at least once to
present in the amount of about 0.1-2.0% by weight. human hair. In some embodiments, the hair-protectant
[0053] In some embodiments of the present invention, compositions also contain conventional cosmetic hair
the one or more crosslinking agents are advantageously conditioning ingredients, botanical products, and other
also used to lower the pH of the formulations, such as, 15 optional cosmetic ingredients, additives, products or ma-
but not limited to, polycarboxylic acids. terials, and cosmetic adjuvants, well known in the hair
[0054] As disclosed above, in certain embodiments of care and personal care formulation arts. For heat-assist-
the present invention, a plurality of crosslinking agents ed, curl minimizing processes, the aqueous curl minimiz-
are used as a mixture. ing composition preferably contains an auxiliary hair pro-
20 tectant, heat-protective ingredient, such as silicone
Keratin Protein Fractions and/or a silicone derivative.
[0058] Cosmetic ingredients optionally employed in
[0055] In certain embodiments, the keratin protein frac- the hair-protectant compositions and systems disclosed
tions used in the inventive formulations include hydro- herein are referred to by their commonly used chemical
lyzed keratin produced by alkaline and/or enzymatic hy- 25 or trade names or by the international nomenclature,
drolysis using methods known in the art. In some em- commonly referred to as an International Nomenclature
bodiments, the keratin hydrolysate has a molecular of Cosmetic Ingredients (INCI) name, designated in any
weight of about 1,000-3,000. In certain embodiments, edition of the International Cosmetic Ingredient Diction-
the keratin used in the inventive methods is derived from ary and Handbooks. Numerous commercial suppliers of
human or other mammalian sources such as goat hair, 30 materials listed by INCI name, trade name, or both, can
hoof or horn meals (9,10). In some embodiments, the be found in any edition of the INCI Dictionary and in nu-
"keratin protein fraction" is a purified form of keratin that merous commercial trade publications (13-14); the rele-
contains predominantly, although not entirely, one dis- vant disclosures of the INCI Dictionary and each of the
tinct protein group (11). In some embodiments, the ker- foregoing publications being incorporated by reference
atin protein fraction is intact intermediate filament protein 35 herein.
capable of acting as a protective keratin layer. In some [0059] The term "cosmetic adjuvant" includes cosmet-
embodiments, the keratin protein fraction includes a ker- ically useful product finishing and promotional additives,
atin hydrolysate and a purified form of keratin. In some well known and conventionally used in the cosmetic arts
embodiments, the invention teaches the use of keratin to maintain the physical stability of a composition during
hydrolysate and one or more intact intermediate filament 40 storage (shelf-life), and the visible aesthetic appearance
proteins capable of acting as a protective keratin layer, of a composition during storage and during the use of
or a mixture of intact intermediate filament proteins. In the composition. In some embodiments, the cosmetic ad-
some embodiments, the keratin protein fraction is about juvants that maintain the stability of the products of the
0.05%-15.0% by weight In some preferred embodiments, present invention include a metal-ion chelating agent, an
the keratin protein fraction is about 0.5-5.0% by weight. 45 antioxidizing agent, a preservative, an emulsifying agent,
In some embodiments, small, approximately 2-100 ami- a perfume solubilizer, and the like. In some embodi-
no acids, peptides are included in the formulation. In cer- ments, cosmetic adjuvants of the present invention aid
tain embodiments of the present invention, epigallocate- in enhancing the aesthetics and marketing appeal of the
chin gallate is also used in the formulation to provide present invention, and include, without limitation, a prod-
additional conditioning. In some embodiments, the con- 50 uct colorant, a fragrance, and the like.
centration of epigallocatechin gallate is from 0.5%-15.0% [0060] Those skilled in the formulation arts can readily
by weight. In preferred embodiments, the range is 1.0%- determine the amount of curl minimizing agent to be used
10.0% by weight. in a formulation by the amount of curl minimization de-
sired. Compositions of the various embodiments can be
Amino Acids 55 prepared and used in the form of aqueous liquids, or for-
mulated as emulsions, by techniques known in the art,
[0056] In some embodiments, the compositions dis- containing cosmetically acceptable conditioners and
closed herein include a mixture of amino acids, including, emulsifiers.

8
15 EP 2 694 834 B1 16

Surfactants myristate, canolamidopropyl betaine, caprylyl/capryl glu-


coside, caprylyl pyrrolidone, carboxymethyl isostearami-
[0061] In certain embodiments, one or more sur- dopropyl morpholine, cellulose acetate propionate car-
factants are included in the hair straightening formula- boxylate, ceteareth-100, ceteareth-15, ceteareth-17, ce-
tions of the present invention. Surfactants are surface- 5 teareth-2 phosphate, ceteareth-20, ceteareth-25, cete-
active agents that are able to reduce the surface tension areth-25 carboxylic acid, ceteareth-27, ceteareth-30, ce-
of water and cause the product to slip across or onto the teareth-4 phosphate, ceteareth-40, ceteareth-5 phos-
skin. Surfactants also include detergents and soap. In phate, ceteareth-50, ceteareth-55, ceteareth-80, cetear-
certain embodiments, one or more of the surfactants in- yl polyglucose, ceteth-12, ceteth-14, ceteth-15, ceteth-
cluded in the formulations of the present invention are 10 16, ceteth-20, ceteth-24, ceteth-25, ceteth-45, cetethyl
amphoteric. In some embodiments, one or more anionic morpholinium ethosulfate, cetethyldimonium bromide,
or cationic surfactants are used. In certain embodiments, cetoleth-15, cetoleth-24, cetoleth-25, cetoleth-6, cetri-
one or more of the surfactants used in the hair straight- monium tosylate, cetyl betaine, cetyl PPG-2 isodeceth-
ening formulations of the present invention are selected 7 carboxylate, cetylpyridinium chloride, cholesteryl/be-
from the group consisting of: 3-aminopropane sulfonic 15 henyl/octyldodecyl lauroyl glutamate, cocamide, coca-
acid, almond amide DEA, almond amidopropyl betaine, mide DEA, cocamide MEA, cocamide MIPA, cocamidoe-
almond amidopropylamine oxide, aluminum hydrogen- thyl betaine, cocamidopropyl betaine, cocamidopropyl
ated tallow glutamate, aluminum lanolate, amino ethyl dimethyl amine, cocamidopropyl dimethylamine dihy-
sulfate, aminopropyl lauryl glutamine, ammonium droxymethylpropionate, cocamidopropyl dimethyl amine
C12-15 alkyl sulfate, ammonium C12-15 pareth sulfate, 20 hydrolyzed collagen, cocamidopropyl dimethylamine
ammonium C12-16 alkyl sulfate, ammonium C9-10 per- lactate, cocamidopropyl dimethylamine propionate, co-
fluoroalkylsulfonate, ammonium capryleth sulfate, am- camidopropyl dimethylaminohydroxypropyl hydrolyzed
monium capryleth-3 sulfate, ammonium cocomonoglyc- collagen, cocamidopropyl dimethylammonium C8-16
eride sulfate, ammonium cocosulfate, ammonium cocoyl isoalkylsuccinyl lactoglobulin sulfonate, cocamidopropyl
isethionate, ammonium cocoyl sarcosinate, ammonium 25 hydroxysultaine, cocamidopropyllauryl ether, cocamido-
cumene sulfonate, ammonium dimethicone copolyol sul- propylamine oxide, cocamidopropyldimonium hydroxy-
fate, ammonium dodecylbenzenesulfonate, ammonium propyl hydrolyzed collagen, cocamine oxide, co camino
isostearate, ammonium laureth sulfate, ammonium lau- butyric acid, cocaminopropionic acid, coceth-4 polyglu-
reth-12 sulfate, ammonium laureth-5 sulfate, ammonium cose, coceth-7 carboxylic acid, coc%leamidopropyl
laureth-6 carboxylate, ammonium laureth-7 sulfate, am- 30 betaine, cocoamphodipropionic acid, cocobetainamido
monium laureth-8 carboxylate, ammonium laureth-9 sul- amphopropionate, cocobetaine, cocodimonium hydrox-
fate, ammonium lauroyl sarcosinate, ammonium lauryl ypropyl silk amino acids, coco-ethyldimonium ethosul-
sulfate, ammonium lauryl sulfosuccinate, ammonium- fate, coco-glucoside, coco-hydroxysultaine, coco-mor-
myreth sulfate, ammonium myristyl sulfate, ammonium pholine oxide, coconut acid, cocopolyglucose, coco-
nonoxynol-30 sulfate, ammonium nonoxynol-4 sulfate, 35 sultaine, cocotrimonium chloride, cocoyl benzyl hydrox-
ammonium oleate, ammonium palm kernel sulfate, am- yethyl imidazolinium chloride, cocoyl hydrolyzed colla-
monium polyacrylate, ammonium stearate, ammonium gen, cocoyl hydroxyethyl imidazoline, cocoyl sarcosina-
tallate, ammonium xylene sulfonate, ammonium xylene mide DEA, 25 cocoyl sarcosine, corn acid, cyclopentane
sulfonate, amp-isostearoyl gelatinikeratin amino ac- carboxylic acid, DEA-C12-15 alkyl sulfate, DEA-cetyl
ids/lysine hydroxypropyltrimonium chloride, amp-iso- 40 phosphate, DEA-cetyl sulfate, DEA-cocoamphodipropi-
stearoyl hydrolyzed collagen, apricot kernel oil PEG-6 onate, DEA-cyclocarboxypropyloleate, DEA-dodecy
esters, apricot amide DEA, apricot amidopropyl betaine, Ibenzenesulfonate, DEA-iso stearate, DEA-Laureth sul-
arachideth-20, avocadamide DEA, avocadamidopropyl fate, DEA-Iauryl sulfate, DEA-methyl myristate sulfonate,
betaine, babassuamide DEA, babassuamidopropyl DEA-myreth sulfate, DEA-myristate, DEA-myristyl sul-
betaine, babassuamidopropylamine oxide, behenalko- 45 fate, DEA-oleth-10 phosphate, DEA-oleth-20 phosphate,
nium chloride, behenamide DEA, behenamide MEA, be- DEA-oleth-3 phosphate, DEA-oleth-5 phosphate, de-
henamidopropyl betaine, behenamine oxide, behentri- ceth-4 phosphate, deceth-7 carboxylic acid, decyl
monium methosulfate, behenyl betaine, buteth-3 carbox- betaine, decyl glucoside, decyl polyglucose, decylamine
ylic acid, butyl polyglucose, C10-14 alkyl benzenesulfon- oxide, diammonium dimethicone copolyol sulfosucci-
ic acid, C11-15 pareth-12, C11-15 pareth-20, C11-15 50 nate, diammonium lauramido-MEA sulfosuccinate, di-
pareth-30, C11-15 pareth-40, C11-15 pareth-7 carboxy- ammonium lauryl sulfosuccinate, diammonium oleamido
lic acid, C11-15 pareth-9, C11-21-pareth-10, C12-13 PEG-2 sulfosuccinate, diamyl sodium sulfosuccinate, di-
pareth-10 phosphate, C12-13 pareth-5 carboxylic acid, capryl sodium sulfosuccinate, dicetyldimonium chloride,
C12-13 pareth-7, C12-15 pareth-11, C12-15 pareth-12, dicocodimonium chloride, dicyclohexyl sodium sulfosuc-
C12-15 pareth-2 phosphate, C12-15 pareth-7 carboxylic 55 cinate, didecyldimonium chloride, diethanolaminooleam-
acid, C12-15 pareth-9, C12-15 pareth-9 hydrogenated ide DEA, diethylamine laureth sulfate, diethylaminoethyl
tallowate, C14-15 pareth-13, C14-15 24 pareth-8 carbox- cocoate, diethylaminoethyl PEG-5 cocoate, diethylami-
ylic acid, C22-24 pareth-33, calcium laurate, calcium noethyl stearate, diheptyl sodium sulfosuccinate, dihexyl

