USOO834.

3238B1

(12) United States Patent (10) Patent No.: US 8,343,238 B1

Lopez et al. (45) Date of Patent: Jan. 1, 2013
(54) PROCESS FOR ALTERING THE 2009,0293899 A1 12/2009 Woodland
APPEARANCE OF HAIR USINGA 2010, O254932 A1 10/2010 Benabdillah
COMPOSITION CONTAINING DYES AND 2010, O297.049 A1 11/2010 Samain et al.
NON-HYDROXDE BASES
2011/OO52520 A1 3/2011 Nguyen et al.
2011/O1589.27 A1 6, 2011 Viravau
(75) Inventors: Gloria Lopez, Fairview, NJ (US); FOREIGN PATENT DOCUMENTS
Jeremy Puco, Budd Lake, NJ (US) CN 101069673. A 11, 2007
CN 101069673. A 11, 2007
(73) Assignee: L'Oreal SA. DE 2359.399 6, 1973
DE 1486576 9/1977
DE 3843892 A1 2, 1990
(*) Notice: Subject to any disclaimer, the term of this DE 4133957 A1 4f1993
patent is extended or adjusted under 35 DE 19543988 A1 5, 1997
U.S.C. 154(b) by 0 days. DE 102006026009 A1 12/2007
EP O560682 9, 1993
EP 898958 A1 3, 1999
(21) Appl. No.: 13/341,473 EP 898960 A1 3, 1999
EP 1216022 A1 6, 2002
(22) Filed: Dec. 30, 2011 EP 1216O23 A1 6, 2002
EP 1221929 A1 T 2002
(51) Int. Cl. EP 1510.197 A1 3, 2005
EP 1862198 A2 12/2007
A61O 5/10 (2006.01) EP 18896O2 2, 2008
(52) U.S. Cl. ............. 8/405; 8/408; 8/431; 8/552; 8/581; EP 1944.062 T 2008
8/585; 8/597; 8/604; 132/202; 132/208 FR 733,749 2, 1932
(58) Field of Classification Search .............. 8/405, 408, FR 263394.0 A1 1, 1990
8/431,552, 581,585,597, 604; 132/202, FR 2750048 A1 12/1997
132/208 FR 2789896 A1 8, 2000
FR 1207842 A1 5, 2002
See application file for complete search history. FR 2836633 A1 9, 2003
FR 283.8960 A1 10, 2003
(56) References Cited
(Continued)
U.S. PATENT DOCUMENTS
4,507,278 A 3, 1985 DeMarco et al. OTHER PUBLICATIONS
4,698,065. A 10, 1987 Hoeffkes et al.
4,844,711 A 7/1989 Hoppe et al. “Chemistry and Technology of Silicones” (1968), Academic Press.
5,160,730 A 11, 1992 Dubief “Volatile Silicone Fluids for Cosmetics” (Jan. 1976, vol. 1, pp.
5, 180,584 A 1/1993 Sebag 29-32), Cosmetics and Toiletries.
5,275,755 A 1/1994 Sebag
5,637,306 A 6, 1997 Cauwet “Industrial Polysaccharides” (vol. 61, No. 7, p. 1315-1322, 1989),
5,766,576 A 6, 1998 Lowe et al. Pure & Appl. Chem.
5,879,414 A 3, 1999 MilaZZO U.S. Appl. No. 61/581,906, filed Dec. 30, 2011, Gloria Lopez et al.
6,306,182 B1 10/2001 Chan et al.
6,338,741 B1 1/2002 Vidal et al.
6,352,699 B1 3, 2002 Mondet et al.
6,368,584 B1 4/2002 Garnier Primary Examiner — Eisa Elhilo
6,551.361 B1 4/2003 Cornwell et al. (74) Attorney, Agent, or Firm — L'Oreal USA
6,607,713 B1 8, 2003 Chodorowski et al.
6,645,258 B2 11/2003 Vidal et al.
6,953,572 B1 10/2005 Samain (57) ABSTRACT
6,953,584 B1 10/2005 Samain
7,037,347 B2 5/2006 Kuzuhara et al.
7,122,062 B2 10/2006 Yamashita et al. A process for altering the appearance of hair, the process
7,176,170 B2 2, 2007 Dubief comprising the steps of (a) providing a composition for dye
7,223,384 B1 5, 2007 Decoster
7,244.420 B1 7/2007 Samain ing and reducing curl and/or frizziness of hair, said compo
7,740,664 B2 6, 2010 Benabdillah sition comprising, in a cosmetically acceptable carrier: (i) at
7,799,093 B2 9, 2010 Brunet al. least one non-hydroxide base; (ii) at least one protein dena
7,879,113 B2 2/2011 Simonet et al. turant different from (a)(i); (iii) at least one dye chosen from
7,901.464 B2 3/2011 Hercouet et al.
7,905,927 B2 3/2011 Hercouet oxidative dye precursors; (iv) at least one thickening agent;
7,909,889 B2 3/2011 Charrier et al. (v) optionally, at least one alkoxysilane comprising at least
7,909,892 B2 3/2011 Lautenbach et al. one solubilizing functional group; and (vi) optionally, at least
7.959,687 B2 6, 2011 Charrier et al. one fatty Substance; (b) contacting the hair with the compo
2002/0041856 A1 4/2002 Jeanne-Rose et al.
2004, OO13632 A1 1/2004 Giroud et al. sition in (a) to form treated hair; (c) Smoothing the treated hair
2004/0045099 A1 3/2004 Kuzuhara et al. using a combination of heat and means for physically
2004/O185020 A1 9/2004 Gawtrey Smoothing hair to form Smoothed hair; (d) optionally, sham
2005, 0071932 A1 4/2005 Lautenbach et al.
2005, 0100523 A1 5, 2005 Maubru pooing the Smoothed hair, and (e) rinsing the Smoothed hair.
2008/02265.76 A1 9, 2008 Benabdillah
2009,0183320 A1 7/2009 Benabdillah
2009,0291058 A1 11/2009 Woodland 45 Claims, No Drawings
 US 8,343,238 B1
Page 2

FOREIGN PATENT DOCUMENTS JP 2002326916. A 11, 2002

JP 2003128527 A 5, 2003
E. 32.92. g: JP 2004217672 A 8, 2004
JP 2008273869 A 11 2008
FR 29.26984 8, 2009 WO WO94,08969 4f1994
FR 292.9112 10/2009 WO WO94,0897O 4f1994
FR 2944963 11, 2010 WO WO96, 15765 5, 1996
FR 2944964 11, 2010 WO WO99,60993 12/1999
FR 2944966 11, 2010 WO WOOO48557 8, 2000
FR 2950531 4/2011 WO WO 2006/O18198 2, 2006
GB 1026978 4, 1966 WO WO 2008/02O730 2, 2008
GB 11531.96 5, 1969 WO WO 2010O23559 A2 * 3, 2010
JP 60004116 A 1, 1985 WO WO 2011/052520 5, 2011
JP O2O19576 A 1, 1990 WO WO 2011/073279 6, 2011
JP T330556. A 12/1995
JP 9110659 4f1997 WO WO 2011/073578 6, 2011
WO WO2O11,074.144 6, 2011
JP 9.175960. A 7/1997 WO WO 2011073,578 6, 2011
JP 92.78636. A 10, 1997 WO WO2O11,089985 T 2011
JP 92.78636. A 10, 1997 WO WO 2011/089985 T 2011
JP 2001.220322 A 8, 2001
JP 3686352 B2 11/2002 * cited by examiner
 US 8,343,238 B1
1. 2
PROCESS FOR ALTERING THE Hair straighteners or reshaping technology can also
APPEARANCE OF HAIR USINGA employ reducing agents such as thighlycolic acid and cys
COMPOSITION CONTAINING DYES AND teine compounds or non-thiol-based reducing agents such as
NON-HYDROXDE BASES sulfites and bisulfites which permanently reduce hair bonds or
protein denaturants in combination with heat.
FIELD OF THE INVENTION Other straightening products contain formalin or formalin
derivatives, which are known to breakdown to formaldehyde
The present invention is directed to a novel process and with high heat, Such as during flat ironing of the hair. One
composition for dyeing hair while reducing the curl pattern 10
major drawback is the generation of formaldehyde fumes
and/or frizziness of the hair. which have been found to cause headaches, respiratory, eye,
and mucous membrane irritations, respiratory illnesses, can
BACKGROUND OF THE INVENTION cer, or even death.
Thus, in view of the potential irritation to the skin or scarp,
Chemical treatments on human hair such as relaxers, 15 and the potential damage to hair caused by available chemical
straighteners, waves, perms, oxidative and direct dyes, high treatments, successive chemical treatments of the hair within
lights, lightening compositions and bleaches are much sought a short period of time, i.e., a few hours, is generally not
after by consumers. Such chemical treatments employ vari recommended. More particularly, conventional and custom
ous reducing and oxidizing agents, alkalizing agents, and ary practice by consumers and hair dressers is to have a
coloring agents that help re-shape, artificially color, decol waiting period of at least 24 hours, preferably, a few days, in
orize, modify the color shade?tone or enhance the appearance between two or more different chemical hair treatments. Such
and color of hair. practices may also help minimize other types of problems
However, Such chemical treatments and the various ingre which may arise from Successively chemically treating the
dients employed in these treatments are generally known to hair as a result of undesired reactions between Successive
result in hair breakage and loss, dryness, roughness and 25 different chemical treatments.
brittleness, and skin and/or scalp irritation. Often times, these An example of a hair treatment process that may result in
chemical treatments are used with the application of heat and the problems described above may consist of a hair straight
mechanical combing or brushing which may cause more ening or relaxing process that is immediately followed by a
damage to the hair. conventional oxidative hair color that employs hydrogen per
One example of a chemical treatment that may adversely 30 oxide. Sucha process can resultina significant decrease in the
affect the quality of hair fibers are conventional permanent quality of the hair fibers, leading to increased roughness and
hair dyeing products which use the combination of composi damage to the hair and/or prevent the hair's color or shade
tions containing oxidative dye precursors, also known as pri from being lightened, bleached, dyed or altered correctly
mary intermediates or oxidation bases, and oxidizing prod after the chemical treatment.
ucts containing oxidizing agents such as hydrogen peroxide. 35 Successive chemical treatments of the hair can also be
Hair dyeing compositions typically contain aqueous ammo inconvenient to the consumer who has to spend a lot of time
nia as an alkalizing agent and for activating the oxidizing going through two different treatments, wait in between treat
agent. These alkalizing agents also cause the hair shaft to ments and return to the hair dresser for the second treatment.
swell, thus allowing the small oxidative dye molecules to Thus, there exists a need to improve existing methods,
penetrate the cuticle and cortex before the oxidation conden 40 compositions and hair treatment regimens or systems that
sation process is completed. The resulting larger-sized col allow the consumer to effectively change the appearance, that
ored complexes from the oxidative reaction are then trapped is, the color and/or shape of their hair in a convenient, efficient
inside the hair fiber, thereby permanently altering the color of and safe manner, while minimizing the damage to the hair and
the hair. However, the use of ammonia may affect the user, not other adverse effects and disadvantages to the consumer.
only because of the undesirable odor of ammonia, but 45 There is also a need for processes and/or compositions which
because it may also pose greater risks of intolerance, for can take the place of Successive chemical treatments.
instance, irritation of the scalp and stinging. For example, it would be desirable to oxidatively dye hair
Chemical treatments products for shaping or changing the and chemically shape or straighten the hair at the same time.
shape and configuration of hair include hair straightening or However, this may require introducing other ingredients into
relaxing products which are generally composed of a strong 50 hair coloring compositions which may affect the Suspension
hydroxide base compound, typically, an alkaline metal and/or solubility of the dye compounds in the dye composi
hydroxide, that breaks the bonds in the hair in order to tion, the hair-lightening properties of the dye composition,
straighten or relax curly/kinky hair. These products are usu the rheology or viscosity of the dye composition, and the dye
ally applied quickly and can only remain in the hair for a very application properties. Thus, the selection of ingredients pre
limited amount of time because the alkalinity of such prod 55 sents an even greater challenge to the manufacturers of hair
ucts, if not rinsed from the hair at the appropriate time, can treatment products because the composition/process not only
damage the hair, as well as cause chemical burns to the scalp has to remain effective, it also has to remain safe to use and
and areas Surrounding the hair. not cause more irritation to the skin and Scalp.