9
17 EP 2 694 834 B1 18

sodium sulfosuccinate, dihydrogenated C16-18 amido sulfosuccinate, disodium palmitamido PEG-2 sulfosuc-
benzoic acid, dihydrogenated tallow benzylmonium chlo- cinate, disodium palmitoleamido PEG-2 sulfosuccinate,
ride, dihydrogenated tallow methylamine, dihydrogenat- disodium PEG-10 laurylcitrate sulfosuccinate, disodium
ed tallow phthalate, dihydroxyethyl C12-15 alkoxypropy PEG-4 cocamido MIPA-sulfosuccinate, disodium PEG-
lamine oxide, dihydroxyethyl C8-10 alkoxypropylamine 5 8 glyceryl caprylate/caprate, disodium PEG-8 ricinosuc-
oxide, dihydroxyethyl C9-11 alkoxypropylamine oxide, cinate, disodium PPG-2- isodeceth-7 carboxyamphodia-
dihydroxyethyl cocamine oxide, dihydroxyethyl lau- cetate, disodium ricinoleamido MEA-sulfosuccinate, dis-
ramine oxide, dihydroxyethyl soya glycinate, dihydrox- odium sitostereth-14 sulfosuccinate, disodium stearami-
yethyl stearamine oxide, dihydroxyethyl tallow glycinate, do MEA-sulfosuccinate, disodium steariminodipropion-
dihydroxyethyl tallowamine HCI, dihydroxyethyl tallowa- 10 ate, disodium stearoamphodiacetate, disodium stearyl
mine oleate, dihydroxyethyl tallowamine oxide, diisobutyl sulfosuccinamate, disodium stearyl sulfosuccinate, dis-
sodium sulfosuccinate, dilaureth-10 phosphate, dilau- odium succinate, disodium succinoyl glycyrrhetinate, dis-
reth-4 dimonium chloride, dilauryldimonium chloride, dili- odium tallamido MEA-sulfosuccinate, disodium tallow
noleamidopropyl dimethylamine dimethicone copolyol sulfosuccinamate, disodium tallow amido MEAsulfosuc-
phosphate, dimethicone propyl PG-betaine, dimethyl co- 15 cinate, disodium tallow amphodiacetate, disodium tallow
camine, dinonoxynol-9 citrate, dioctyl sodium sulfosuc- iminodipropionate, disodium tetrapropenyl succinate,
cinate, dioctyldodeceth-2 lauroyl glutamate, dioctyldo- disodium tridecylsulfosuccinate, disodium undecylena-
decyllauroyl 26 glutamate, dioleth-8 phosphate, dipropyl- mido MEA-sulfosuccinate, disodium undecylenamido
ene glycol salicylate, disodium bisethylphenyl triaminot- PEG-2 sulfosuccinate, disodium wheat germamido
riazine stilbenedisulfonate, disodium C12-15 pareth sul- 20 MEA-sulfosuccinate, disodium wheat germamido PEG-
fosuccinate, disodium caproamphodiacetate, disodium 2 sulfosuccinate, disodium wheat germ amphodiacetate,
caproamphodipropionate, disodium capryloamphodiac- disoyadimonium chloride, disteareth-2 lauroyl glutama-
etate, disodium capryloamphodipropionate, disodium te, disteareth-5 lauroyl glutamate, disteareth-6 dimonium
cetearyl sulfosuccinate, disodium cocamido MEAsulfo- chloride, ditallowamidoethyl hydroxypropylamine, dital-
succinate, disodium cocamido MIPA-sulfosuccinate, dis- 25 lowedimonium chloride, di-TEA-oleamido PEG-2 sulfo-
odium cocamido PEG-3 sulfosuccinate, disodium co- succinate, di-TEA-palmitoyl aspartate, ditridecyl sodium
caminopropyl iminodiacetate, disodium cocoamphocar- sulfosuccinate, dodecylbenzene sulfonic acid, dodecyl-
boxyethy Ihydroxypropy Isulfonate, disodium cocoam- benzyltrimonium chloride, dodecylxyIylditrimonium chlo-
phodiacetate, disodium cocoamphodipropionate, diso- ride, dodoxynol- 12, dodoxynol-5, dodoxynol-6, dodoxy-
dium cocopolyglucose citrate, disodium cocopolyglu- 30 nol-7, dodoxynol-9, erucamidopropyl hydroxysultaine,
cose sulfosuccinate, disodium cocoyl butyl gluceth-10 ethyl butylacetylaminopropionate, ethyl guiazulene sul-
sulfosuccinate, disodium cocoyl glutamate, disodium de- fonate, ethyl PEG-15 cocamine sulfate, glycol stearate,
ceth-5 sulfosuccinate, disodium deceth-6 sulfosucci- hexeth-4 carboxylic acid, hydrogenated castor oil, hydro-
nate, disodium dicarboxyethyl cocopropylenediamine, genated coconut acid, hydrogenated ditallowamine, hy-
disodium dihydroxyethyl sulfosuccinylundecylenate, dis- 35 drogenated menhaden acid, hydrogenated tallow amide,
odium dimethicone copolyol sulfosuccinate, disodium 28 hydrogenated tallow betaine, hydrogenated tallowa-
distyrylbiphenyl disulfonate, disodium hydrogenated cot- mide DEA, hydrogenated tallowamine, hydrogenated tal-
tonseed glyceride sulfosuccinate, disodium hydrogenat- lowamine oxide, hydrogenated tallowtrimonium chloride,
ed tallow glutamate, disodium hydroxydecyl sorbitol cit- hydrolyzed beeswax, hydroxyceteth-60, hydroxyethyl
rate, disodium isodecyl sulfosuccinate, disodium iso- 40 carboxymethyl cocamidopropylamine, hydroxyethyl ce-
stearamido MEA-sulfosuccinate, disodium isostearami- tyldimonium chloride, hydroxyethyl cetyldimonium phos-
do MIPA-sulfosuccinate, disodium isostearoamphodiac- phate, hydroxyethyl hydroxypropyl C12-15 alkoxypro-
etate, disodium isostearoamphodipropionate, disodium pylamine oxide, hydroxyethylbutylamine laureth sulfate,
isostearylsulfosuccinate, disodium laneth-5 sulfosucci- isoceteth-30, isopropanolamine lanolate, isopropyl hy-
nate, disodium lauramido MEA-sulfosuccinate, disodium 45 droxycetyl ether, isopropylamine dodecylbenzenesul-
lauramido PEG-2 sulfosuccinate, disodium lauramido fonate, isostearamidomorpholine stearate, isostearami-
PEG-5 sulfosuccinate, disodium laureth sulfosuccinate, dopropyl betaine, isostearamidopropyl morpholine ox-
disodium laureth-12 sulfosuccinate, disodium laureth-5 ide, isostearamidopropylamine oxide, isosteareth-11
carboxyamphodiacetate, disodium laureth-6 sulfosucci- carboxylic acid, isosteareth-50, isosteareth-6 carboxylic
nate, disodium laureth-7 citrate, disodium laureth-9 sul- 50 acid, isostearic acid, isostearoyl hydrolyzed collagen,
fosuccinate, disodium lauriminodipropionate, disodium laneth-40, laneth-50, laneth-75, lanolinamide DEA, lau-
lauroamphodiacetate, disodium lauroamphodipropion- ramide/ myristamide DEA, lauramidopropyl betaine, lau-
ate, disodium lauryl sulfosuccinate, disodium myristami- ramidopropylamine oxide, lauramine oxide, laureth-1,
do MEA-sulfosuccinate, disodium nonoxynol-10 sulfo- laureth-10, laureth-10 carboxylic acid, laureth-11 carbox-
succinate, disodium oleamido MEA-sulfosuccinate, dis- 55 ylic acid, laureth-13 carboxylic acid, laureth-14 carboxylic
odium oleamido 27 MIPA-sulfosuccinate, disodium olea- acid, laureth-17 carboxylic acid, laureth-2, laureth-20,
mido PEG-2 sulfosuccinate, disodium oleoamphodipro- laureth-23, laureth-25, laureth-3, laureth-3 carboxylic ac-
pionate, disodium oleth-3 sulfosuccinate, disodium oleyl id, laureth-3 phosphate, laureth-30, laureth-4, laureth-4

10
19 EP 2 694 834 B1 20

carboxylic acid, laureth-40, laureth-5, laureth-5 carbox- lyzed collagen, oleoyl sarcosine, oleth-10, oleth-10 car-
ylic acid, laureth-6, laureth-6 carboxylic acid, laureth-6 boxylic acid, oleth-10 phosphate, oleth-12, oleth-15,
citrate, laureth-7, laureth-7 citrate, laureth-7 tartrate, lau- oleth-16, oleth-2, oleth-20, oleth-20 phosphate, oleth-23,
reth-8 phosphate, lauroamphodipropionic acid, lauroyl oleth-25, oleth-3 carboxylic acid, oleth-3 phosphate,
hydrolyzed collagen, lauroyl sarcosine, lauryl betaine, 5 oleth-4 phosphate, oleth-44, oleth-5 phosphate, oleth-
lauryl hydroxysultaine, lauryl isoquinolinium bromide, 50, oleth-6 carboxylic acid, oleyl betaine, olivamide DEA,
lauryl polyglucose, lauryl pyrrolidone, lauryl sultaine, lau- olivamidopropyl betaine, olivamidopropylamine oxide,
rylpyridinium chloride, lysine thiazolidine carboxylate, olive oil PEG-10 esters, palm kemelamide DEA, palm
magnesium cocoate, magnesium coco-sulfate, magne- kemelamide MEA, palm kemelamide MIPA, palm
sium lanolate, magnesium laureth sulfate, magnesium 10 kemelamidopropyl betaine, palmamide DEA, palmamide
laureth-11 carboxylate, magnesium laureth-16 sulfate, MEA, palmamide MIPA, palmamidopropyl betaine,
magnesium laureth-5 sulfate, magnesium laureth-8 sul- palmitamidopropyl betaine, palmitamidopropylamine ox-
fate, magnesium lauryl hydroxypropyl sulfonate, magne- ide, palmitamine oxide, palmitoyl hydrolyzed collagen,
sium lauryl sulfate, magnesium myreth sulfate, magne- palmitoyl hydrolyzed wheat protein, pea ethyl cocoyl ar-
sium oleth sulfate, magnesium PEG-3 cocamide 29 sul- 15 ginate, peanutamide MEA, peanutamide MIPA,
fate, magnesium tallowate, mannitan oleate, MEA-di- PEG/PPG-300/55 copolymer, PEG-10 castor oil, PEG-
cetearyl phosphate, MEA-laureth sulfate, MEA-laureth- 10 cocamine, PEG-10 coco-benzonium chloride, PEG-
6 carboxylate, MEA-lauryl sulfate, MEA-PPG-6-laureth- 10 isostearate, PEG-10 soyamine, PEG-10 stearate,
7-carboxylate, meroxapol105, meroxapol 108, meroxa- PEG-10 stearyl benzonium chloride, PEG-100 castor oil,
pol 171, meroxapol 172, meroxapol 174, meroxapol 178, 20 PEG-100 hydrogenated castor oil, PEG-100 lanolin,
meroxapol 251, meroxapol 252, meroxapol 254, PEG-100 stearate, PEG-11 cocamide, PEG- 120 glyc-
meroxapol255, meroxapol258, meroxapol311, eryl stearate, PEG-120 stearate, PEG-15 castor oil,
meroxapol312, meroxapol314, methoxy-PEG-7 rutinyl PEG-15 cocamine, PEG-15 cocomonium chloride, PEG-
succinate, methyl morpho line oxide, methylpyrrolidone, 15 hydrogenated tallow amine, PEG-15 oleammonium
methylbenzethonium chloride, minkamide DEA, minka- 25 chloride, PEG-15 soyamine, PEG-15 stearmonium chlo-
midopropyl betaine, minkamidopropyl dimethylamine, ride, PEG-150 distearate, PEG-150 laurate, PEG- 150
minkamidopropylamine oxide, MIPA C12-15 pareth sul- oleate, PEG-150 stearate, PEG-16 hydrogenated castor
fate, MIPA-dodecylbenzenesulfonate, MIPA-laureth sul- oil, PEG-175 distearate, PEG-2 castor oil, PEG-2 coco-
fate, MIPA-lauryl sulfate, mixed isopropanolamines benzonium chloride, PEG-2 cocomonium chloride, PEG-
lanolate, mixed isopropanolamines lauryl sulfate, mixed 30 2 hydrogenated tallow amine, PEG-2 oleammonium
isopropanolamines myristate, myreth-2 myristate, chloride, PEG-2 sorbitan isostearate, PEG-2 soyamine,
myreth-3 carboxylic acid, myreth-3 myristate, myreth-5 PEG-2 stearamide carboxylic acid, PEG-20 castor oil,
carboxylic acid, myristamidopropyl betaine, myristami- PEG-20 cocamine, PEG-20 glyceryl isostearate, PEG-
dopropyl dimethyl amine dimethicone copolyol phos- 20 hydrogenated castor oil, PEG-20 hydrogenated tallow
phate, myristamidopropyl dimethylamine phosphate, 35 amine, PEG-20 31 laurate, PEG-20 myristate, PEG-20
myristamidopropylamine oxide, myristamine oxide, myr- oleate, PEG-20 palmitate, PEG-20 sorbitan beeswax,
istaminopropionic acid, myristoyl hydrolyzed collagen, PEG- 20 sorbitan isostearate, PEG-20 stearate, PEG-20
myristoyl sarcosine, myristyl/cetyl amine oxide, myristyl tallate, PEG-200 castor oil, PEG-200 glyceryl stearate,
betaine, noneth-8, nonoxynol-10 carboxylic acid, nonox- PEG-200 glyceryl tallowate, PEG-200 hydrogenated
ynol-10 phosphate, nonoxynol-100, nonoxynol-11, non- 40 castor oil, PEG-200 trihydroxystearin, PEG-23 oleate,
oxynol-12, nonoxynol-13, nonoxynol-14, nonoxynol-15, PEG-25 castor oil, PEG-25 diethylmonium chloride,
nonoxynol-18, nonoxynol-2, nonoxynol-20, nonoxynol- PEG-25 glyceryl stearate, PEG-25 hydrogenated castor
23, nonoxynol-30, nonoxynol-4, nonoxynol-40, nonoxy- oil, PEG-28 glyceryl tallowate, PEG-29 castor oil, PEG-
nol-44, nonoxynol-5, nonoxynol-5 carboxylic acid, non- 3 castor oil, PEG-3 cocamide, PEG-3 lauramine oxide,
oxynol-50, nonoxynol-6, nonoxynol-6 phosphate, nonox- 45 PEG-3 oleamide, PEG-30 castor oil, PEG-30 glyceryl co-
ynol-7, nonoxynol- 8, nonoxynol-8 carboxylic acid, non- coate, PEG-30 glyceryl isostearate, PEG-30 glyceryl
oxynol-9, nonoxynol-9 phosphate, nonyl nonoxynol-10, oleate, PEG-30 glyceryl stearate, PEG-30 hydrogenated
nonyl nonoxynol-10 phosphate, nonyl nonoxynol-100, castor oil, PEG-30 hydrogenated tallow amine, PEG-30
nonyl nonoxynol-15 phosphate, nonyl nonoxynol-150, oleamine, PEG-30 stearate, PEG-32 laurate, PEG-32
nonyl nonoxynol-24 phosphate, nonyl nonoxynol-49, no- 50 oleate, PEG-32 stearate, PEG-33 castor oil, PEG-35 cas-
nyl nonoxynol-7 phosphate, nonyl nonoxynol-9 phos- tor oil, PEG-35 hydrogenated castor oil, PEG-35 stear-
phate, octeth-3 carboxylic acid, octoxynol-1, octoxynol- ate, PEG-36 castor oil, PEG-36 oleate, PEG-36 stearate,
10, octoxynol-11, octoxynol-13, octoxynol-16, octoxynol- PEG-4 castor oil, PEG-4 laurate, PEG-4 stearamide,
20 carboxylic acid, octoxynol-3, 30 octoxynol-30, octox- PEG-40 castor oil, PEG-40 hydrogenated castor oil,
ynol-40, octoxynol-5, octoxynol-7, octoxynol-70, octoxy- 55 PEG-40 hydrogenated tallow amine, PEG-40 sorbitan di-
nol-8, octoxynol-9, octoxynol-9 carboxylic acid, oleami- isostearate, PEG-40 sorbitan peri so stearate, PEG-40
dopropyl betaine, oleamidopropyl hydroxysultaine, olea- sorbitan peroleate, PEG-40 sorbitan stearate, PEG-40
midopropylamine oxide, oleamine oxide, oleoyl hydro- sorbitol hexaoleate, PEG-40 stearate, PEG-44 sorbitan

11
21 EP 2 694 834 B1 22

laurate, PEG-45 hydrogenated castor oil, PEG-45 stea- ether phosphate, PPG- 15-PEG-II hydrogenated lauryl
rate, PEG-45 stearate phosphate, PEG-4-PPG-7 alcohol ether, PPG-17 butyl ether, PPG-20 butyl ether,
C13/CI5 alcohol, PEG-5 castor oil, PEG-5 cocamide, PPG- 24 butyl ether, PPG-25 diethylmonium chloride,
PEG-5 ditridecylmonium chloride, PEG-5 glyceryl stea- PPG-3 hydrogenated castor oil, PPG-30-buteth-30,
rate, PEG-5 hydrogenated castor oil, PEG-5 hydrogen- 5 PPG-4 laureth-5, PPG-40 diethylmonium chloride, PPG-
ated com glycerides, PEG-5 soyamine, PEG-5 stearate, 50 cetyl ether, PPG-5-ceteth-10 phosphate, PPG-5-ce-
PEG-5 stearyl ammonium chloride, PEG-5 stearyl am- teth-20, PPG-8-ceteth-lO, PPG-8-ceteth-20, PPG-9 di-
monium lactate, PEG-5 tallow benzonium chloride, PEG- ethylmonium chloride, propylene glycol soyate, quater-
50 castor oil, PEG-50 hydrogenated castor oil, PEG-50 nium-14, quaternium-18, quatemium- 24, quatemium-
stearamine, PEG-50 stearate, PEG-6 cocamide, PEG-6 10 52, raffinose oleate, rapeseedamidopropyl benzyldimo-
oleate, PEG-6 palmitate, PEG-6 sorbitan beeswax, PEG- nium chloride, ricinoleamidopropyl betaine, ricinoleth-
60 castor oil, PEG-60 glyceryl isostearate, PEG-60 hy- 40, saponins, sesamide DEA, sesamidopropyl betaine,
drogenated castor oil, PEG- 60 sorbitan stearate, PEG- sesamidopropyl dimethylamine, sesamidopropylamine
66 trihydroxystearin, PEG-7 cocamide, PEG-7 glyceryl oxide, sodium/MEA laureth-2 sulfosuccinate, sodi-
cocoate, PEG- 7 hydrogenated castor oil, PEG-7 oleate, 15 um/TEA-lauroyl collagen amino acids, sodium/TEAlau-
PEG- 75 castor oil, PEG-75 dioleate, PEG-75 lanolin, 32 royl hydrolyzed collagen, sodiumlTEA-lauroyl hydro-
PEG-75 lanolin oil, PEG-75 lanolin wax, PEG-75 laurate, lyzed keratin, sodiumlTEA-lauroyl keratin amino acids,
PEG-75 oleate, PEG-75 sorbitan laurate, PEG-75 stea- sodium/TEA-undecylenoyl collagen amino acids, sodi-
rate, PEG-78 glyceryl cocoate, PEG-8 castor oil, PEG-8 um/TEA-undecylenoyl hydrolyzed collagen, sodium be-
laurate, PEG-8 propylene glycol cocoate, PEG-8 rici- 20 henoyl lactylate, sodium bisglycol ricinosulfosuccinate,
noleate, PEG-8 sorbitan beeswax, PEG-8 soyamine, sodium butoxynol- 12 sulfate, sodium C11-15 pareth-7
PEG-8 stearate, PEG-80 glyceryl cocoate, PEG-80 hy- carboxylate, sodium C12-13 pareth sulfate, sodium
drogenated castor oil, PEG-80 jojoba acid, PEG- 80 jo- C12-14 olefin sulfonate, sodium C12-15 alkoxypropyl im-
joba alcohol, PEG-80 sorbitan laurate, PEG- 80 sorbitan inodipropionate, sodium C12-15 alkyl sulfate, sodium
palmitate, PEG-85 lanolin, PEG-9 castor oil, PEG-9 rici- 25 C12-15 pareth sulfate, sodium C12-15 pareth-15 sul-
noleate, PEG-90 stearate, pentaerythrityl tetraisostear- fonate, sodium C12-15 pareth-3 sulfonate, sodium
ate, poloxamer 101, poloxamer 105, poloxamer 108, C12-15 pareth-6 carboxylate, sodium C12-15 pareth-7
poloxamer 122, poloxamer 123, poloxamer 124, carboxylate, sodium C12-15 pareth-7 sulfonate, sodium
poloxamer 181, poloxamer 182, poloxamer 183, C12-18 alkyl sulfate, sodium C13-17 alkane sulfonate,
poloxamer 184, poloxamer 185, poloxamer 188, 30 sodium C14-16 olefin sulfonate, sodium C14-17 alkyl sec
poloxamer 212, poloxamer 215, poloxamer 217, sulfonate, sodium C14-18 olefin sulfonate, sodium
poloxamer 231, poloxamer 234, poloxamer 235, C16-18 olefin sulfonate, sodium C16-20 alkyl sulfate, so-
poloxamer 237, poloxamer 238, poloxamer 282, dium C8-16 isoalkylsuccinyl lactoglobulin sulfonate, so-
poloxamer 284, poloxamer 288, poloxamer 331, dium C9-22 alkyl sec sulfonate, sodium caproamphoac-
poloxamer 333, poloxamer 334, poloxamer 335, 35 etate, sodium caproamphohydroxypropylsulfonate, so-
poloxamer 338, poloxamer 401, poloxamer 402, dium caproamphopropionate, sodium caprylate, sodium
poloxamer 403, poloxamer 407, polyglyceryl- 4-PEG-2 capryleth-2 carboxylate, sodium capryleth-9 34 carbox-
cocamide, polysorbate 20, polysorbate 40, polysorbate ylate, sodium capryloamphoacetate, sodium capryloam-
60, polysorbate 65, polysorbate 80, polysorbate 85, po- phohydroxypropylsulfonate, sodium capryloamphopro-
tassium abietoyl hydrolyzed collagen, potassium C9-15 40 pionate, sodium caprylyl sulfonate, sodium carboxyethyl
alkyl phosphate, potassium castorate, potassium cetyl tallow polypropylamine, sodium carboxymethyl cocopol-
phosphate, potassium cocoate, potassium cocoyl gluta- ypropylamine, sodium carboxymethyl oleyl polypro-
mate, potassium cocoyl hydrolyzed collagen, potassium pylamine, sodium carboxymethyl tallow polypro-
cornate, potassium cyclocarboxypropyloleate, potassi- pylamine, sodium castorate, sodium cetearyl sulfate, so-
um dihydroxyethyl cocamine oxide phosphate, potassi- 45 dium ceteth-13 carboxylate, sodium cetyl sulfate, sodium
um dodecylbenzenesulfonate, potassium laurate, potas- cocaminopropionate, sodium coceth sulfate, sodium co-
sium lauroyl collagen amino acids, potassium lauroyl hy- co/hydrogenated tallow sulfate, sodium cocoamphoace-
drolyzed collagen, potassium lauroyl hydrolyzed soy pro- tate, sodium cocoamphohydroxypropylsulfonate, sodi-
tein, potassium lauryl hydroxypropyl sulfonate, potassi- umcocoamphopropionate, sodium cocoate, sodium co-
um lauryl sulfate, potassium methyl cocoyl taurate, po- 50 coglyceryl ether sulfonate, sodium cocomonoglyceride
tassium myristate, potassium myristoyl hydrolyzed col- sulfate, sodium cocomonoglyceride sulfonate, sodium
lagen, potassium octoxynol-12 phosphate, potassium cocopolyglucose tartrate, sodium coco-sulfate, sodium
oleate, potassium oleoyl hydrolyzed collagen, potassium cocoyl collagen amino acids, sodium cocoyl glutamate,
olivate, potassium palmitate, potassium ricinoleate, po- sodium cocoyl hydrolyzed collagen, sodium cocoyl hy-
tassium stearate, potassium stearoyl hydrolyzed colla- 55 drolyzed keratin, sodium cocoyl hydrolyzed rice protein,
gen, potassium tallowate, potassium toluenesulfonate, sodium cocoyl hydrolyzed soy protein, sodium cocoyl hy-
potassium undecylenoyl hydrolyzed 33 collagen, potas- drolyzed wheat protein, sodium cocoyl isethionate, sodi-
sium xylene sulfonate, PPG-IO cetyl ether, PPG-IO cetyl um cocoyllactylate, sodium cocoyl sarcosinate, sodium