Other straightening or relaxing formulations use guani Thus, there is still an ongoing need and desire to provide a
dinium hydroxide which can be formed from the reaction of 60 composition and process for effectively coloring and/or light
guanidine carbonate and a soluble hydroxide Such as calcium ening the color of hair such as achieving chromaticity of the
hydroxide. While such a system may provide a better relaxing color and homogeneity of the coloration along the hair fiberin
efficacy and better skin tolerance, the reaction also forms a manner that is efficient, yet safe and minimizes damage to
calcium carbonate which makes the final rinsing of the hair the hair fiber. At the same time, it is highly desirable that these
much more difficult, and leaves on the hair and the scalp. 65 composition and process are able to impart other cosmetic
mineral particles that give the hair a coarse feel and an unat and functional benefits to the hair such as curl and frizz
tractive appearance resembling dandruff. reduction, greater and longer lasting curl pattern, increased
 US 8,343,238 B1
3 4
manageability of hair and fiber strength and less hair treat water or contains Substantially no unbound water, such as, for
ment or processing times to achieve these attributes. example, no more than about 1% by weight, such as no more
than about 0.5% by weight, based on the weight of each
BRIEF SUMMARY OF THE INVENTION composition.
As used herein, the phrase “salts and derivatives thereof is
The present invention is directed to a process for altering intended to mean all salts and derivatives comprising the
the appearance of hair, the process comprising the steps of same functional structure as the compound they are referring
(a) providing a composition for dyeing and reducing curl to, and that have similar properties.
and/or frizziness of hair, said composition, in a cosmeti As used herein, the terms “pre-alkalizing” and “pre-alkal
cally acceptable carrier: 10 ized” mean that the hair has a higher pH than when it has not
(i) at least one non-hydroxide base; been subjected to chemical treatment, as described herein.
(ii) at least one protein denaturant different from (a)(i); As used herein, the phrase “minimizing damage' to the
(iii) at least one dye chosen from oxidative dye precur hair and/or skin is intended to mean that the breakage of the
Sors; hair has been reduced or eliminated.
(iv) at least one thickening agent; 15 As used herein, the term “ready-to-use composition'
(v) optionally, at least one alkoxysilane comprising at means a composition intended to be applied in unmodified
least one solubilizing functional group; and form to the keratin fibers, i.e. it may be stored in unmodified
(vi) optionally, at least one fatty Substance; form before use or may result from the extemporaneous mix
(b) contacting the hair with the composition in (a) to form ing of two or more compositions.
treated hair; As used herein, the expression “altering the appearance of
(c) Smoothing the treated hair using a combination of heat hair’ means contacting the hair with at least one composition
and means for physically smoothing hair to form containing at least one chemical ingredient that changes or
Smoothed hair, contributes to changing the shape and/or the color of the hair,
(d) optionally, shampooing the Smoothed hair, and to any degree.
(e) rinsing the Smoothed hair. 25 As used herein, the term “applying a composition to the
The present invention is also directed to a composition for hair or “treating the hair with a composition is intended to
dyeing and reducing curl and/or frizziness of hair, said com mean contacting the hair with at least one of the compositions
position comprising, in a cosmetically acceptable carrier: of the invention, in any manner.
(a) from about 1 to about 5% by weight of at least one As used herein, the terms “straightening or “straighten' or
non-hydroxide base chosen from monoethanolamine 30 “relaxing or “relax” the hair mean to remove the curl from
and triethanolamine; the hair or reduce the degree of curl of the hair for a period of
(b) from about 2 to about 20% by weight of by weight of a time, permanently and/or temporarily. It also means changing
protein denaturant comprising urea and hydroxyethy the shape of hair or the degree of curl in the hair to make the
lurea present in a ratio by weight ranging from about 5:1 hair more straight. It can also mean removing or reducing the
to about 2:1; 35 frizziness of the hair.
(c) at least one dye chosen from oxidative dye precursors; As used herein, "cosmetically acceptable' means that the
(d) at least one thickening agent chosen from Xanthan gum item in question is compatible with any human keratin mate
and guar gum, rial and in particular human keratinous fibers. Such as human
(e) at least one fatty substance in an amount of at least 10% hair.
by weight; and 40 As used herein, "cosmetically acceptable carrier” means a
(f) from about 1 to about 10% by weight of at least one carrier that is compatible with any human keratin material and
alkoxysilane comprising at least one solubilizing func in particular human keratinous fibers, such as human hair.
tional group; “Lifting as used herein is defined as the process by which
wherein all weights are based on the weight of the compo the natural hair melanin is removed which is typically
sition. 45 achieved in an alkaline environment whereby the cuticles of
the hair are opened to allow penetration of an oxidizing agent.
DETAILED DESCRIPTION OF THE INVENTION Such an oxidizing agent breaks down the melanin by provid
ing it with oxygen, and the melanin molecule is colorless
As used herein, the expression “at least one' means one or when oxidized. This leaves the hair lightened from its natural
more and thus includes individual components as well as 50 color.
mixtures/combinations. The term “composition for dyeing and reducing curl and/or
Other than in the operating examples, or where otherwise frizziness of hair as used herein refers to the hair curl and/or
indicated, all numbers expressing quantities of ingredients frizz recuding and dyeing composition as described in the
and/or reaction conditions are to be understood as being present disclosure.
modified in all instances by the term “about meaning within 55 The term 'suspending agent' as used herein refers to raw
10% to 15% of the indicated number. materials and ingredients which aid in homogeneously/uni
As used herein, the term "hair is meant to include kerati formly dispersing other ingredients, such as dyeing agents, in
nous fibers. As used, the term “hair may include “living the compositions of the present disclosure. Suspending
hair, i.e. on a living body, or may be “non-living” i.e. in a wig, agents are also employed in order to provide a suitable con
hairpiece or other aggregation of non-living fibers, such as 60 sistency or rheology and other cosmetic benefits to the com
though used in textiles and fabrics. Mammalian hair, e.g. positions of the present disclosure and to hair, skin or scalp.
human hair, is preferred in various embodiments. However As used herein, “natural hair color” refers to the color of
wool, fur and other melanin-containing fibers are Suitable for hair resulting from the melanin pigments present in the hair.
use in the methods and with the compositions described As used herein, "conditioning means imparting to at least
herein. 65 one keratinous fiber at least one property chosen, from
The term “anhydrous” as used herein is intended to mean combability, manageability, moisture-retentivity, luster,
that the composition is either completely free of unbound shine, and softness. In case of combing, the level of condi
 US 8,343,238 B1
5 6
tioning is evaluated by measuring, and comparing, the ease of ods. It should also be noted that by varying the pH of the
combability of the treated hair and of the untreated hair in system, different levels of color vibrancy on hair can be
terms of combing work (gm-in). achieved.
As used herein, “formed from, means obtained from It was also surprisingly found that the curl/frizz reduction
chemical reaction of, wherein “chemical reaction, includes and the color retention capabilities as provided by the present
spontaneous chemical reactions and induced chemical reac disclosure are long lasting and comparable to, if not better
tions. As used herein, the phrase “formed from', is open than the results provided by commercial products and may
ended and does not limit the components of the composition last for several Weeks such as from about 4 weeks to about 8
to those listed. weeks.
10
As used herein, the term "rheology-modifying agent” or Without intending to be bound by theory, it is believed that
“rheology modifier” means any compound capable of giving the present invention's composition for dyeing and reducing
a viscosity to the oxidizing composition Such that, once it is curl and/or friZZiness of hair results in a unique synergy
applied onto hair, this composition does not run, and remains between the non-hydroxide base, the two protein denaturants,
perfectly localized at the point of application. 15 and the thickening agent. This believed synergy translates to
As used herein, the term “aqueous ammonia' refers to a composition that provides overall improved dyeing and hair
ammonia derived from ammonium compounds which are lightening and curl reduction/straightening and improved
added to a composition, Such as ammonium hydroxide. Thus, frizz reduction for longer periods of time.
the use of the term "ammonia' refers to aqueous ammonia. Furthermore, by employing the process of the present
As used herein, the methods and compositions disclosed invention, Straightening/relaxing or curl reduction of hair can
may be used on the hair that has not been artificially dyed or beachieved in a manner which is less harmful to a user's skin
pigmented. and hair than conventional hair straightening/relaxing or curl
As used herein, the methods and compositions disclosed reducing processes which employ large amounts of strong
may be also used on the hair that has been artificially dyed or hydroxide compounds that can cause skin irritation, as well as
pigmented. 25 damage to the hair itself.
The methods and compositions disclosed are also used to Moreover, the Subject composition and process avoids the
reduce the frizziness of hair and/or improve the condition of use of formalin/formol or formaldehyde derivatives or form
the hair or keep hair conditioned. When the amount of mois aldehyde-generating compounds that are employed in some
ture in hair decreases due to weather conditions or exposure to conventional hair straightening/relaxing products and which
high temperatures during styling processes, the hair gives up 30
are known to breakdown to formaldehyde with high heat and
Surface electrons more readily and develops a positive elec generate dangerous fumes.
trostatic charge. The positive charge of individual hair fibers In addition, the present invention does not require the use
causes the hair fibers to repel one another resulting in a “static of ammonia, and/or peroxide compounds that are tradition
flyaway” condition (i.e., frizzy hair). Loss of moisture in the ally used in permanent hair coloring systems, and yet, is able
hair also causes hair to become brittle and damaged resulting 35
in less shiny and more unattractive hair. Hair is often exposed to achieve the desired lightening/dyeing effects while mini
to dry weather conditions in arid regions and/or during the mizing damage to the hair fibers. Conversely, when greater
winter months. Furthermore, many styling processes utilize lift of color is desired, ammonia may be used in the compo
heat to drive out moisture in the hair in order to lock in a sitions of the present disclosure. Furthermore, the process
temporary style that persists until the hair reabsorbs moisture. 40 according to the present disclosure can resultinadequate gray
Alkoxysilanes are not typically used in formulating cos hair coverage.
metic products/personal care products. In particular, alkox The compositions and methods of the present disclosure
ysilanes are not usually employed in hair products, including also provide a means for treating hair in an efficient and less
manageability products for reducing curl and frizz. However, messy or cleaner manner. A major disadvantage associated
alkoxysilanes, particularly those with at least one solubilizing 45 with the use of conventional permanent hair dye formulations
functional group can attract water molecules, thereby causing and systems is that they are very messy to apply because the
a gelling effect when exposed to the water. Without intending color is developed before it is applied onto the hair; they also
to be bound by theory, the use of alkoxysilanes is believed to have a tendency to cause scalp staining. Thus, it was found
help with reducing the adverse effects of the use ofheat on the that the present disclosure provides a process for developing
hair which would tend to reduce the moisture of the hair, 50 the color of the dye in situ, i.e., on the hair.
thereby resulting in unattractive and dry hair. Moreover, the compositions of the present disclosure are
The present invention is based on the Surprising and unex easy and convenient to apply, do not run but remain localized
pected finding that the methods and compositions of the at the point of application, and have improved dyeing prop
present disclosure resulted in significantly improved curland erties. The term “improved dyeing properties” is understood
frizz reducing capability and hair dyeing and/or lightening 55 to mean an improvement in the power/intensity, chromaticity
capability, thus, eliminating the need for two separate proce and/or uniformity of the dyeing result.
dures and the long wait between the procedures. It is to be understood that the foregoing describes various
It has been Surprisingly found that by employing the meth exemplary embodiments of the invention, but that modifica
ods and compositions of the present disclosure, the following tions may be made therein without departing from the spirit or
several significant advantages can be realized, as compared to 60 Scope of the invention as set forth in the claims.
conventional methods of dyeing and straightening hair: Composition for Dyeing and Reducing Curland/or Frizziness
shorter processing times; comparable color-fastness to con of Hair
ventional dyeing methods using oxidative developers; Non-Hydroxide Base
improved color deposit on the hair; little to no odor. In some Suitable non-hydroxide bases for use in the composition
instances, depending on the oxidative dye and/or coupler 65 for dyeing and reducing curl and/or frizziness of hair of the
molecule used, different colors/shades may be obtained com present invention are those curl and/or frizziness of hair are
pared to the conventional hair coloring compositions/meth bases having a pKa of from about 0 to about 15, preferably
 US 8,343,238 B1
7 8
from about 1 to about 14, and more preferably from about 2 to phenyl optionally substituted with a chlorine atom or a
about 13. These may be chosen from organic bases and inor hydroxyl radical; benzyl; or 2,5-dioxo-4-imidazolidinyl.
ganic bases. When R1 and R3 represent a hydrogen atom, R2 may also
Organic bases generally include nitrogen-containing bases representahydrogenatom or a methyl or ethyl radical and R4
which do not completely disassociate in water. Examples an acetyl radical.
thereof include, but are not limited to, ethylamines, ethylene When R1=R2=H, R3 and R4 may also form, with the
amines, ethanolamines, quinoline, aniline, pyridine, basic nitrogen atom that bears them, a piperidine or 3-methylpyra
amino acids, and their derivatives. Particularly preferred Zole or 3,5-dimethylpyrazole or maleimide ring.
nitrogen-containing bases include ethylenediamines, mono 10
Finally, R1 and R2, and also R3 and R4, may also form,
ethanolamines, triethanolamines, arginine, lysine, and their with the nitrogen atom that bears them, an imidazole ring.
derivatives, and mixtures thereof. Most preferably, the non
hydroxide base is chosen from monoethanolamine (MEA)
and triethanolamine. (II)
Inorganic bases generally include alkali metal phosphates 15
and carbonates Such as, for example, sodium phosphate,
potassium phosphate, Sodium carbonate, sodium bicarbon R5-N NHR6
ate, potassium carbonate, potassium bicarbonate, and their
derivatives.
Inorganic bases may also include alkali metals of carboxy in which:
lates such as, for example, sodium acetate, potassium acetate, R5 and R6 represent, independently of each other:
Sodium citrate, and potassium citrate, and their derivatives. (i) a hydrogen atom, or
Particularly preferred inorganic bases include potassium (ii) a linear or branched C1-C4 lower alkyl radical, option
phosphate, Sodium phosphate, and Sodium carbonate. ally Substituted with a radical chosen from: hydroxyl, amino,
The non-hydroxide base is typically employed in the com 25 dimethylamino, carboxyl or carboxamide.
position for dyeing and reducing curl and/or frizziness of hair and A represents the radicals: CH2—CH2 or
of the present disclosure in an amount of from about 0.1% to CH-CH or CH2-CO or CO. NH or CH-N or
about 50% by weight, preferably from about 0.1% to about CO CO or CHOH CHOH or (HOOC)CH CH or
30% by weight, preferably from about 0.1% to about 10% by CHOH CO or CH2 CH2 CH2 or CH2-NH
weight, based on the total weight of the composition for 30
CO or CH=C(CH3). CO or NH CO. NH or
dyeing and reducing curl and/or frizziness of hair. CH2 CH2 CO or CH2-N(CH3) CH2 or
Protein Denaturant NH CH2 NH or CO CH(CH3). CH2 or
Suitable protein denaturants for use in the composition for CO CH2 CO or CO. NH CO or CO CH
dyeing and reducing curl and/or frizziness of hair of the (COOH) CH2 or CO CH=C(COOH) or CO
present invention can be chosen from ureas, guanidines, 35
CH=C(CH3) or CO C(NH2)—CH or CO C
amidines, urethanes, aromatic monohydroxylated, dihy (CH3)—N or CO CH=CH or CO CH==
droxylated, trihydroxylated or polyhydroxylated derivatives, or CO
nitrogen heterocycles of the imidazole or triazole family, As "guanidine' that may be used as relaxing active agent,
carboxylic acids and amide and thioamide derivatives this term means any derivative comprising in its chemical
thereof, thioureas, amino acids, alcohols, polyols, amine 40 formula at least one carbonatom doubly bonded to a nitrogen
oxides, Surfactants containing Sugar, choline, deoxycholine atom and singly bonded to two other nitrogen atoms. These
or polyethylene glycol units, metal salts and Sulfamides. guanidines are more particularly selected from the com
As “urea” that may be used as relaxing active agent, this pounds of general formula (III) below:
term refers to any derivative comprising in its chemical for
mula a carbonyl group simply bonded to 2 nitrogen atoms. 45
These ureas are more particularly selected from the com (III)
pounds of general formulae (I) and (II) below:

(I) 50

in which:
55 R1, R2, R3, R4 and R5 represent, independently:
(iii) a hydrogen atom, or
in which: (iv) a linear or branched C1-C4 lower alkyl or alkenyl
R1, R2, R3 and R4 represent, independently: radical, optionally Substituted with one or two radicals chosen
(i) a hydrogen atom, or from: hydroxyl, amino, dimethylamino, methoxy, ethoxy,
(ii) a linear or branched lower C1-C4 alkyl or alkenyl 60 carboxyl, carboxamide, N-methylcarboxamide or SO3H
radical, optionally substituted with a radical chosen from: When R1, R2, R3 and R4 represent a hydrogen atom, R5
hydroxyl, amino, dimethylamino, carboxyl or carboxamide may also denote a radical chosen from the following: acetyl:
or N-methylcarboxamide. chloroacetyl; carboxamide; methoxy; ethoxy; 1,2,4-triazolyl,
When R1,R2 and R3 represent a hydrogen atom, R4 may cyclopentyl: methoxycarbonyl: ethoxycarbonyl: CO
also denote a radical chosen from the following: carboxam 65 CH=CH COOH; phenyl optionally substituted with a
ide; methoxy; ethoxy; 1,2,4-triazolyl, cyclopentyl; methoxy chlorine atom or a hydroxyl radical; benzyl; thiazolidone:
carbonyl; ethoxycarbonyl: CO CH=CH COOH: benzimidazole; benzoxazole; benzothiazole; O
 US 8,343,238 B1
9 10
C(—NH) NR6R7 in which R6 and R7 denote, inde By way of non-limiting example, oxidative dye precursors
pendently of each other, a hydrogen atom or a linear or may be chosen from ortho- or para-aminophenols, ortho- or
branched C1-C4 lower alkyl radical, optionally substituted para-phenylenediamines, double bases, heterocyclic bases,
with one or two radicals chosen from: hydroxyl, amino, dim and the acid addition salts thereof.
ethylamino, carboxyl and carboxamide; or N-methylcar Exemplary para-phenylenediamines which may be chosen
boxamide; or alternatively a phenyl radical. include compounds of the general formula (IV) and their
When R1=R2=R3-H. R4 and R5 may also form, with the addition salts with an acid:
nitrogenatom that bears them, apyrrolidine, piperidine, pyra
Zole or 1,2,4-triazole ring, optionally Substituted with one or
two radicals chosen from: hydroxyl, amino and carboxyl. 10 NRsRo
When R1 =R2=H, and R4-H or methyl, R3 and R5 may
also together form a 5-membered ring optionally containing
an oxo group, and the organic or mineral salts thereof.
In particularly preferred embodiments of the present dis
closure, the at least one protein denaturant is chosen from 15
urea, hydroxyethyl urea, and their derivatives.
In other particular embodiments of the present disclosure,
the composition for dyeing and reducing curl and/or friZZi
ness of hair comprises at least two protein denaturants. Theat wherein, in formula (IV):
least two protein denaturants are preferably chosen from a R8 represents a hydrogen atom, a C1-C4 alkyl radical, a
urea or a guanidine, urea derivatives and/or salts, guanidine C1-C4 monohydroxyalkyl radical, a C2-C4 polyhy
derivatives and/or salts, arginine, other compounds and their droxyalkyl radical, a (C1-C4)alkoxy(C1-C4)alkyl radi
salts containing a guanidine moiety, and mixtures thereof. cal, a C1-C4 alkyl radical Substituted by a nitrogenous
Preferably, the at least two protein denaturants may be chosen group, a phenyl radical or a 4-aminophenyl radical;
from urea and hydroxyethyl urea. 25 R9 represents a hydrogen atom, a C1-C4 alkyl radical, a
Preferably, the at least two protein denaturants are used in C1-C4 monohydroxyalkyl radical, a C2-C4 polyhy
combination, present in a ratio by weight ranging from about droxyalkyl radical, a (C1-C4)alkoxy(C1-C4)alkyl radi
10:1 to about 1:10, or such as from about 8:1 to about 1:8, or cal or a C1-C4 radical substituted by a nitrogenous
such as from about 5:1 to about 2:1. In certain embodiments, group;
the at least two protein denaturants are used in combination, 30 R8 and R9 can also form, with the nitrogen atom which
present in a ratio by weight of such as from about 5:1, or Such carries them, a 5- or 6-membered nitrogenous hetero
as from about 3:1, or such as from about 1:1, or preferably, cycle optionally substituted by one or more alkyl,
from about 2:1. hydroxyl or ureido groups;
Preferably, at least one of the protein denaturants is an R10 represents a hydrogenatom, a halogenatom, Such as a
organic amine having a pKb greater than 12; and more pref 35 chlorine atom, a C1-C4 alkyl radical, a Sulpho radical, a
erably, having a pKb greater than 13 at 25°C., such as for carboxyl radical, a C1-C4 monohydroxyalkyl radical, a
example, urea. C1-C4 hydroxyalkoxy radical, a C1-C4 acetylami
Some of the protein denaturants may also fit the description noalkoxy radical, a C1-C4 meSylaminoalkoxy radical or
of the non-hydroxide base and therefore, can be used as the C1-C4 carbamoylaminoalkoxy radicals; and
non-hydroxide base according to the invention. In Such a 40 R11 represents a hydrogen atom, a halogen atom or a
case, the protein denaturant(s) in the composition for dyeing C1-C4 alkyl radical.