12
23 EP 2 694 834 B1 24

comamphopropionate, sodium cumenesulfonate, sodi- sodium trideceth-8 carboxylate, sodium tridecyl sulfate,
um cyclopentane carboxylate, sodium deceth sulfate, so- sodium tridecylbenzenesulfonate, sodium trilaureth-4
dium deceth-2 carboxylate, sodium decylbenzenesul- phosphate, sodium undecy lenoamphoacetate, sodium
fonate, sodium dicarboxyethylcoco phosphoethyl imida- undecy lenoamphopropionate, sodium wheat germam-
zoline, sodium diethylaminopropyl cocoaspartamide, so- 5 phoacetate, sodium xylenesulfonate, soya hydroxyethyl
dium dihydroxycetyl phosphate, sodium dilaureth-7 cit- imidazoline, soyamide DEA, soyamidopropyl betaine,
rate, sodium dodecylbenzenesulfonate, sodium ethyl 2- soyamidopropyl dimethylamine, soyamidopropyl ethyld-
sulfolaurate, sodium glycereth-I polyphosphate, sodium imonium ethosulfate, soytrimonium chloride, stearami-
glyceryl oleate phosphate, sodium guiazulene sulfonate, dopropyl betaine, stearamidopropyl dimethyl amine,
sodium hydrogenated tallow glutamate, sodium iso- 10 stearamidopropylamine oxide, stearamine oxide,
stearoamphoacetate, sodium isostearoamphopropion- steareth-10, steareth-100, steareth-2, steareth-20,
ate, sodium laneth sulfate, sodium lauramido diacetate, steareth- 21, steareth-2S, steareth-27, steareth-30,
sodium lauramidopropyl hydroxyphostaine, sodium lau- steareth-40, steareth-50, stearoyl sarcosine, stearyl
raminopropionate, sodium laurate, sodium laureth sul- betaine, sucrose laurate, sucrose palmitate, sulfated
fate, sodium laureth-11 carboxylate, sodium laureth-12 15 castor oil, sulfated glyceryl oleate, sulfated olive oil, sul-
sulfate, sodium laureth-13 carboxylate, sodium laureth- fated peanut oil, sulfonated castor oil, tallow amide, tallow
14 carboxylate, sodium laureth-17 carboxylate, sodium amine, tallow betaine, tallow dihydroxyethyl betaine, tal-
laureth-4 35 carboxylate, sodium laureth-4 phosphate, low hydroxy ethyl imidazoline, tallowalkonium chloride,
sodium laureth-5 carboxylate, sodium laureth-5 sulfate, tallowamidopropyl betaine, tallowamidopropyl dimethyl-
sodium laureth-6 carboxylate, sodium laureth-7 sulfate, 20 amine, tallowamidopropyl hydroxysultaine, tallowamido-
sodium laureth-7 tartrate, sodium laureth -8 sulfate, so- propylamine oxide, tallowamine oxide, tallowedimonium
dium lauriminodipropionate, sodium lauroampho PG-ac- propyltrimonium dichloride, tallowtrimonium chloride,
etate phosphate, sodium lauroamphoacetate, sodium TEA-abietoyl hydrolyzed collagen, TEA-C10-12 alkyl sul-
lauroamphohydroxypropylsulfonate, sodium lauroyl as- fate, TEA-C10-14 alkyl benzenesulfonate, TEA-C10-15
partate, sodium lauroyl glutamate, sodium lauroyl hydro- 25 alkyl sulfate, TEA-C12-15 alkyl sulfate, TEA-cocoate,
lyzed collagen, sodium lauroyl isethionate, sodium lau- TEA-cocosulfate, TEA-cocoyl glutamate, TEA-cocoyl
royl methylaminopropionate, sodium lauroyl sarcosinate, hydrolyzed collagen, TEA-cocoyl sarcosinate, TEA-do-
sodium lauroyl taurate, sodium lauryl phosphate, sodium decylbenzenesulfonate, TEAhydrogenated tallow gluta-
lauryl sulfate, sodium lauryl sulfoacetate, sodium ligno- mate, TEA-isostearate, TEA-isostearoyl hydrolyzed col-
sulfonate, sodium methyl-2-sulfolaurate, sodium methyl 30 lagen, TEAlauraminopropionate, TEA-laureth sulfate,
cocoyl taurate, sodium methyl lauroyl taurate, sodium TEA-lauroyl collagen amino acids, TEA-lauroyl glutama-
methyl myristoyl taurate, sodium methyl oleoyl taurate, te, TEA-lauroyl hydrolyzed collagen, TEA-lauroyl keratin
sodium methyl palmitoyl taurate, sodium methyl stearoyl amino acids, TEA-lauroyl lactylate, TEA-lauroyl sarcosi-
taurate, sodiummethylnaphthalenesulfonate, sodium nate, TEA-lauryl sulfate, TEA-myristaminopropionate,
myreth sulfate, sodium myristate, sodium myristoam- 35 TEAmyristate, TEA-myristoyl hydrolyzed collagen, TEA-
phoacetate, sodium myristoyl glutamate, sodium myris- oleate, TEA-oleoyl hydrolyzed collagen, 37 TEA-oleoyl
toyl isethionate, sodium myristoyl sarcosinate, sodium sarcosinate, TEA-oleyl sulfate, TEA-palm kernel sarcosi-
myristyl sulfate, sodium nonoxynol-1 sulfate, sodium nate, TEA-palmitate, TEAPEG-3 cocamide sulfate, TEA-
nonoxynol-10 sulfate, sodium nonoxynol-4 sulfate, sodi- stearate, TEA-tallate, TEA-tridecylbenzenesulfonate,
um nonoxynol-6 phosphate, sodium nonoxynol-9 phos- 40 TEAundecylenoyl hydrolyzed collagen, tetrasodium di-
phate, sodium octoxynol-2 ethane sulfonate, sodium oc- carboxyethyl stearyl sulfosuccinamate, TIPAlaureth sul-
tyl sulfate, sodium oleate, sodium oleoamphoacetate, so- fate, TLPA-Iauryl sulfate, TIPA-stearate, tocophereth-
dium oleoamphohydroxypropylsulfonate, sodium ole- 10, tocophereth-12, tocophereth- 18, tocophereth-5, to-
oamphopropionate, sodium oleoyl isethionate, sodium cophereth-50, toluene sulfonic acid, triceteareth-4 phos-
oleth-7 phosphate, sodium oleth-8 phosphate, sodium 45 phate, triceteth-5 phosphate, trideceth-12, trideceth-15
olivate, sodium palm kemelate, sodium palmate, sodium carboxylic acid, trideceth-19 carboxylic acid, trideceth-3
palmitate, sodium PEG-6 cocamide carboxylate, sodium carboxylic acid, trideceth-4 carboxylic acid, trideceth-6,
polydimethylglycinophenolsulfonate, sodium polynaph- trideceth-6 phosphate, trideceth-7 carboxylic acid, tride-
thalenesulfonate, sodium polystyrene sulfonate, sodium ceth-8, tridecylbenzenesulfonic acid, triheptanoin, trilau-
ricinoleoamphoacetate, sodium shale oil sulfonate, so- 50 ryl phosphate, triolein PEG-6 esters, trisodium lauroam-
dium soya hydrolyzed collagen, sodium stearate, sodium pho PG-acetate phosphate chloride, tristearyl phos-
stearoamphoacetate, sodium stearoamphopropionate, phate, undecyl polyglucose, undecylenamidopropyl
sodium stearyl betaine, sodium stearyl sulfate, sodium betaine, undecylenamidopropylamine oxide, unde-
tallamphopropionate, sodium tallow sulfate, sodium tal- cylenoyl wheat amino acids, wheat germamide DEA,
lowamphoacetate, sodium tallowate, sodium toluenesul- 55 wheat germamidopropyl betaine, wheat germamidopro-
fonate, sodium trideceth 36 sulfate, sodium trideceth-12 pyl dimethylamine, wheat germamidopropyl dimethyl
carboxylate, sodium trideceth-3 carboxylate, sodium tri- amine lactate, wheat germamidopropylamine oxide, xy-
deceth-6 carboxylate, sodium trideceth-7 carboxylate, lene sulfonic acid, zinc pentadecene tricarboxylate, and