and reducing curl and/or frizziness of hair are different from By way of example, among the nitrogenous groups in the
the non-hydroxide base. above formula (IV), of the amino, mono(C1-C4)alkylamino,
The protein denaturant is typically employed in the com di(C1-C4)alkylamino, tri(C1-C4)alkylamino, monohydroxy
position for dyeing and reducing curland/or frizziness of hair 45 (C1-C4)alkylamino, imidazolinium and ammonium radicals
of the present disclosure in an amount of from about 0.1% to may be chosen. Exemplary para-phenylenediamines of above
about 50% by weight, preferably from about 0.5% to about formula (XXIII), include para-phenylenediamine, para-tolu
30% by weight, preferably from about 1% to about 25% by oylenediamine, 2-chloro-para-phenylenediamine, 2,3-dim
weight, even preferably from about 2% to about 20% by ethyl-para-phenylenediamine, 2,6-dimethyl-para-phe
weight, based on the total weight of the composition for 50 nylenediamine, 2,6-diethyl-para-phenylenediamine, 2.5-
dyeing and reducing curl and/or frizziness of hair. dimethyl-para-phenylenediamine, N,N-dimethyl-para
Dyes phenylenediamine, N,N-diethyl-para-phenylenediamine,
The process of the present disclosure includes permanent N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-di
or oxidation dyeing wherein the composition for dyeing and ethyl-3-methylaniline, N.N-bis(beta-hydroxyethyl)-para
reducing curl and/or frizziness of hair comprises oxidative 55 phenylenediamine, 4-N,N-bis(beta-hydroxyethyl)amino-2-
dye precursors. Typically the oxidative dye precursors ere methylaniline, 4-N,N-bis(beta-hydroxyethyl)amino-2-
selected from ortho- or para-phenylenediamines, ortho- or chloroaniline, 2-(beta-hydroxyethyl)-para
para-aminophenols and heterocyclic compounds. These oxi phenylenediamine, 2-fluoro-para-phenylenediamine,
dation bases are colourless or lightly coloured compounds 2-isopropyl-para-phenylenediamine, N-(beta-hydroxypro
which, in combination with oxidizing products, allow 60 pyl)-para-phenylenediamine, 2-hydroxymethyl-para-phe
coloured species to be obtained, by a process of oxidative nylenediamine, N,N-dimethyl-beta-methyl-para-phenylene
condensation. diamine, N-ethyl-N-(beta-hydroxyethyl)-para
Useful oxidative dye precursors of the present disclosure phenylenediamine, N-(betagamma-dihydroxypropyl)-para
include, by way of example only, aromatic diamines, polyhy phenylenediamine, N-(4-aminophenyl)-para
dric phenols, amino phenols, and derivatives of these com 65 phenylenediamine, N-phenyl-para-phenylenediamine,
pounds, such as, for example, N-substituted derivatives of the 2-((beta-hydroxyethyloxy)-para-phenylenediamine,
amines, and ethers of the phenols. 2-((beta-acetylaminoethyloxy)-para-phenylenediamine,
 US 8,343,238 B1
11 12
N-(beta-methoxyethyl)-para-phenylenediamine, 2-methyl particular from the compounds corresponding to the follow
1-N-(beta-hydroxyethyl)-para-phenylenediamine and their ing formula (VI): and their addition salts with an acid:
addition salts with an acid.
Exemplary ortho-phenylenediamines, include N1-(2-hy 5 OH
droxyethyl)-4-nitro-o-phenylenediamine, 4-methyl-o-phe
nylenediamine, and 4-nitro-o-phenylenediamine and acid
addition salts thereof.
As used herein, the term “double bases' means compounds eXR21
comprising at least two aromatic nuclei having at least one of 10
amino and hydroxyl groups. For example, double bases may
be chosen from compounds of the formula (V) and their
addition salts with an acid:
wherein, in formula (VI):
15 R20 is chosen from a hydrogenatom, a halogenatom, Such
Z1 Z2 as fluorine, a C1-C4 alkyl radical, a C1-C4 monohy
droxyalkyl radical, a (C1-C4)alkoxy(C1-C4)alkyl radi
N
R14 R15
N cal, a C1-C4 aminoalkyl radical or a hydroxy(C1-C4)
alkylamino-(C1-C4)alkyl radical, and
RI-ii- Y --Rs R21 is chosen from a hydrogenatom, a halogenatom, Such
21 2 as fluorine, a C1-C4 alkyl radical, a C1-C4 monohy
droxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a
NRR17 NR8R19 C1-C4 aminoalkyl radical, a C1-C4 cyanoalkyl radical
or a (C1-C4)alkoxy(C1-C4)alkyl radical.
25 By way of example only, para-aminophenol, 4-amino-3-
wherein, in formula (V): methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hy
Z1 and Z2 may independently be chosen from a hydroxyl droxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-
O NH2 radical which can be substituted by a hydroxymethyl phenol, 4-amino-2-methoxymethylphenol,
C1-C4 alkyl radical or by a connecting arm Y: 4-amino-2-aminomethylphenol, 4-amino-2-(beta-hydroxy
30 ethylaminomethyl)phenol, N-methyl-para-aminophenol, and
the connecting arm Y is chosen from a linear or branched the acid addition salts thereof may be chosen.
alkylene chain comprising from 1 to 14 carbon atoms Exemplary ortho-aminophenols may be chosen from
which can be interrupted or terminated by one or more 2-aminophenol, 2-amino-1-hydroxy-5-methylbenzene,
nitrogenous groups and/or by one or more heteroatoms, 2-amino-1-hydroxy-6-methylbenzene, 5-acetamido-2-ami
Such as oxygen, Sulphur or nitrogenatoms, and which is 35 nophenol, and the acid addition salts thereof.
optionally substituted by one or more hydroxyl or Exemplary heterocyclic bases may be chosen from pyri
C1-C6 alkoxy radicals; dine derivatives, pyrimidine derivatives, pyrazole derivatives,
R12 and R13 are independently chosen from a hydrogen or pyrazolinone derivatives, and the acid addition salts thereof.
halogen atom, a C1-C4 alkyl radical, a C1-C4 monohy Non-limiting examples of pyridine derivatives include, for
droxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a 40 example, those disclosed in GB1026978 and GB1153196,
C1-C4 aminoalkyl radical or a connecting arm Y: both incorporated by reference herein, such as 2,5-diami
nopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine,
R14, R15, R16, R17, R18 and R19 are independently cho 2,3-diamino-6-methoxypyridine, 2-(beta-methoxyethyl)
Sen from a hydrogen atom, a connecting arm Y or a amino-3-amino-6 methoxypyridine, 3,4-diaminopyridine,
C1-C4 alkyl radical; 45 and the acid addition salts thereof.
wherein compounds of formula (V) only comprise a single Non-limiting examples of pyrimidine derivatives include,
connecting arm Y per molecule. for example, those described in DE 23593.99, JP88-169571,
In various embodiments, nitrogenous groups of the above JP 91-10659 and WO96/15765, all incorporated by reference
herein, such as 2.4.5,6-tetra-aminopyrimidine, 4-hydroxy-2,
formula (V), may be chosen from amino, mono(C1-C4)alky 50 5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triamino-pyrimi
lamino, di(C1-C4)alkylamino, tri(C1-C4)alkylamino, mono dine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2.5,6-triami
hydroxy(C1-C4)alkylamino, imidazolinium and ammonium nopyrimidine, and the pyrazolopyrimidine derivatives, such
radicals. as those mentioned in French Application FR-A-2 750 048
Nonlimiting examples of double bases include N,N'-bis and among which may be mentioned pyrazolo 1.5-alpyrimi
(beta-hydroxyethyl)-N,N'-bis(4-aminophenyl)-1,3-di 55 dine-3,7-diamine; 2,5-dimethylpyrazolo 1.5-apyrimidine
amino-propan-ol, N,N'-bis(beta-hydroxyethyl)-N,N'-bis(4- 3,7-diamine; pyrazolo 1.5-alpyrimidine-3,5-diamine; 2.7-
aminophenyl)ethylenediamine, N,N'-bis(beta dimethylpyrazolo 1.5-alpyrimidine-3,5-diamine;
aminophenyl)-tetramethylenediamine, N,N'-bis(4- 3-aminopyrazolo 1.5-alpyrimidin-7-ol: 3-aminopyrazolol,
hydroxyethyl)-N,N'-bis(4-aminophenyl) 5-alpyrimidin-5-ol: 2-(3-aminopyrazolo 1.5-alpyrimidin-7-
tetramethylenediamine, N,N'-bis(4-methylaminophenyl) 60 ylamino)ethanol: 2-(7-aminopyrazolo 1.5-alpyrimidin-3-
tetramethylenediamine, N,N'-diethyl-N,N'-bis(4-amino-3'- ylamino)ethanol: 2-(3-aminopyrazolo 1.5-alpyrimidin-7-
methylphenyl)ethylenediamine, 1.8-bis(2,5-diamino yl)(2-hydroxyethyl)aminoethanol: 2-(7-aminopyrazolol,
5-alpyrimidin-3-yl)(2-hydroxyethyl)aminoethanol: 5,6-
phenoxy)-3,5-dioxaoctane, and their addition salts with an dimethyl-pyrazolo 1.5-alpyrimidine-3,7-diamine; 2,6-
acid. 65 dimethylpyrazolo 1.5-alpyrimidine-3,7-diamine; 2.5.N7.
Non-limiting examples of para-aminophenols which can N7-tetramethylpyrazolo 1.5-apyrimidine-3,7-diamine;
be used in the context of the invention can be chosen in 3-amino-5-methyl-7-(imidazolylpropylamino)pyrazolo 1.5-
 US 8,343,238 B1
13 14
apyrimidine; and their addition salts and their tautomeric >C=C- and—N=C- in which the two atoms are not simul
forms, when there exists a tautomeric equilibrium, and their taneously engaged in a ring. However, it is pointed out that
addition salts with an acid. one of the nitrogen or carbon atoms of the sequences may be
Non-limiting examples of pyrazole and pyrazolinone engaged in a ring. More particularly, the dyes of this family
derivatives include the compounds described in DE 3,843, are derived from compounds of true methine type (compris
892, DE 4,133,957, WO 94/08969, WO 94/08970, FR-A-2, ing one or more abovementioned sequences —C=C- ); of
733,749, and DE 19543.988, all of which are incorporated by aZomethine type (comprising at least one, or more, sequences
reference herein, Such as 4.5-diamino-1-methyl-pyrazole, —C=N ) with, for example, aZacarbocyanins and their
3,4-diaminopyrazole, 4.5-diamino-1-(4'-chlorobenzyl)pyra isomers, diaZacarbocyanins and their isomers, and tetraazac
Zole, 4.5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-me 10
arbocyanins; of mono- and diarylmethane type; of indoamine
thyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phe (or diphenylamine) type; of indophenol type; or of indoa
nylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole,
1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3- niline type.
tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-me As regards the dyes of the carbonyl family, examples that
thylpyrazole, 4.5-diamino-1-(beta-hydroxyethyl)-3-meth 15 may be mentioned include dyes chosen from acridone, ben
ylpyrazole, 4.5-diamino-1-(beta-hydroxyethyl)pyrazole, Zoquinone, anthraquinone, naphthoduinone, benzanthrone,
4,5-diamino-1-ethyl-3-methylpyrazole, 4.5-diamino-1- anthranthrone, pyranthrone, pyrazol-anthrone, pyrimidi
ethyl-3-(4-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl noanthrone, flavanthrone, idanthrone, flavone, (iso) violan
3-hydroxymethylpyrazole, 4.5-diamino-3-hydroxymethyl throne, isoindolinone, benzimid-azolone, isoquinolinone,
1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1- anthrapyridone, pyrazolo-quinazolone, perinone, quinacri
isopropylpyrazole, 4,5-diamino-3-methyl-1- done, quinophthalone, indigoid, thioindigo, naphthalimide,
isopropylpyrazole, 4-amino-5-(2-aminoethyl)amino-1,3- anthrapyrimidine, diketopyrrolopyrrole and coumarin dyes.
dimethyl-pyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5- As regards the dyes of the azine family, mention may be
triaminopyrazole, 3,5-diamino-1-methyl-4- made, for example, of azine, Xanthene, thioxanthene, fluorin
methylaminopyrazole, 3,5-diamino-4-(p-hydroxyethyl) 25 dine, acridine, (di)oxazine, (di)thiazine and pyronin dyes.
amino-1-methylpyrazole, 2-(4,5-diamino-1H-pyrazol-1-yl), As regards the dyes of porphyrin orphthalocyanin type, it
H2SO4, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo 1.2-Z is possible to use cationic or non-cationic compounds, option
pyrazol-1-one, 1-methyl-3-phenyl-2-pyrazolinone, and the ally comprising one or more metals or metalions, for instance
acid addition salts thereof. alkali metals, alkaline-earth metals, Zinc and silicon.
The at least one oxidation dye precursor may be present in 30 Other suitable synthetic direct dyes include monochro
the composition for dyeing and reducing curl and/or friZZi mophoric cationic direct dyes of the following types: azos;
ness of hair of the present disclosure in an amount ranging methines; azomethines with diazacarbocyanins and isomers
from, for example, about 0.0001% to about 12%, such as from thereof, and tetraazacarbocyanins; anthraquinones; naphtho
about 0.0001% to about 8.0%, or from about 0.005% to about quinone or benzoquinone dyes; indoamine direct dyes; indi
5% by weight, based on the total weight of the composition 35 goid direct dyes; phthalocyanin and porphyrin direct dyes;
for dyeing and reducing curl and/or frizziness of hair. alone or as mixtures.
This mode of coloring makes use, more particularly, of one As other dyes that may be used according to the invention,
or more oxidative dye precursors, even more particularly, of mention may also be made, among the azo direct dyes, of the
one or more oxidative dye precursors incombination with one following dyes: Disperse Red 17; Disperse Red 13: Basic Red
or more couplers. 40 22: Basic Red 76; Basic Yellow 57; Basic Brown 16; Basic
The shades obtained with the use of oxidative dye precur Brown 17; Disperse Green 9: Disperse Black 9: Solvent
sors are very often varied by combining them with one or Black 3: Disperse Blue 148; Disperse Violet 63; and Solvent
more couplers, the latter being selected in particular from Orange 7.
aromatic meta-diamines, meta-aminophenols, meta-diphe Mention may also be made of 1-(4'-aminodiphenylazo)-2-
nols and certain heterocyclic compounds, such as indole com 45 methyl-4-bis(beta-hydroxyethyl)amino-benzene (INCI
pounds. name: HC Yellow 7).
The variety of the molecules employed for the oxidation Among the quinone direct dyes that may be mentioned are
bases and couplers allows a rich palette of colours to be the following dyes: Disperse Red 15; Solvent Violet 13: Sol
obtained. vent Blue 14: Disperse Violet 1: Disperse Violet 4: Disperse
Direct dyes may be used in combination with oxidative 50 Blue 1: Disperse Violet 8: Disperse Blue 3: Disperse Red 11:
dyes to produce a lightening effect. The direct dyes are col Disperse Blue 7: Disperse Blue 14: Basic Blue 22: Disperse
ored molecules and are generally chosen from nitro (hetero) Violet 15: Disperse Blue 377; Disperse Blue 60; Basic Blue
aryl direct dyes, especially nitrobenzene and nitropyridine, 99; and also the following compounds: 1-N-methylmorpho
anthraxquinone, nitropyridine, azo, methine, azomethine, liniumpropylamino-4-hydroxyanthra-quinone, 1-aminopro
Xanthene, acridine, azine, carbonyl and tri (hetero) aryl 55 pylamino-4-methylaminoanthraquinone; 1-aminopropy
methane direct dyes, and the addition salts thereof, alone oras lamino-anthraquinone; 5-beta-hydroxyethyl-1,4-
mixtures. The presence of Such compounds enables the diaminoanthraquinone; 2-aminoethylaminoanthraquinone;
obtained coloration to be further enriched with tints or and 1,4-bis(beta-dihydroxypropylamino) anthraquinone.
enables the chromaticity of the obtained coloration to be Mention may also be made of the coumarin compound
increased. 60 Disperse Yellow 82.
More particularly, the azo dyes comprise an—N=N-func Among the azine dyes that may be mentioned are the
tion in which the two nitrogen atoms are not simultaneously following compounds: Basic Blue 17: Basic Red 2: Solvent
engaged in a ring. However, it is not excluded for one of the Orange 15.
two nitrogenatoms of the sequence—N=N- to be engaged Among the triarylmethane dyes that may be used accord
in a ring. 65 ing to the invention, mention may be made of the following
The dyes of the methine family are, for example, com compounds: Basic Green 1: Basic Violet 3: Basic Violet 14:
pounds comprising at least one sequence chosen from Basic Blue 7: Basic Blue 26.
 US 8,343,238 B1
15 16
Among the indoamine dyes that may be used according to include, but are not limited to, direct dyes, pigments, lipo
the invention, mention may be made of the following com soluble dyes, nacreous pigments, pearling agents, leuco dyes,
pounds: 2-hydroxyethylamino-5-bis(beta-4'-hydroxyethyl) optical lightening colorants, natural colorants and optically
aminoanilino-1,4-benzoquinone; 2-hydroxyethylamino-5- variable pigments, which are coloured, and colouring mol
(2'-methoxy-4-amino)anilino-1,4-benzoquinone; 3-N(2'- ecules that have affinity for fibers.
chloro-4'-hydroxy)phenylacetylamino-6-methoxy-1,4- Non-limiting examples of natural dyes that may be chosen
benzoquinone imine; 3-N(3'-chloro-4'-methylamino) include lawsone, juglone, alizarin, purpurin, carminic acid,
phenylureido-6-methyl-1,4-benzoquinone imine: 3-4'-N- kermesic acid, laccaic acid, purpurogallin, anthragallol, pro
(ethylcarbamylmethyl)aminophenylureido-6-methyl-1,4- tocatechaldehyde, indigo, isatin, curcumin, spinulosin, chlo
benzoquinone imine. 10
rophylls, chlorophyllines, orceins, haematin, haematoxylin,
Exemplary direct dyes that may be used include those that brazilin, brazileine, safflower dyes (for instance carthamine),
are nonionic, anionic, and cationic. flavonoids (with, for example, morin, apigenidin and sandal
The cationic direct dyes may be, for example, chosen from wood), anthocyans (of the apigeninidin type), carotenoids,
direct dyes of the following types: azos, methines; azome
thines, with diaZacarbocyanins and isomers thereof, and tet 15 tannins, Sorghum and cochineal carmine, or mixtures thereof.
raazacarbocyanins (tetraazapentamethines); anthraquinones; Extracts or decoctions containing these natural dyes, and
alone or as a mixture. especially henna-based extracts, may also be used.
Suitable cationic direct dyes, may be chosen from cationic For example, the natural dyes are chosen from lawsone,
mixed dyes including at least one chromophore, such as at juglone, alizarin, purpurin, carminic acid, kermesic acid,
least two chromophores. As used herein, "cationic mixed laccaic acid, purpurogallin, protocatechaldehyde, indigo,
dye means a dye whose cationic charge can form an integral isatin, curcumin, spinulosin, apigenidin, chlorophylline, Sor
part of the chromophore and/or of the linker, or alternatively ghum, orceins, cochineal carmine, haematin, haematoxylin,
a dye whose cationic charge is present via a Substituent on the brazilin and brazileine, and mixtures thereof.
chromophore and/or on the linker. As used herein, "chro These dyes may optionally be used in the presence of
mophore” means a radical derived from a dye, i.e. a radical of 25 mordants (for example Zinc, manganese, aluminium, iron,
a molecule that has at least one absorption maximum in the etc. salts).
visible region between 400 and 800 nm, this absorbance Thickening Agent
requiring no prior oxidation or any combination with other The thickening agents of the present disclosure may also
chemical species. function as rheology-modifying agents.
In various embodiments where the at least one dye is cho 30 The at least one thickening agent may be chosen from:
Sen from mixed cationic dyes, the at least one chromophore silicas, notably hydrophobic, such as those described in
may be chosen from acridine, acridone, anthranthrone, document EP-A-898960, and for examplemarketed under the
anthrapyrimidine, anthraquinone, azine, azo, azomethine, references AEROSIL R812 by the company Degussa,
benzanthrone, benzimidazole, benzimidazolone, benzindole, “CAB-O-SIL TS-530”, “CAB-O-SIL TS-610”, “CAB-O-
benzoxazole, benzopyran, benzothiazole, benzoquinone, bis 35 SIL TS-720” by the company Cabot, “AEROSIL R972,
azine, bis-isoindoline, carboxanilide, coumarin, cyanins, “AEROSIL R974” by the company Degussa;
diazine, diketopyrrolopyrrole, dioxazine, diphenylamine, clays, such as montmorillonite, modified clays such as the
diphenylmethane and dithiazine chromophores, flavonoids, bentones for example, Stearalkonium hectorite, Stearalko
fluorindines, formazans, hydrazones, hydroxy ketones, nium bentonite;
indamines, indanthrones, indigoids, pseudo-indigoids, 40 polysaccharide alkyl ethers (notably with the alkyl group
indophenols, indoanilines, isoindolines, isoindolines, isoin having from 1 to 24 carbon atoms, preferably 1 to 10, more
dolinones, isoviolanthrones, lactones, methines, naphthalim preferably 1 to 6, and more especially 1 to 3) such as those
ides, naphthanilides, naphtholactams, naphthoduinones, described in document EP-A-898958.