13
25 EP 2 694 834 B1 26

combinations thereof. In some embodiments, the sur- tives are included in the hair straightening formulations
factants are present in an amount of about 0.1%-15.0% disclosed herein. In some embodiments, one or more of
by weight. In some embodiments, the preferred range is the preservatives includes one or more glycerin contain-
about 1.0%-10.0% by weight. ing compounds. In some embodiments the preservatives
5 include a chemical selected from the group consisting of:
Emollients glycerin, ethylhexylglycerin, and phenoxyethanol. In
some embodiments, the preservatives further include
[0062] In certain embodiments, the hair straightening benzyl alcohol, EDTA, and/or potassium sorbate. In
formulations include one or more emollients. As defined some embodiments, the preservatives of the formula-
herein, an "emollient" is a material that protects against 10 tions disclosed herein include plant-derived compounds
wetness or irritation, softens, soothes, supples, coats, or compound mixtures. In certain embodiments, the
lubricates, moisturizes, protects, and/or cleanses the plant-derived compounds or compound mixtures are se-
skin. In certain embodiments, one or more of the emol- lected from the group consisting of: grapefruit seed ex-
lients included in the hair straightening formulations dis- tract, radish root ferment filtrate, Aloe barbadensis leaf
closed herein is a silicone compound. In certain embod- 15 ferment filtrate, Sorbus aucuparia fruit ferment filtrate,
iments, the silicone compound is selected from the group Ribes nigrum (black currant) fruit extract, Sambucus ni-
consisting of: dimethicone, cyclomethicone, dimethicone gra fruit extract, japonica root extract, Zingiber officinale
copolyol, a mixture of cyclopentasiloxane and cyclopen- (ginger) root extract, Allium sativum (garlic) bulb extract,
tasiloxane polysilicone. In certain embodiments, the in- Origanum vulgare leaf extract, Thymus vulgaris (thyme)
ventive formulations disclosed herein include polyols. In 20 leaf extract, Rosmarinus officinalis (rosemary) leaf ex-
some embodiments, the polyols are selected from the tract, and combinations thereof. In preferred embodi-
group consisting of: sorbitol, glycerin, propylene glycol, ments, the hair straightening formulations are paraben-
ethylene glycol, polyethylene glycol, caprylyl glycol, poly- free. In certain embodiments, the preservative compo-
propylene glycol, 1,3-butane diol, hexylene glycol, iso- nent is from about 0.05-15% by weight of the hair straight-
prene glycol, xylitol. In some embodiments, the present 25 ening formulations disclosed herein. In preferred embod-
invention discloses the use of ethylhexyl palmitate, a trig- iments, the preservative component is from about
lyceride such as caprylic/capric triglyceride, and fatty acid 0.1-5.0% by weight of the hair straightening formulations
ester such as cetearyl isononanoate or cetyl palmitate disclosed herein.
as emollients. In certain embodiments, the emollient is
selected from the group consisting of: dimethicone, ami- 30 Skin Protecting Agents
dodimethicone, dimethiconol, cyclopentasiloxane, po-
tassium dimethicone PEG-7 panthenyl phosphate, cete- [0065] In certain embodiments, the hair straightening
aryl isononanoate, cetyl palmitate, and combinations formulations disclosed herein include one or more skin
thereof. In some embodiments, the emollient is about protecting agents. In some embodiments, the skin pro-
0.5-15.0% by weight of the hair straightening formula- 35 tecting agents include one or more agents that prevent
tions. In certain preferred embodiments, the emollient is the transmission of microbes. In some embodiments, the
about 1.0-10.0% by weight of the hair straightening for- hair straightening formulations disclosed herein include
mulations. antibacterial agents. In some embodiments, the skin pro-
tecting agents include skin cleansing agents. In certain
Emulsifiers 40 embodiments, the skin cleansing agents include one or
more disinfectants and/or antiseptic agents. In some em-
[0063] In certain embodiments, formulations of the bodiments, the skin protecting agents include ultraviolet
present invention include one or more emulsifiers. Emul- to visible radiation blocking agents. In some embodi-
sifiers used in the hair straightening formulations of the ments, skin protecting agents included in the hair
present invention include a copolymer of an unsaturated 45 straightening formulations of the present invention in-
ester and styrene sulphonate monomer, cetearyl alcohol, clude cleansing agents. In some embodiments, the
glyceryl ester, polyoxyethylene glycol ether of cetearyl cleansing agents are selected from the group consisting
alcohol, stearic acid, polysorbate-20, ceteareth-20, leci- of: sodium cocyl amino acids, benzalkonium chloride,
thin, glycol stearate, polysorbate-60 and/or polysorbate- centrimonium chloride, and combinations thereof. In
80. In some embodiments, the emulsifier is about 50 some embodiments, the skin protecting component is
0.05-15.0% by weight of the hair straightening formula- about 0.1-10.0% by weight of the hair straightening for-
tions disclosed herein. In preferred embodiments, the mulations disclosed herein. In some preferred embodi-
emulsifier is about 0.1-10.0% by weight of the hair ments, the skin protecting component is about 0.5-5.0%
straightening formulations disclosed herein. by weight of the formulations disclosed herein.
55
Preservatives Botanicals

[0064] In some embodiments, one or more preserva- [0066] In certain embodiments, the hair straightening

14
27 EP 2 694 834 B1 28

formulations disclosed herein include one or more bo- the group consisting of: caramel, vanilla, coconut, and
tanical, or botanical-derived ingredients. In some embod- jasmine. One of skill in the art would readily appreciate
iments, one or more botanicals are derived from the that almost any fragrance could be used in the formula-
group consisting of: Castanha do Brasil (Brazil nut, tions of the present invention. In some embodiments, the
Bertholletia excelsa) oil and butter, Mauritia fruit, essen- 5 fragrance component is about 0.1-10.0% by weight of
tial Buriti fruit oil (Mauritia flexuosa), Andiroba seed oil, the formulations disclosed herein. More preferably, the
Mango seed oil and butter, Jojoba oil, Olive squalane, fragrance component is about 0.1-1.0% by weight of the
oil, and leaf extract, Sunflower oil, Sangre de Drago, Sa- formulations disclosed herein.
mambaia, Una de Gato, Camu Camu, Cupuacu oil and
butter, Espinheira Santa, Maracuja (passion flower) oil, 10 Product Application
Vitamin E, Sandelwood essential oil, avocado oil, coco-
nut (Cocos nucifera) oil, sweet almond oil, Aloe Vera (Al- [0070] In some embodiments, the present invention
oe Barbadensis) leaf juice, butter, and oil, Shea butter, teaches a method in which a hair straightening formula-
Macadamia nut oil, Blueberry seed oil, Pomegranate tion disclosed herein, or any component thereof, is ap-
seed oil, Green tea extract, Lemon essential oil, Lime 15 plied to pre-cleaned, substantially dry, naturally curly
essential oil, Mandarin oil and butter, Tangerine oil and hair, and distributed through the hair for a period sufficient
butter, Orange blossom, sweet Orange oil, Orange wild to saturate the hair. The hair is then optionally styled by
oil, Orange essence oil, Vanilla extract, Guarana extract, blow drying with a hand-held hair dryer or by another
Palm butter, and Wheat proteins. One of skill in the art means with a substantially similar effect.
would readily appreciate that additional botanicals could 20 [0071] In some embodiments, the hair is washed with
be used in addition to those disclosed herein. a shampoo that is slightly basic, before applying a for-
mulation disclosed herein, or any component thereof. In
Diluents some embodiments, the hair is washed with a shampoo
that is slightly basic about 0.1-3.0 hours before applying
[0067] The term "diluent," as used herein refers to sub- 25 the formulation. In some embodiments, the pH of the
stances that may be used to dilute the active ingredient, shampoo is about 7.0-8.0. In some embodiments, the
as disclosed above. In some embodiments, water is used shampoo contains citric acid buffered with sodium citrate.
as the diluent In some embodiments, the formulations In some embodiments, alternative acids and/or buffers
require use of greater than 1.0% water to be effective. with substantially similar chemical effects are used.
Advantageously, greater than 5.0% water is used. Pref- 30 [0072] When the above-mentioned methods of apply-
erably, greater than 50% water is used. Even more pref- ing shampoo and treatment are used, the slightly alkaline
erably, greater than 70% water is used. In certain em- pH swells the hair and breaks down the disulfide double
bodiments, alcohols are used. In some embodiments, bond of the cysteine portion of the keratin molecule. The
the alcohols are used at low concentrations to enhance porosity of the cuticle layer (the outer layer of the hair) is
shaft penetration and/or reduce odor. In some embodi- 35 important since it determines the amount of treatment
ments the concentration of the alcohols used is about (fixative) agent that can subsequently enter the cortex of
0.5%. In some embodiments, the alcohols used in the the hair.
inventive formulations are ethyl alcohol and isopropyl al- [0073] In other embodiments of the present invention,
cohol. High concentrations above about 35.0% and the hair straightening formulation disclosed herein, or
greater of alcohols are not preferred, as they disrupt the 40 one or more components thereof, is (1) applied to pre-
effectiveness of the formulations. cleaned, optionally substantially dry, naturally curly hair,
(2) distributed through the hair and maintained in contact
Auxiliary Ingredients with the hair for a period sufficient to saturate the hair,
preferably at least about ten minutes, (3) optionally dried
[0068] In some embodiments, the hair straightening 45 by blow drying the hair with a hand-held electric hair dryer
formulations disclosed herein include one or more thick- or substantially equivalent means until the hair feels sub-
eners, particularly when the formulation is in the form of stantially dry to the touch and (4) styled with a heated
a cream, lotion or gel. In some embodiments, the thick- ceramic flat hair iron having a platen, wherein tempera-
eners include polyethylene glycol and/or sodium polyacr- ture setting of the flat iron is in the range 150-235°C.
ylate. In some embodiments, the thickener component 50 [0074] In certain embodiments, a preconditioning com-
is present in an amount of about 0.1-5.0% by weight of position is applied to the hair, by spraying, brushing or
the formulations disclosed herein. More preferably, the equivalent means. The preconditioning composition is
thickener component is present in an amount of about distributed through the hair, and maintained in contact
0.2-1.0% by weight of the formulations disclosed herein. with the hair for a period sufficient to saturate the hair. In
[0069] In some embodiments of the present invention, 55 certain embodiments, the preconditioning composition is
fragrances are added to mask the odor of various other applied and allowed to saturate the hair for at least about
components in the formulations of the present invention. 5-10 minutes. In some embodiments, the preconditioned
In some embodiments, the fragrances are selected from hair is then rinsed with tepid water for at least about 30