nitro dyes, oxadiazoles, oxazines, perilones, perinones, The at least one thickening agent may be chosen from
perylenes, phenazines, phenothiazines, phthalocyanin, poly 45 nonionic amphiphilic polymers containing a hydrophobic
enes/carotenoids, porphyrins, pyranthrones, pyrazolan chain, mention may be made, interalia, of
thrones, pyrazolones, pyrimidinoanthrones, pyronines, (1) celluloses modified with groups comprising at least one
quinacridones, quinolines, quinophthalones, squaranes, stil saturated or unsaturated, linear or branched C6-C30 hydro
benes, tetrazoliums, thiazines, thioindigo, thiopyronines, tri carbon-based chain, for instance hydroxyethylcelluloses
arylmethanes, and Xanthenes. 50 modified with groups comprising at least one hydrophobic
For the nonionic dyes, compounds with a log P of greater chain as defined previously, such as especially Natrosol Plus
than or equal to 2 may be chosen; log Pvalue conventionally Grade 330 CS (C16 alkyls sold by the company Aqua
represents the partition coefficient of the dye between octanol lon); Bermocol EHM 100 (sold by the company Berol
and water. Nobel), Amercell Polymer HM-1500 (hydroxyethylcellulose
Among the anionic direct dyes, mention may be made in 55 modified with a polyethylene glycol (15) nonylphenyl ether
particular of Disperse Red 17: Acid Yellow 9: Acid Black 1: group-sold by the company Amerchol);
Acid Yellow 36: Acid Orange 7: Acid Red 33: Acid Red 35: (2) hydroxypropyl guars modified with groups comprising
Acid Yellow 23: Acid Orange 24: Acid Violet 43; Acid Blue at least one hydrophobic chain as defined, for example Jaguar
62: Acid Blue 9: Acid Violet 49; and Acid Blue 7. XC-95/3 (C14 alkyl chain-sold by the company Rhodia
In various embodiments, the at least one direct dye may be 60 Chimie); Esaflor HM 22 (C22 alkyl chain-sold by the com
present in an amount ranging from about 0.001% to about pany Lamberti); RE210-18 (C14 alkyl chain) and RE.205-1
20% by weight, such as from about 0.005% to about 10% by (C20 alkyl chain-sold by the company Rhodia Chimie);
weight, or from about 0.01% to about 5% by weight, based on (3) copolymers of vinylpyrrolidone and of hydrophobic
the total weight of the composition. monomers containing a hydrophobic chain as defined above,
It is also possible to add other non-oxidative colorants or 65 for instance Antaron or Ganex V216 (vinylpyrrolidone/hexa
dyes to the dyeing and curl/frizz reducing compositions of the decene copolymers); Antaron or Ganex V220 (vinylpyrroli
present disclosure. Exemplary non-oxidative hair colorants done/eicosene copolymers), sold by the company I.S.P.,
 US 8,343,238 B1
17 18
(4) copolymers of C1-C6 alkyl (meth)acrylates and of Among these gums, mention will be made of scleroglucans
amphiphilic monomers containing a hydrophobic chain; such as, for example, Actigum CS from SanofiBio Industries:
(5) copolymers of hydrophilic (meth)acrylates and of Amigel from Alban Muller International, and also the gly
hydrophobic monomers comprising at least one hydrophobic oxal-treated scleroglucans described in FR2633940); xan
chain, for instance the polyethylene glycol methacrylate/lau than gums, for instance Keltrol R, Keltrol R. T. Keltrol(R) Tf.
ryl methacrylate copolymer; KeltrolR Bt, KeltrolR Rd, KeltrolR Cg (Nutrasweet Kelco),
(6) polymers with an aminoplast ether skeleton containing Rhodicare(R) S and Rhodicare(R) H (Rhodia Chimie); starch
at least one fatty chain, Such as the Pure Thix compounds sold derivatives, for instance Primogel(R) (Avebe); hydroxyethyl
by the company Sud-Chemie; celluloses such as Cellosize R. QP3L, QP4400H, QP30000H,
(7) linear (block structure), grafted, or starburst polyure 10 HEC30000A and Polymer PCG10 (Amerchol), Natrosol
thane polyethers comprising in their chain at least one hydro 250HHRR, 250MR, 250M, 250HHXR 250HHX, 250HR,
philic block, which is generally a polyoxyethylene block HX (Hercules) and Tylose(R) H1000 (Hoechst); hydroxypro
which may comprise between 50 and 1000 oxyethylene units pylcelluloses, for instance Klucel(R) EF. H. LHF, MF and G
approximately, and at least one hydrophobic block, which (Aqualon); carboxymethylcelluloses, for instance Blanose R.
may comprise aliphatic groups alone, optionally combined 15 7M8/SF, refined 7M, 7LF,7MF, 9M31F, 12M31XP 12M31P,
with cycloaliphatic and/or aromatic blocks. In various 9M31XF, 7H, 7M31, 7H3SXF (Aqualon), Aquasorb(RA500
embodiments, the polyurethane polyethers comprise at least (Hercules), Ambergum(R) 1221 (Hercules), Cellogen R.
two C6-C30 hydrocarbon-based hydrophobic chains, sepa HP810A, HP6HS9 (Montello) and Primellose(R) (Avebe).
rated by a hydrophilic block; the hydrophobic chains may be In other preferred embodiments, the at least one thickening
pendent chains or chains with one or more of the end groups agent are chosen from nonionic polymers which include, but
of the hydrophilic block(s). are not limited to, nonionic cellulose derivatives such as
The polyurethane polyethers may comprise a urethane hydroxyethylcelluloses modified by groups comprising at
bond between the hydrophilic blocks, but may also contain least one hydrophobic chain, such as alkyl, arylalkyl or alky
hydrophilic blocks linked to the lipophilic blocks via other laryl groups, or their blends, and in which the alkyl groups
chemical bonds. Examples of polyurethane polyethers that 25 are, for example, C8-C22 alkyl groups, such as the product
may be used include, but are not limited to, Nuvis FX 1100 Natrosol Plus Grade 330 CS(R) (C16 alkyls) sold by Aqualon
(European and US INCI name “Steareth-100/PEG-136/ or the product Bermocol EHM 100R) sold by Berol Nobel.
HMDI Copolymer sold by the company Elementis Special Cellulose derivatives modified by alkylphenyl polyalky
ties); RheolateR 205, 208, 204 or 212 (sold by the company lene glycol ether groups may also be chosen, Such as the
Rheox) and also Acrysol RM 184R) (sold by the company 30 product Amercell Polymer HM-1500R sold by Amerchol.
Rohm & Haas); Elfacos T210R (C12-C14 alkyl chain) and In certain exemplary embodiments, the at least one thick
Elfacos T212(R) (C18 alkyl chain) sold by the company Akzo. ening agent is chosen from cellulose derivatives, polysaccha
The product DW 1206B(R) from Rohm and Haas comprising rides, gums, clays, fumed silica, acrylates, polyacrylamides,
a C20 alkyl chain and comprising a urethane bond, provided crosslinked polyacrylic acids, crosslinked acrylamide poly
at a solids content of 20 percent in water, can also be used. 35 mers and copolymers, crosslinked methacryloyloxyethltrim
Use may also be made of solutions or dispersions of these ethyl-ammonium chloride homopolymers, and associative
polymers, for example in water or in an aqueous/alcoholic polymers. Said rheology-modifying agents may include, in
medium, such as polymers of RheolateR 255, RheolateR 278 particular embodiments, Xanthan gum, gum arabic, ghatti
and RheolateR 244, sold by Rheox, and DW 1206F and DW gum, karaya gum, gum tragacanth, carrageenan gum, agar
1206J provided by Rohm and Haas. 40 gum, carob gum, pectins, alginates, starches, hydroxy(C-C)
In some embodiments, the at least one thickening agent are alkylcelluloses, carboxy(C-C)alkylcelluloses, and mix
chosen from polymers of natural origin may include, for tures thereof.
example, thickening polymers comprising at least one Sugar In preferred embodiments, the at least one thickening agent
unit, for instance nonionic guar gums, optionally modified is nonionic or is an uncharged compound. Without intending
with C1-C6 hydroxyalkyl groups; biopolysaccharide gums of 45 to be bound by theory, it is believed that a thickening agent
microbial origin, Such as Scleroglucan gum or Xanthan gum, comprising a charged compound could adversely interact
gums derived from plant exudates, such as gum arabic, ghatti with the dyes compounds, thereby affecting the solubility and
gum, karaya gum, gum tragacanth, carrageenan gum, agar stability of the dye compounds in the compositions of the
gum and carob gum, pectins; alginates; Starches; hydroxy present disclosure.
(C1-C6)alkylcelluloses and carboxy(C1-C6)alkylcelluloses. 50 In particularly preferred embodiments, the at least one
It should be noted that the term "sugar unit denotes a thickening agent is chosen from Xanthan gum and guar gum.
monosaccharide (i.e. monosaccharide or oside or simple The at least one thickening agent of the present disclosure
Sugar) portion, an oligosaccharide portion (short chains may be employed in the composition for dyeing and reducing
formed from a sequence of monosaccharide units, which may curland/or frizziness of hair of the of the present disclosure in
be different) or a polysaccharide portion long chains consist 55 an amount ranging from, for example, about 0.05 to about
ing of monosaccharide units, which may be different, i.e. 20% by weight, preferably from about 0.5 to about 15% by
polyholosides or polyosides. The saccharide units may also weight and more preferably from about 1 to about 10% by
be substituted with alkyl, hydroxyalkyl, alkoxy, acyloxy or weight, based on the total weight of the composition for
carboxyl radicals, the alkyl radicals containing from 1 to 4 dyeing and reducing curl and/or frizziness of hair.
carbon atoms. 60 Fatty Substance
Non-limiting examples of nonionic, unmodified guar gums Exemplary fatty Substances that may be used in various
that may be used in various embodiments include Guargel embodiments of the disclosure include, but are not limited to,
D/15 (Noveon); Vidogum GH 175 (Unipectine), Meypro organic compounds that are insoluble in water at normal
Guar 50 and Jaguar C (Meyhall/Rhodia Chimie). Non-limit temperature (25° C.) and at atmospheric pressure (760
ing examples of modified nonionic guar gums include Jaguar 65 mmHg) (solubility below 5% and such as below 1% and
HP8, HP60, HP120, DC 293 and HP 105 (Meyhall/Rhodia further such as below 0.1%). Fatty substances have in their
Chimie); Galactasol 4H4FD2 (Aqualon). structure a chain of at least two siloxane groups, or at least one
 US 8,343,238 B1
19 20
hydrocarbon chain having at least 6 carbon atoms. Moreover, waxes such as that sold by the company SOPHIM under
fatty Substances are generally soluble in organic solvents in reference M82, or waxes of polyethylene, or of polyolefins in
the same conditions oftemperature and pressure, for example general.
in chloroform, ethanol, benzene or decamethylcyclopenta Exemplary fatty acid esters are the esters of saturated or
siloxane. unsaturated, linear or branched C1-C26 aliphatic mono- or
Fatty Substances may be, for example, chosen from lower polyacids and of saturated or unsaturated, linear or branched
alkanes, fatty alcohols, esters of fatty acid, esters of fatty C1-C26 aliphatic mono- or polyalcohols, the total number of
alcohol, oils such as mineral, vegetable, animal and synthetic carbons of the esters being, for example, greater than or equal
to 10.
non-silicone oils, non-silicone waxes and silicones. 10 Among the monoesters, non-limiting mentions can be
In Some embodiments, the alcohols and esters have at least made of dihydroabietyl behenate; octyldodecyl behenate;
one linear or branched, Saturated or unsaturated hydrocarbon isocetyl behenate; cetyl lactate; C12-C15 alkyl lactate; isos
group, comprising 6 to 30 carbon atoms, optionally Substi tearyl lactate; lauryl lactate; linoleyl lactate, oleyl lactate;
tuted, for example, with at least one hydroxyl group (for (iso)Stearyl octanoate; isocetyl octanoate; octyl octanoate;
example 1 to 4). If they are unsaturated, these compounds can 15 cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl
have one to three, conjugated or unconjugated, carbon-carbon laurate; isocetyl Stearate; isodecyl octanoate; isodecyl oleate;
double bonds. isononyl isononanoate; isostearyl palmitate; methyl acetyl
With regard to the lower alkanes, in some embodiments, ricinoleate; myristyl Stearate; octyl isononanoate: 2-ethyl
these have from 6 to 16 carbon atoms and are linear or hexyl isononate; octyl palmitate; octyl pelargonate; octyl
branched, optionally cyclic. As examples, alkanes can be Stearate; octyldodecyl erucate; oleyl erucate; ethyl and iso
chosen from hexane and dodecane, isoparaffins such as iso propyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl
hexadecane and isodecane. palmitate, alkyl myristates such as isopropyl, butyl, cetyl,
Examples of non-silicone oils that may be used in various 2-octyldodecyl, mirystyl, Stearyl myristate, hexyl Stearate,
embodiments of the disclosure, include, but are not limited to, butyl Stearate, isobutyl Stearate; dioctyl malate, hexyl laurate,
hydrocarbon oils of animal origin, Such as perhydrosqualene; 25 and 2-hexyldecyl laurate.
hydrocarbon oils of vegetable origin, Such as liquid triglyc Further non-limiting examples of esters include esters of
erides offatty acids having from 6 to 30 carbonatoms such as C4-C22 di- or tricarboxylic acids and of C1-C22 alcohols and
triglycerides of heptanoic or octanoic acids, or for example the esters of mono-, di- or tricarboxylic acids and of C2-C26
Sunflower oil, maize oil, soya oil, cucurbit oil, grapeseed oil, di-, tri-, tetra- or pentahydroxy alcohols.
sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, 30 Even further non-limiting examples of esters include:
Sunflower oil, castor oil, avocado oil, triglycerides of diethyl sebacate; diisopropyl sebacate; diisopropyl adipate;
caprylic?capric acids such as those sold by the company di-n-propyladipate; dioctyladipate; diisostearyladipate; dio
Stearineries Dubois or those sold under the names MIG
ctyl maleate; glyceryl undecylenate; octyldodecyl Stearoyl
Stearate; pentaerythrityl monoricinoleate; pentaerythrity1 tet
LYOLR 810, 812 and 818 by the company Dynamit Nobel, 35 raisononanoate; pentaerythrityl tetrapelargonate; pentaeryth
jojoba oil, shea butter oil; hydrocarbons with more than 16 rity1 tetraisostearate; pentaerythrity1 tetraoctanoate; propy
carbon atoms, linear or branched, of mineral or synthetic lene glycol dicaprylate; propylene glycol dicaprate, tridecyl
origin, such as paraffin oils, petroleum jelly, liquid paraffin, erucate; triisopropyl citrate; trisotearyl citrate; glyceryl
polydecenes, hydrogenated polyisobutene Such as Parleam(R), trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trio
fluorinated, partially hydrocarbon oils; as fluorinated oils, 40 leyl citrate, propylene glycol dioctanoate; neopentyl glycol
non-limiting examples include perfluoromethylcyclopentane diheptanoate; diethylene glycol diisanonate; and polyethyl
and perfluoro-1,3-dimethylcyclohexane, sold under the ene glycol distearates.
names “FLUTEC(R) PC1 and “FLUTEC(R) PC3 by the com Among the esters mentioned above, exemplary esters
pany BNFL Fluorochemicals; perfluoro-1,2-dimethylcy include ethyl, isopropyl, myristyl, cetyl, Stearyl palmitates,
clobutane; perfluoroalkanes Such as dodecafluoropentane and 45 ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl
tetradecafluorohexane, sold under the names "PF 5050” and myristates Such as isopropyl, butyl, cetyl, 2-octyldodecyl
“PF 5060R” by the 3M Company, or bromoperfluorooctyl myristate, hexyl Stearate, butyl Stearate, isobutyl Stearate;
sold under the name “FORALKYL(R)” by the company dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and
Atochem; nonafluoro-methoxybutane and nonafluoroet isononyl isononanate, cetyl octanoate.
hoxyisobutane; derivatives of perfluoromorpholine. Such as 50 The composition can also comprise, as fatty ester, esters
4-trifluoromethyl perfluoromorpholine sold under the name and di-esters of sugars of C6-C30, such as C12-C22 fatty
“PF 5052(R” by the 3M Company. acids. "Sugar as used here means oxygen-containing hydro
The fatty alcohols that may be chosen as the at least one carbon compounds that possess several alcohol functions,
fatty Substance include, but are not limited to, non-alkoxy with or without aldehyde or ketone functions, and having at
lated, saturated or unsaturated, linear or branched, and have 55 least 4 carbon atoms. These Sugars can be monosaccharides,
from 6 to 30 carbonatoms and more particularly from 8 to 30 oligosaccharides or polysaccharides.
carbon atoms, such ascetyl alcohol, Stearyl alcohol and their As suitable Sugars, non-limiting examples include Sucrose,
mixture (cetylstearyl alcohol), octyldodecanol, 2-butyloc glucose, galactose, ribose, fucose, maltose, fructose, man
tanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol nose, arabinose, Xylose, lactose, and their derivatives, for
or linoleic alcohol. 60 example alkylated. Such as methylated derivatives such as
The exemplary non-silicone wax or waxes that can be used methylglucose.
may be chosen from carnauba wax, candelilla wax, Alfa wax, The esters of Sugars and offatty acids may be, for example,
paraffin wax, oZokerite, vegetable waxes such as olive wax, chosen from the esters or mixtures of esters of Sugars
rice wax, hydrogenated jojoba wax, or absolute waxes of described previously and of linear or branched, saturated or
flowers, such as the essential wax of blackcurrant flower sold 65 unsaturated C6-C30, such as C12-C22 fatty acids. If they are
by the company BERTIN (France), animal waxes such as unsaturated, these compounds can have one to three, conju
beeswaxes, or modified beeswaxes (cerabellina), or marine gated or unconjugated, carbon-carbon double bonds.
 US 8,343,238 B1
21 22
The esters according to at least one embodiment can also be
chosen from mono-, di-, tri- and tetra-esters, polyesters and D-D-D-D'
mixtures thereof.
These esters can be, for example, oleate, laurate, palmitate,
myristate, behenate, cocoate, Stearate, linoleate, linolenate, t t
caprate, arachidonates, or mixtures thereof Such as the oleo with D': -i-o- with D': -i-o-
palmitate, oleo-Stearate, palmito-stearate mixed esters. CH3 C8H17
For example, the mono- and di-esters can be used, and Such
as the mono- or di-oleate, Stearate, behenate, oleopalmitate, 10 Further non-limiting examples may include mixtures of
linoleate, linolenate, oleoStearate, of Sucrose, of glucose or of cyclic polydialkylsiloxanes with organic compounds derived
methylglucose. from silicon, Such as the mixture of octamethylcyclotetrasi
One non-limiting example useful in various embodiments loxane and tetratrimethylsilylpentaerythritol (50/50) and the
mixture of octamethylcyclotetrasiloxane and oxy-11'-(hexa
includes the product sold under the name GLUCATER DO 15 2.2.2.2.3,3'-trimethylsilyloxy)bis-neopentane.
by the company Amerchol, which is a dioleate of methylglu Other suitable volatile silicones include the linear volatile
COSC.
polydialkylsiloxanes having 2 to 9 silicon atoms and with a
Exemplary esters or mixtures of esters of Sugar offatty acid viscosity less than or equal to 5x10-6 m2/s at 25°C. One
include: the products sold under the names F160, F140, F110, non-limiting example is decamethyltetrasiloxane, marketed
F90, F70, SL40 by the company Crodesta, denoting respec under the name “SH 200” by the company TORAY SILI
tively the palmito-stearates of sucrose formed from 73% of CONE. Silicones included in this class are also described in
monoester and 27% of di- and tri-ester, from 61% of the article published in Cosmetics and Toiletries, Vol. 91, Jan.
monoester and 39% of di-, tri-, and tetra-ester, from 52% of 76, p.27-32-TODDBYERS“Volatile Silicone fluids for cos
monoester and 48% of di-, tri-, and tetra-ester, from 45% of metics, which is incorporated by reference herein.
monoester and 55% of di-, tri-, and tetra-ester, from 39% of 25 Even further non-limiting mentions can be made of non
monoester and 61% of di-, tri-, and tetra-ester, and the mono Volatile polydialkylsiloxanes, gums and resins of polydi
laurate of Sucrose; the products sold under the name Ryoto alkylsiloxanes, polyorganosiloxanes modified with the afore
Sugar Esters for example with the reference B370 and corre mentioned organofunctional groups, and mixtures thereof.
sponding to the behenate of sucrose formed from 20% of These silicones may be, for example, chosen from the
30 polydialkylsiloxanes, such as the polydimethylsiloxanes with
monoester and 80% of di-triester-polyester; sucrose mono trimethylsilyl end groups. The viscosity of the silicones is
di-palmito-stearate marketed by the company Goldschmidt measured at 25° C. according to Standard Test Method for
under the name TEGOSOFTR) PSE. Kinematic Viscosity of Transparent and Opaque Liquids (and
Silicones usable in the composition of the present disclo Calculation of Dynamic Viscosity).
sure include but are not limited to volatile or non-volatile, 35 Among these polydialkylsiloxanes, mention can be made
cyclic, linear or branched silicones, modified or not with of non-exhaustively, the following commercial products: the
organic groups, having a viscosity from 5x10-6 to 2.5 m2/s at SILBIONER) oils of Series 47 and 70 047 or the MIRASILOR)
25°C., such as from 1 x 10-5 to 1 m2/s. oils marketed by RHODIA, for example the oil 70 047 V
The silicones usable according to the disclosure can be in 500,000; the oils of the MIRASILR) series marketed by the
the form of oils, waxes, resins or gums.
40 company RHODIA; the oils of the 200 series from the com
pany DOW CORNING such as DC200, with a viscosity of
In some embodiments, the silicone may be chosen from the 60,000 mm2/s; the VISCASILR) oils from GENERAL
polydialkylsiloxanes, such as the polydimethylsiloxanes ELECTRIC and certain oils of the SF series (SF 96, SF 18)
(PDMS), and the organo-modified polysiloxanes having at from GENERAL ELECTRIC.
least one functional group chosen from the poly(alkoxylated) 45 Non-limiting mention can also be made of the polydimeth
groups, the amine groups and the alkoxy groups. ylsiloxanes with dimethylsilanol end groups known under the
The organopolysiloxanes are defined in more detail in the name of dimethiconol (CTFA), such as the oils of the 48 series
work of Walter NOLL “Chemistry and Technology of Sili from the company RHODIA.
cones' (1968), Academic Press. They can be volatile or non In this class of polydialkylsiloxanes, non-limiting men
volatile. 50 tions can be made of the products marketed under the names
“ABIL WAX(R) 9800 and 9801 by the company GOLD
When they are volatile, the silicones are, for example, SCHMIDT, which are polydialkyl (C1-C20) siloxanes.
chosen from those with a boiling point between 60° C. and The silicone gums usable according to the disclosure are,
260° C. By way of example, the silicones may be chosen from for example, polydialkylsiloxanes, such as polydimethylsi
cyclic polydialkylsiloxanes having from 3 to 7. Such as from 55 loxanes with high number-average molecular weights
4 to 5, silicon atoms. Various exemplary silicones may be the between 200,000 and 1,000,000 used alone or mixed in a
octamethylcyclotetrasiloxane marketed under the name solvent. This solvent can be chosen from the volatile sili
VOLATILE SILICONER 7207 by UNION CARBIDE or cones, the polydimethylsiloxane (PDMS) oils, the polyphe
SILBIONER 70045 V2 by RHODIA, the decamethylcyclo nylmethylsiloxane (PPMS) oils, the isoparaffins, the poly
pentasiloxane marketed under the name VOLATILE SILI 60 isobutylenes, methylene chloride, pentane, dodecane,
CONER 7158 by UNION CARBIDE, and SILBIONER tridecane and mixtures thereof.