15
29 EP 2 694 834 B1 30

seconds, towel blotted and then contacted with a hair mainder of the hair straightening formulation, or one or
straightening formulation. more components therof. In yet other embodiments, the
[0075] The hair straightening formulations of the one or more pH lowering agents and one or more reduc-
present invention, or one or more components thereof, ing agents are applied together, but separately from the
are preferably applied with a brush, distributed through 5 remainder of the hair straightening formulation, or one or
the hair, and maintained in contact with the hair for a more components therof.
period sufficient to saturate the hair. Preferably, the hair [0081] The present invention is also directed to a kit
straightening formulation, or one or more components with an intended function of facilitating the straightening
thereof, is in contact with the hair for at least about 5-10 of hair. The kit can be configured in numerous ways to
minutes. 10 be useful for practicing any of the inventive methods dis-
[0076] In some embodiments, the hair is then contact- closed herein, including straightening hair with one or
ed with a thermal protectant composition distributed more of the inventive formulations, or one or more com-
through the hair, the hair is then optionally blow-dried ponents thereof, disclosed herein.
using a hand-held electric hair dryer or substantially [0082] The kit is an assemblage of materials or com-
equivalent means for drying, set at a heat of about 105°C 15 ponents, including at least one of the inventive formula-
until the hair feels substantially dry to the touch, and is tions, or one or more components thereof. Thus, in some
then styled with a heated ceramic flat hair iron having a embodiments the kit contains a formulation including
platen temperature setting in the range 150-235°C. In substances selected from the group consisting of: one
some embodiments, the entire hair straightening process or more keratin hydrolysates, one or more pH-lowering
is completed in about 40-120 minutes. 20 agents, one or more reducing agents, one or more
[0077] In some embodiments of the present invention, crosslinking agents, and combinations thereof, with or
the hair straightening formulation, or one or more com- without shampoo, conditioner, or other categories of ad-
ponents therof, is present in the preconditioning compo- ditional components and/or agents described above and
sition, in the thermal protectant composition, or in the below.
preconditioning composition and thermal protectant 25 [0083] In some embodiments, the kit is configured par-
composition. In certain embodiments, neither a precon- ticularly for use with mammalian subjects. In some em-
ditioning composition nor thermal protectant composition bodiments, the kit is configured particularly for use with
are used, and the hair straightening formulation, or one human subjects.
or more components therof, is applied directly to clean, [0084] Instructions for use may be included in the kit.
damp hair. 30 "Instructions for use" typically include a tangible expres-
[0078] In some embodiments, the preconditioning sion describing the technique to be employed in using
composition contains a cationic conditioning agent. In the components of the kit to affect a desired outcome,
certain embodiments, the cationic conditioning agent is including straightening hair with one or more of the for-
a monomeric or polymeric quaternary ammonium com- mulations, or components thereof, as disclosed herein.
pound and is preferably alkaline in the presence of a curl 35 [0085] The materials and/or components assembled
minimizing agent. The thermal protectant compositions in the kit can be provided and stored in any convenient
of the inventive method preferably contain a silicone com- and suitable way that preserves their operability and util-
ponent and are slightly acidic to substantially neutral in ity. For example, the formulations, or one or more com-
the presence of the hair straightening formulations, or ponents thereof, can be in dissolved, dehydrated, or
components therof. 40 lyophilized form; they can be provided at room, refriger-
[0079] In certain embodiments, the hair straightening ated or frozen temperatures. The components are typi-
system includes the use of at least one "leave-in" condi- cally contained in suitable packaging material(s). As em-
tioner applied after the straightening procedure and left ployed herein, the phrase "packaging material" refers to
in the hair. one or more physical structures used to house the con-
[0080] In certain embodiments, one or more of the re- 45 tents of the kit, such as one or more of the inventive for-
ducing agents is applied before and separately from the mulations and the like. The packaging material is con-
remainder of the hair straightening formulation, or one or structed by well-known methods, preferably to provide a
more components therof. In some embodiments, this ap- sterile, contaminant-free environment. As used herein,
plication is carried out to clean, damp hair and the solution the term "package" refers to a suitable solid matrix or
is left in contact with the hair for about 5-30 minutes before 50 material such as glass, plastic, paper, foil, Styrofoam and
applying the remainder of the hair straightening formu- the like, capable of holding the individual kit components.
lation, or one or more components thereof. In yet other Thus, for example, a package can be a glass, plastic, or
embodiments, the pH-lowering agent is applied before paper vessel used to contain suitable quantities of an
and separately from the remainder of the hair straight- inventive formulation containing hair straightener includ-
ening formulation, or one or more components thereof. 55 ing: one or more keratin hydrolysates, one or more pH-
In some embodiments, this application is carried out to lowering agents, one or more reducing agents, one or
clean, damp hair and the solution is left in contact with more crosslinking agents, and optionally one or more
the hair for about 5-10 minutes before applying the re- substances of the other categories of agents disclosed

16
31 EP 2 694 834 B1 32

herein. The packaging material generally has an external [0089] One skilled in the art will recognize many meth-
label which indicates the contents and/or purpose of the ods and materials similar or equivalent to those described
kit and/or its components, as well as its various market- herein, which could be used in the practice of the present
able attributes. invention. Indeed, the present invention is in no way lim-
[0086] In some embodiments, the invention teaches a 5 ited to the methods and materials described.
kit with components selected from the group consisting [0090] The following examples are for illustrative pur-
of: a hair straightening formulation, a thermal protectant poses only and are not intended to limit the scope of the
composition, and combinations thereof. In some embod- disclosure or its various embodiments in any way.
iments, the kit also contains one or more implements for
performing a curl minimizing procedure. In certain em- 10 EXAMPLES
bodiments, the implements are selected from the group
consisting of: disposable gloves, a brush, a comb, a Example 1
hand-held blow dryer, a flat hair iron, combinations there-
of, and the like. The kit components preferably are sep- Formulation #1
arately packaged and contained in an outer package. 15
The outer package can be a box or carton or shrink wrap, [0091] The hair straightening formulation may have the
and preferably has instructional indicia printed thereon following composition:
or visible therethrough.
Ingredients Weight%
Product and Method Promotion 20
keratin protein fraction 0.5-2.0
[0087] In certain embodiments, the invention includes pH adjusting agent 0.25-2.0
one or more forms of instructional indicia. In some em-
crosslinking agent 0.25-2.0
bodiments of the present invention, instructional indicia
are selected from the group consisting of: printed media, 25 reducing agent 0.25-2.0
aural media, visual aids, electronic media, and combina-
propylene glycol 1.0-5.0
tions thereof, which instruct the user on the use of the
hair product. In some embodiments of the present inven- dimethicone 0.25-1.0
tion, printed media used with the formulations and ac- cyclomethicone 0.5-2.0
companying products disclosed herein are selected from 30
the group consisting of: labels attached to, or imprinted phenyl trimethicone 0.5-2.0
on, the components of the kit, package inserts, pam- cetyl alcohol 0.25-1.5
phlets, books, flyers, combinations thereof, and the like.
cetrimonium chloride 0.25-1.0
In some embodiments of the present invention, aural me-
dia used with the formulations and accompanying prod- 35 glutamine 0.25-1.0
ucts disclosed herein are selected from the group con-
glycine 0.25-1.0
sisting of: tape recordings, audio compact discs, records,
combinations thereof, and the like. In some embodiments alanine 0.25-1.0
of the present invention, visual aids used with the formu- proline 0.25-1.0
lations and accompanying products disclosed herein are 40
selected from the group consisting of: slides, movies, vid- serine 0.25-1.0
eos, DVDs, and the like. In some embodiments of the threonine 0.25-1.0
present invention, electronic media used with the formu-
lations and accompanying products disclosed herein in- arginine 0.25-1.0
clude electronic data storage media. In some embodi- 45 lysine 0.25-1.0
ments, the electronic data storage media is selected from
glutamic acid 0.25-1.0
the group consisting of: diskettes, interactive CD-ROMs,
interactive DVDs, combinations thereof, and the like. silk amino acids 0.25-2.0
[0088] While the foregoing written description of the
Mauritia flexuosa (buriti) Fruit oil 0.25-2.0
invention enables one of ordinary skill to make and use 50
what is considered presently to be the best mode thereof, Cocos nucifera (coconut) oil 0.25-2.0
those of ordinary skill will understand and appreciate the
existence of variations, combinations, and equivalents
[0092] In order to apply the hair straightening formula-
of the specific embodiments, methods, and examples
tion, the hair is thoroughly washed with a clarifying sham-
herein. The invention should therefore not be limited by 55
poo and towel-dried. The formulation is then applied to
the above described embodiments, methods, and exam-
the damp hair, combed or brushed into the hair, and left
ples, but by all embodiments and methods within the
to process for 20-30 min. The hair is then blow-dried thor-
scope and spirit of the invention.

17
33 EP 2 694 834 B1 34

oughly and then flat-ironed at 220°C. embodiments herein is intended merely to better illumi-
[0093] Alternatively, the shampooed hair is dried fully nate the application and does not pose a limitation on
with a hair drier. The formulation is then applied to the the scope of the application otherwise claimed. No lan-
dry hair, combed or brushed into the hair, and left to proc- guage in the specification should be construed as indi-
ess for 20-30 min. At that point, the hair can be rinsed 5 cating any non-claimed element essential to the practice
out with water, dried thoroughly with a blow drier and of the application.
then flat-ironed at 220°C. The processed hair can also [0098] Preferred embodiments of this application are
be blow-dried thoroughly and then flat-ironed at 220°C, described herein, including the best mode known to the
without the rinsing step. inventors for carrying out the application. Variations on
[0094] The various methods and techniques described 10 those preferred embodiments will become apparent to
above provide a number of ways to carry out the appli- those of ordinary skill in the art upon reading the foregoing
cation. Of course, it is to be understood that not neces- description. It is contemplated that skilled artisans can
sarily all objectives or advantages described can be employ such variations as appropriate, and the applica-
achieved in accordance with any particular embodiment tion can be practiced otherwise than specifically de-
described herein. Thus, for example, those skilled in the 15 scribed herein. Accordingly, many embodiments of this
art will recognize that the methods can be performed in application include all modifications and equivalents of
a manner that achieves or optimizes one advantage or the subject matter recited in the claims appended hereto
group of advantages as taught herein without necessarily as permitted by applicable law. Moreover, any combina-
achieving other objectives or advantages as taught or tion of the above-described elements in all possible var-
suggested herein. A variety of alternatives are mentioned 20 iations thereof is encompassed by the application unless
herein. It is to be understood that some preferred em- otherwise indicated herein or otherwise clearly contra-
bodiments specifically include one, another, or several dicted by context.
features, while others specifically exclude one, another,
or several features, while still others mitigate a particular REFERENCES
feature by inclusion of one, another, or several advanta- 25
geous features. [0099]
[0095] Furthermore, the skilled artisan will recognize
the applicability of various features from different embod- 1. Resnick, L.; Grams, I.; Goodfellow, A.; Allice, D.
iments. Similarly, the various elements, features and Hair Straightening Formulations, Methods, and Sys-
steps discussed above, as well as other known equiva- 30 tems. US 2009/0165812 A1, Sep. 8, 2008.
lents for each such element, feature or step, can be em- 2. Syed, A. N.; Askar, N. A.; Milczarek, P. Keratin-
ployed in various combinations by one of ordinary skill in protective Curl Minimizer Compositions, Method,
this art to perform methods in accordance with the prin- and Kit Therefor. WO 2007/032762 A1, Sep. 12,
ciples described herein. Among the various elements, 2005.
features, and steps some will be specifically included and 35 3. Whewell, C. S., The Chemistry of Hair. J. Soc.
others specifically excluded in diverse embodiments. Cosmetic Chem. 1964, 15, 423-436.
[0096] Although the application has been disclosed in 4. Robbins, C. R., Chemical and Physical Behavior
the context of certain embodiments and examples, it will of Human Hair 3rd ed.; Springer-Verlag: 1994.
be understood by those skilled in the art that the embod- 5. Cook; Smith, Appl. Polym. Symp. 1971, 18 (50),
iments of the application extend beyond the specifically 40 663.
disclosed embodiments to other alternative embodi- 6. Parreira, H. C., On the Isoelectric Point of Human
ments and/or uses and modifications and equivalents Hair. J. Colloid Interface Sci. 1980, 75 (1), 212-217.
thereof. 7. Miyata, T.; Noishiki, Y. Medical Material. US
[0097] In some embodiments, the terms "a" and "an" 4,695,281, Mar. 25, 1983.
and "the" and similar references used in the context of 45 8. Imamura, E.; Noishiki, Y.; Koyanagi, H.; Miyata,
describing a particular embodiment of the application (es- T.; Furuse, M. Bioprosthetic Valve. US 5,080,670,
pecially in the context of certain of the following claims) Aug. 30, 1988
can be construed to cover both the singular and the plural. 9. Harmalker, S.; Ash, K. Moisturizing Compositions.
The recitation of ranges of values herein is merely in- US 2007/0048235, Aug. 24, 2006.
tended to serve as a shorthand method of referring indi- 50 10. King, K.; Chatterji, J. Foamed Acidizing Fluids,
vidually to each separate value falling within the range. Additives and Methods of Acidizing Subterranean
Unless otherwise indicated herein, each individual value Zones US 6,555, 505, Apr. 29, 2003
is incorporated into the specification as if it were individ- 11. Kelly, R. J.; Worth, G. H.; Roddick-lanzilotta, A.
ually recited herein. All methods described herein can be D.; Rankin, D. A.; Ellis, G. D.; Mesman, P. J. R.;
performed in any suitable order unless otherwise indicat- 55 Summers, C. G.; Singleton, D. J. Production of Sol-
ed herein or otherwise clearly contradicted by context. uble Keratin Derivatives. US 7,148,327, Jul. 17,
The use of any and all examples, or exemplary language 2002.
(for example, "such as") provided with respect to certain 12. International Cosmetic Ingredient Dictionary and

18
35 EP 2 694 834 B1 36

Handbook. 9th ed.; Cosmetic, Toiletry, and Fra- in one or more of the crosslinking agents comprises
grance Association: Washington DC, 2002; Vol. 1-3. one or more substances selected from the group
13. 2001 McCutcheon’s Directories. McCutcheon’s consisting of monofunctional aldehydes, polyfunc-
Division, The Manufacturing Confectioner Publish- tional aldehydes, ketones, hydroxyketones, ketoal-
ing Co.: Glen Rock, NJ, 2001; Vol. 1-2. 5 dehydes, activated olefin-containing compounds,
14. DiBerardino, L., CBR Cosmetic Bench Refer- polycarboxylic acids, mono-epoxy compounds, po-
ence - Directory of Cosmetic Ingredients 2005. Cos- ly-epoxy compounds, carbonates, imidoesters, car-
metics and Toiletries, Allured Publishing Corpora- bodiimides, hexamethylene diisocyanate, N-hydrox-
tion: Carol Stream, IL, 2005. ysuccinimide esters, haloacetyls, pyridyl disulfide,
10 hydrazides, aryl azides, and combinations thereof.

Claims 7. A method for straightening a quantity of hair, com-


prising:
1. A hair straightening composition, having a pH of from
3.0 to 4.5, comprising: 15 providing a composition having a pH of from 3.0
to 4.5, the composition comprising one or more
an organic acid; reducing agents capable of breaking at least a
one or more reducing agents capable of break- portion of the S-S bonds in human hair when
ing at least a portion of the S-S bonds in human applied to said human hair wherein said reduc-
hair when applied to said human hair wherein 20 ing agents are compatible with a pH of from 3.0
said reducing agents are compatible with a pH to 4.5, and said reducing agents are selected
of from 3.0 to 4.5, wherein said reducing agents from the group consisting of naturally-occurring
are selected from the group consisting of natu- amino acids, non-naturally occurring amino ac-
rally-occurring amino acids, non-naturally oc- ids, members of the thiazoline family, members
curring amino acids, members of the thiazoline 25 of the 2-mercapto-ethane family, dithiothreitol,
family, members of the 2-mercapto-ethane fam- tris(2-carboxyethyl)phosphine, tris(2-carboxye-
ily, dithiothreitol, tris(2-carboxyethyl)phosphine, thyl phosphine-HCl, sulfamic acid, sulfamates,
tris(2-carboxyethyl phosphine-HCl, sulfamic ac- FeCl2, and combinations thereof, and one or
id, sulfamates, FeCl2, and combinations thereof; more keratin protein fractions, one or more pH
a keratin protein fraction; 30 lowering agents, and one or more crosslinking
a crosslinking agent comprising a non-formal- agents, and
dehyde aldehyde; and applying the composition to the quantity of hair.
optionally a Lewis acid catalyst.
8. The method of claim 7, further comprising applying
2. The hair straightening composition of claim 1, further 35 to the quantity of hair one or more substances se-
comprising one or more substances selected from lected from the group consisting of amino acids, bo-
the group consisting of amino acids, botanicals, sur- tanicals, surfactants, emollients, emulsifiers, skin-
factants, emollients, emulsifiers, skin-cleaning cleaning agents, preservatives, fragrances, pre-con-
agents, preservatives, fragrances, pre-conditioners, ditioners, thermal protectants, and aqueous-based
thermal protectants, and aqueous-based diluents. 40 diluents.

3. The hair straightening composition of claim 1, where- 9. The method of claim 7, wherein the quantity of hair
in the organic acid is a naturally-occurring organic is substantially dry when the one or more pH lowering
acid. agents, reducing agents, crosslinking agents and
45 keratin protein fractions are applied to the quantity
4. The hair straightening composition of claim 1, where- of hair.
in the organic acid is an aliphatic or aromatic mono-
carboxylic acid or a poly-carboxylic acid, preferably 10. The method of claim 7, wherein the quantity of hair
selected from the group consisting of formic acid, is wet when the one or more pH lowering agents,
acetic acid, propionic acid, tartaric acid, adipic acid, 50 reducing agents, crosslinking agents and keratin
succinic acid, ascorbic acid, malonic acid, oxalic ac- protein fractions are applied to the quantity of hair.
id, pyruvic acid, picolinic acid, dipicolinic acid, citric
acid, and combinations thereof. 11. The method of claim 7, further comprising washing
the quantity of hair with a shampoo no more than
5. The hair straightening composition of claim 1, where- 55 three hours prior to applying the one or more pH
in one or more of the reducing agents is organic. lowering agents and reducing agents.

6. The hair straightening composition of claim 1, where- 12. The method of claim 7, further comprising applying

19
37 EP 2 694 834 B1 38

a straightening iron to the quantity of hair. Bernsteinsäure, Ascorbinsäure, Malonsäure, Oxal-


säure, Brenztraubensäure, Picolinsäure, Dipicolin-
13. A kit for straightening a quantity of hair, comprising: säure, Citronensäure und Kombinationen davon.

a hair straightening composition as set forth in 5 5. Haarglättungszusammensetzung nach Anspruch 1,


claim 1; and wobei eines oder mehrere der Reduktionsmittel or-
instructions for the use thereof for straightening ganisch sind.
the quantity of hair, optionally further comprising
a shampoo, a conditioner, a flat iron, a hair dryer, 6. Haarglättungszusammensetzung nach Anspruch 1,
one or more disposable gloves, a brush, and/or 10 wobei eines oder mehrere der Vernetzungsmittel ei-
a comb. ne oder mehrere Substanzen umfassen, die aus der
Gruppe ausgewählt sind, die aus Folgenden be-
steht: monofunktionellen Aldehyden, polyfunktionel-
Patentansprüche len Aldehyden, Ketonen, Hydroxyketonen, Ketoal-
15 dehyden, aktivierten Olefin-enthaltenden Verbin-
1. Haarglättungszusammensetzung mit einem pH von dungen, Polycarbonsäuren, Monoepoxyverbindun-
3,0 bis 4,5, die Folgendes umfasst: gen, Polyepoxyverbindungen, Carbonaten, Imi-
doestern, Carbodiimiden, Hexamethylendiisocya-
eine organische Säure; nat, N-Hydroxysuccinimidestern, Halogenacetylver-
ein oder mehrere Reduktionsmittel, die zumin- 20 bindungen, Pyridyldisulfid, Hydraziden, Arylaziden
dest einen Teil der S-S-Bindungen im mensch- und Kombinationen davon.
lichen Haar bei Anwendung an dem menschli-
chen Haar spalten können, wobei die Redukti- 7. Verfahren für die Glättung einer Menge von Haar,
onsmittel mit einem pH von 3,0 bis 4,5 kompa- das Folgendes umfasst: Bereitstellen einer Zusam-
tibel sind, wobei die Reduktionsmittel aus der 25 mensetzung mit einem pH von 3,0 bis 4,5, wobei die
Gruppe ausgewählt sind, die aus Folgenden be- Zusammensetzung Folgendes umfasst: ein oder
steht: natürlich vorkommenden Aminosäuren, mehrere Reduktionsmittel, die zumindest einen Teil
nicht natürlich vorkommenden Aminosäuren, der S-S-Bindungen im menschlichen Haar bei An-
Zugehörigen der Thiazolin-Familie, Zugehöri- wendung an dem menschlichen Haar spalten kön-
gen der 2-Mercaptoethan-Familie, Dithiothrei- 30 nen, wobei die Reduktionsmittel mit einem pH von
tol, Tris(2-carboxyethyl)phosphan, Tris(2-carb- 3,0 bis 4,5 kompatibel sind und die Reduktionsmittel
oxyethyl)phosphan-HCl, Sulfamsäure, Sulfa- aus der Gruppe ausgewählt sind, die aus Folgenden
maten, FeCl2 und Kombinationen davon; besteht: natürlich vorkommenden Aminosäuren,
eine Keratin-Proteinfraktion; nicht natürlich vorkommenden Aminosäuren, Zuge-
ein Vernetzungsmittel, das einen Aldehyd um- 35 hörigen der Thiazolin-Familie, Zugehörigen der 2-
fasst, der nicht Formaldehyd ist; und Mercaptoethan-Familie, Dithiothreitol, Tris(2-carbo-
optional einen Lewis-Säurekatalysator. xyethyl)phosphan, Tris(2-carboxyethyl)phosphan-
HCl, Sulfamsäure, Sulfamaten, FeCl2 und Kombina-
2. Haarglättungszusammensetzung nach Anspruch 1, tionen davon, und eine oder mehrere Keratin-Prote-
die weiter eine oder mehrere Substanzen umfasst, 40 infraktionen, eine oder mehrere pHsenkende Mittel
die aus der Gruppe ausgewählt sind, die aus Fol- und ein oder mehrere Vernetzungsmittel, und An-
genden besteht: wenden der Zusammensetzung an der Menge von
Aminosäuren, Pflanzenpräparaten, Tensiden, Haar.
Weichmachern, Emulgatoren, Hautreinigungsmit-
teln, Konservierungsmitteln, Duftstoffen, Vorbe- 45 8. Verfahren nach Anspruch 7, das weiter das Anwen-
handlungsmitteln, Wärmeschutzmitteln und wasser- den an der Menge von Haar von einer oder mehreren
basierten Verdünnungsmitteln. Substanzen umfasst, die aus der Gruppe ausge-
wählt sind, die aus Folgenden besteht: Aminosäu-
3. Haarglättungszusammensetzung nach Anspruch 1, ren, Pflanzenpräparaten, Tensiden, Weichmachern,
wobei die organische Säure eine natürlich vorkom- 50 Emulgatoren, Hautreinigungsmitteln, Konservie-
mende organische Säure ist. rungsmitteln, Duftstoffen, Vorbehandlungsmitteln,
Wärmeschutzmitteln und wasserbasierten Verdün-
4. Haarglättungszusammensetzung nach Anspruch 1, nungsmitteln.
wobei die organische Säure eine aliphatische oder
aromatische Monocarbonsäure oder eine Polycar- 55 9. Verfahren nach Anspruch 7, wobei die Menge von
bonsäure ist, die bevorzugt aus der Gruppe ausge- Haar im Wesentlichen trocken ist, wenn das eine
wählt ist, die aus Folgenden besteht: Ameisensäure, oder die mehreren pH-senkenden Mittel, Redukti-
Essigsäure, Propionsäure, Weinsäure, Adipinsäure, onsmittel, Vernetzungsmittel und Keratin-Protein-

20
39 EP 2 694 834 B1 40

fraktionen an der Menge von Haar angewendet wer- 2. Composition de lissage des cheveux selon la reven-
den. dication 1, comprenant en outre une ou plusieurs
substances choisies dans le groupe constitué par
10. Verfahren nach Anspruch 7, wobei die Menge von les acides aminés, les herbes médicinales, les
Haar nass ist, wenn das eine oder die mehreren pH- 5 agents tensioactifs, les émollients, les émulsifiants,
senkenden Mittel, Reduktionsmittel, Vernetzungs- les agents de nettoyage de la peau, les conserva-
mittel und Keratin-Proteinfraktionen an der Menge teurs, les parfums, les pré-conditionneurs, les pro-
von Haar angewendet werden. tecteurs thermiques, et les diluants à base aqueuse.

11. Verfahren nach Anspruch 7, das weiter das Wa- 10 3. Composition de lissage des cheveux selon la reven-
schen der Menge von Haar mit einem Haarwasch- dication 1, dans laquelle l’acide organique est un aci-
mittel nicht länger als drei Stunden vor dem Anwen- de organique naturellement présent.
den des einen oder der mehreren pH-senkenden
Mittel und Reduktionsmittel umfasst. 4. Composition de lissage des cheveux selon la reven-
15 dication 1, dans laquelle l’acide organique est un aci-
12. Verfahren nach Anspruch 7, das weiter das Anwen- de monocarboxylique aliphatique ou aromatique ou
den eines Glätteisens an der Menge von Haar um- un acide polycarboxylique, choisi de préférence
fasst. dans le groupe constitué par l’acide formique, l’acide
acétique, l’acide propionique, l’acide tartrique, l’aci-
13. Kit für das Glätten einer Menge von Haar, der Fol- 20 de adipique, l’acide succinique, l’acide ascorbique,
gendes umfasst: l’acide malonique, l’acide oxalique, l’acide pyruvi-
que, l’acide picolinique, l’acide dipicolinique, l’acide
eine Haarglättungszusammensetzung wie in citrique, et des combinaisons de ceux-ci.
Anspruch 1 dargelegt; und
Anweisungen für die Verwendung davon für das 25 5. Composition de lissage des cheveux selon la reven-
Glätten der Menge von Haar, der weiter optional dication 1, dans laquelle un ou plusieurs parmi les
Folgendes umfasst: ein Haarwaschmittel, eine agents réducteurs est organique.
Haarspülung, ein Glätteisen, einen Haartrock-
ner, einen oder mehrere Einweghandschuhe, 6. Composition de lissage des cheveux selon la reven-
eine Bürste und/oder einen Kamm. 30 dication 1, dans laquelle un ou plusieurs parmi les
agents de réticulation comprend une ou plusieurs
substances choisies dans le groupe constitué par
Revendications les aldéhydes monofonctionnels, les aldéhydes po-
lyfonctionnels, les cétones, les hydroxycétones, les
1. Composition de lissage des cheveux, ayant un pH 35 cétoaldéhydes, les composés contenant des oléfi-
allant de 3,0 à 4,5, comprenant : nes activées, les acides polycarboxyliques, les com-
posés mono-époxy, les composés poly-époxy, les
un acide organique ; carbonates, les imidoesters, les carbodiimides, le
un ou plusieurs agents réducteurs capables diisocyanate d’hexaméthylène, les esters de N-hy-
d’hydrolyser au moins une portion des liaisons 40 droxysuccinimide, les halogéno-acétyles, le disulfu-
S-S dans les cheveux humains lors de l’appli- re de pyridyle, les hydrazides, les azotures d’aryle,
cation auxdits cheveux humains, et des combinaisons de ceux-ci.
où lesdits agents réducteurs sont compatibles
avec un pH allant de 3,0 à 4,5, où lesdits agents 7. Méthode destinée à lisser une quantité de cheveux,
réducteurs sont choisis dans le groupe constitué 45 comprenant :
par les acides aminés naturellement présents,
les acides aminés non naturellement présents, la fourniture d’une composition ayant un pH al-
les membres de la famille thiazoline, les mem- lant de 3,0 à 4,5, la composition comprenant un
bres de la famille 2-mercaptoéthane, le di- ou plusieurs agents réducteurs capables d’hy-
thiothréitol, la tris(2-carboxyéthyl)phosphine, la 50 drolyser au moins une portion des liaisons S-S
tris(2-carboxyéthyl)phosphine-HCl, l’acide sul- dans les cheveux humains lors de l’application
famique, les sulfamates, FeCl2, et des combi- auxdits cheveux humains, où lesdits agents ré-
naisons de ceux-ci ; ducteurs sont compatibles avec un pH allant de
une fraction de protéine de type kératine ; 3,0 à 4,5, et lesdits agents réducteurs sont choi-
un agent de réticulation comprenant un aldéhy- 55 sis dans le groupe constitué par les acides ami-
de différent du formaldéhyde ; et nés naturellement présents, les acides aminés
éventuellement un catalyseur à base d’acide de non naturellement présents, les membres de la
Lewis. famille thiazoline, les membres de la famille 2-

21
41 EP 2 694 834 B1 42

mercaptoéthane, le dithiothréitol, la tris(2-car-


boxyéthyl)phosphine, la tris(2-carboxyé-
thyl)phosphine-HCl, l’acide sulfamique, les sul-
famates, FeCl2, et des combinaisons de ceux-
ci, et une ou plusieurs fractions de protéine de 5
type kératine, un ou plusieurs agents d’abaisse-
ment du pH, et un ou plusieurs agents de réti-
culation, et
l’application de la composition à la quantité de
cheveux. 10

8. Méthode selon la revendication 7, comprenant en


outre l’application à la quantité de cheveux d’une ou
plusieurs substances choisies dans le groupe cons-
titué par les acides aminés, les herbes médicinales, 15
les agents tensioactifs, les émollients, les émulsi-
fiants, les agents de nettoyage de la peau, les con-
servateurs, les parfums, les pré-conditionneurs, les
protecteurs thermiques, et les diluants à base
aqueuse. 20

9. Méthode selon la revendication 7, dans laquelle la


quantité de cheveux est sensiblement sèche lorsque
les un(e) ou plusieurs agents d’abaissement du pH,
agents réducteurs, agents de réticulation et fractions 25
de protéine de type kératine sont appliqué(e)s à la
quantité de cheveux.

10. Méthode selon la revendication 7, dans laquelle la


quantité de cheveux est humide lorsque les un(e) ou 30
plusieurs agents d’abaissement du pH, agents ré-
ducteurs, agents de réticulation et fractions de pro-
téine de type kératine sont appliqué(e)s à la quantité
de cheveux.
35
11. Méthode selon la revendication 7, comprenant en
outre le lavage de la quantité de cheveux à l’aide
d’un shampooing pas plus de trois heures avant l’ap-
plication des un ou plusieurs agents d’abaissement
du pH et agents réducteurs. 40

12. Méthode selon la revendication 7, comprenant en


outre l’application d’un fer à lisser à la quantité de
cheveux.
45
13. Kit destiné à lisser une quantité de cheveux,
comprenant :

une composition de lissage des cheveux telle


qu’exposée selon la revendication 1 ; et 50
des instructions pour son utilisation afin de lisser
la quantité de cheveux, comprenant en outre
éventuellement un shampooing, un après-
shampooing, un fer plat, un sèche-cheveux, un
ou plusieurs gants jetables, une brosse et/ou un 55
peigne.

22
EP 2 694 834 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 2009165812 A [0007] • US 5080670 A [0099]


• US 6488920 B [0008] • US 20070048235 A [0099]
• US 20090165812 A1 [0099] • US 6555505 B [0099]
• WO 2007032762 A1 [0099] • US 7148327 B [0099]
• US 4695281 A [0099]

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• DIBERARDINO, L. CBR Cosmetic Bench Reference • HARMALKER, S. ; ASH, K. Moisturizing Composi-
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23

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