70045 V5 by RHODIA, and mixtures thereof. Products useful according to various embodiments of the
Non-limiting examples may also include the cyclocopoly disclosure include, for example, mixtures such as those
mers of the dimethylsiloxanes/methylalkylsiloxane type, formed from a chain end hydroxylated polydimethylsiloxane,
such as SILICONE VOLATILE(R) FZ3109 marketed by the 65 or dimethiconol (CTFA) and a cyclic polydimethylsiloxane
company UNION CARBIDE, of the following formula also called cyclomethicone (CTFA), such as the product Q2
(VVI): 1401 marketed by the company DOW CORNING: mixtures
 US 8,343,238 B1
23 24
of a polydimethylsiloxane gum and a cyclic silicone such as groups, such as the product marketed under the name "SILI
the product SF 1214 Silicone Fluid from the company GEN CONE COPOLYMER F-755” by SWS SILICONES and
ERAL ELECTRIC, said product being a gum SF 30 corre ABIL WAX(R) 2428, 2434 and 2440 by the company GOLD
sponding to a dimethicone, having a number-average molecu SCHMIDT.
lar weight of 500,000, dissolved in the oil SF 1202 Silicone In various exemplary embodiments, the at least one fatty
Fluid corresponding to decamethylcyclopentasiloxane; mix Substance is neither alkoxylated, nor glycerolated. For
tures of two PDMS of different viscosities, for example, of a example, the at least one fatty Substance may be chosen from
PDMS gum and a PDMS oil, such as the product SF 1236 compounds that are liquid or pasty at room temperature and
from the company GENERAL ELECTRIC. The product SF atmospheric pressure. By way of example, the at least one
1236 is a mixture of a gum SE 30 as defined above having a 10 fatty Substance may be a compound that is liquid at a tem
viscosity of 20 m2/s and an oil SF 96 with a viscosity of perature of 25°C., and atmospheric pressure.
5x10-6 m2/s. This product, for example, has 15% of gum SE Exemplary fatty Substances may be, for example, chosen
30 and 85% of oil SF 96. from the lower alkanes, fatty alcohols, esters of fatty acid,
The organopolysiloxane resins usable according to the dis esters of fatty alcohol, and oils such as non-silicone mineral,
closure include, but are not limited to, crosslinked siloxane 15 Vegetable and synthetic oils, the silicones.
systems containing the units: R2SiO2/2, R3SiO1/2, RSiO3/2 According to at least one embodiment, the at least one fatty
and SiO4/2, wherein R represents an alkyl having from 1 to 16 Substance, is chosen from liquid paraffin, polydecenes, liquid
carbon atoms. For example, R may denote a C1-C4 lower esters offatty acids and offatty alcohols, non-silicone oils and
alkyl group, Such as methyl. mixtures thereof.
Among these resins, non-limiting mention can be made of In some embodiments, the at least one fatty Substance is
the product marketed under the name “DOW CORNING(R) chosen from alkanes, hydrocarbons and silicones.
593 or those marketed under the names “SILICONE FLUID In further exemplary embodiments, the at least one fatty
SS 4230 and SS 4267” by the company GENERAL ELEC Substance may be chosen from fatty acids having from
TRIC, which are silicones of dimethyl/trimethyl siloxane example, from about 6 to about 40 carbon atoms such as
Structure. 25 Arachidic Acid, Arachidonic Acid, Beeswax Acid, Capric
Non-limiting mention can also be made of the resins of the Acid, Caproic Acid, Caprylic Acid, Coconut Acid, IsoStearic
trimethylsiloxysilicate type, such as those marketed under the Acid, Lauric Acid, Linoleic Acid, Linolenic Acid, Myristic
names X22-4914, X21-5034 and X21-5037 by the company Acid, Oleic Acid, Olive Acid, Palmitic Acid, Rapeseed Acid,
SHIN-ETSU. Stearic Acid, Tallow Acid, Undecanoic Acid, Undecylenic
The organomodified silicones usable according to the dis 30 Acid, Wheat Germ Acid.
closure include but are not limited to silicones as defined In various exemplary embodiments, fatty acids having
previously, having in their structure at least one organofunc from about 6 to about 40 carbon atoms are chosen from
tional group fixed by a hydrocarbon group. Capric Acid, Caprylic Acid, Lauric Acid, Oleic Acid, Isos
In addition to the silicones described above, the organo tearic Acid, and Stearic Acid.
modified silicones can be polydiaryl siloxanes, such as poly 35 In various embodiments, the at least one fatty Substance
diphenylsiloxanes, and polyalkyl-arylsiloxanes functional may be present in the composition for dyeing and reducing
ized by the aforementioned organofunctional groups. curland/or frizziness of hair of the of the present disclosure in
The polyalkarylsiloxanes are, for example, chosen from an amount of at least about 10% by weight, such as from about
the polydimethyl/methylphenylsiloxanes, the polydimethyl/ 10% to about 80% by weight, such as from about 15% to
diphenylsiloxanes, linear and/or branched, with Viscosity 40 about 65% by weight, or from about 20% to about 55% by
ranging from 1x10-5 to 5x102 m2/s at 25D. weight, based on the total weight of the composition for
Among these polyalkarylsiloxanes, non-limiting mention dyeing and reducing curl and/or frizziness of hair.
can be made of the products marketed under the following Alkoxysilane
names: the SILBIONER) oils of series 70641 from RHODIA: The composition for dyeing and reducing curl and/or
the oils of the Series RHODORSILR) 70 633 and 763 from 45 frizziness of hair described above may include at least one
RHODIA; the oil DOW CORNING(R) 556 COSMETIC alkoxysilane comprising at least one solubilizing functional
GRADE FLUID from DOW CORNING: the silicones of the group.
PK series from BAYER such as the product PK20; the sili Suitable alkoxysilanes comprising at least one solubilizing
cones of the series PN, PH from BAYER such as the products functional group for use in the present invention include, but
PN1000 and PH1000; certain oils of the SF series from GEN 50 are not limited to, primary, secondary, and tertiary amine,
ERAL ELECTRIC such as SF 1023, SF 1154, SF 1250, SF aromatic amine, alcohol, carboxylic acid, Sulfonic acid, anhy
1265. dride, carbamate, urea, guanidine, aldehyde, ester, amide,
Among the organomodified silicones, non-limiting men epoxy, pyrrole, dihydroimidazole, gluconamide, pyridyle,
tion can be made of the polyorganosiloxanes having: poly and polyether groups.
oxyethylene and/or polyoxypropylene groups optionally 55 The at least one alkoxysilane present in the composition
with C6-C24 alkyl groups such as the products called dime comprises at least one solubilizing functional group, which
thicone copolyol marketed by the company DOW CORNING may be identical or different, such as those previously
under the name DC 1248 or the oils SILWETRL 722, L7500, defined.
L 77, L 711 from the company UNION CARBIDE and the The at least one alkoxysilane comprising at least one solu
alkyl (C12)-methicone copolyol marketed by the company 60 bilizing functional group present in the composition of the
DOW CORNING under the name Q2 5200; substituted or present disclosure may comprise at least one silicon atom, for
unsubstituted amine groups such as the products marketed example, one silicon atom.
under the name GP 4 Silicone Fluid and GP 7100 by the The at least one alkoxysilane comprising at least one solu
company GENESEE or the products marketed under the bilizing functional group present in the composition may, in
names Q2 8220 and DOW CORNING(R) 929 or 939 by the 65 at least one embodiment, comprise two or three alkoxy func
company DOW CORNING. The substituted amine groups tions. In another embodiment, the alkoxy functional groups
are, for example, C1-C4 aminoalkyl groups; alkoxylated are chosen from methoxy and ethoxy functional groups.
 US 8,343,238 B1
25 26
According to a further embodiment, the at least one alkox lizing functional group present in the composition of the
ysilane comprising at least one solubilizing functional group present disclosure is chosen from compounds of formula
present in the composition of the present disclosure is chosen (III):
from compounds of formula (I):
(III)
(I)
R R4
Y -R-Si-Rs
A R
/ V 10
R R6
wherein:
wherein: R is chosen from halogen atoms, OR groups, and R.
R is chosen from halogen atoms, OR groups, and R. groups:
groups: 15 R is chosen from halogen atoms, OR's groups, and R'
Rs is chosen from halogen atoms, OR" groups, and R2 groups:
groups: Ra is chosen from halogen atoms, OR groups, and R",
groups:
R is chosen from halogen atoms, OR" groups, and R.
groups: wherein at least two groups R2, R1s and Ra are different
R. R. R. R. R", R", R. R. and R, which may be from R. R', and R" groups;
R is a group chosen from groups bearing at least one
identical or different, are chosen from linear and branched, function chosen from: carboxylic acids and salts thereof,
saturated and unsaturated hydrocarbon groups, optionally Sulfonic acids and salts thereof, and polyalkylethers; and
bearing at least one additional chemical group, wherein R. Ro, R'o, R"o, R. R', and R', which may be identical or
R. R', R", and R" may also be chosen from hydrogen; at least 25 different, are chosen from linear and branched, saturated and
two groups R. Rs, and R are different from R, R2, and unsaturated, C-C hydrocarbon groups optionally bearing
R, and at least two groups R', R", and R" are not hydrogen. at least one additional chemical functional group chosen
In at least one embodiment, the R. R. R. R. R. R's, R", from: carboxylic acids and salts thereof. Sulfonic acids and
and R" groups are chosen from C-C alkyl, C-C aryl, salts thereof, and polyalkylether functions, wherein R',
C-C alkyl-C-C aryl, and C-C aryl-C-C-alkyl radi 30 R', and Ramay also be chosen from hydrogen, and wherein
cals. at least two of the groups R', R's, and Rare not hydrogen.
According to a second embodiment of the present disclo In at least one embodiment, the R. R. R. R. R. and
Sure, the at least one alkoxysilane comprising at least one R" groups are chosen from C-C alkyl groups, Ca-Caryl
solubilizing functional group present in the composition is groups, C-Cs alkyl-Co-Caryl groups, and Co-Caryl-C-
chosen from compounds of formula (II): 35 Cs alkyl groups.
According to another embodiment of the present disclo
Sure, the at least one alkoxysilane comprising at least one
(II) solubilizing functional group present in the composition of
R7 n. Si -R9 the present disclosure is chosen from compounds of formula
R1 a.
R10 40 (IV):

wherein: —Si-(R22)(OR), (IV)

Ro is chosen from halogenatoms and OR's groups and Rio wherein:
is chosen from halogen atoms and OR groups; wherein at 45 R. R. R', and R', which may be identical or differ
least one of R and Rio is not a halogen; ent, are chosen from linear and branched, saturated and unsat
R's and R', which may be identical or different, are cho urated hydrocarbon chains, optionally comprising at least one
Sen from hydrogen, and linear and branched, Saturated and heteroatom, optionally interrupted by or substituted with at
unsaturated C-C hydrocarbon groups; wherein at least one least one group chosen from ether, ester, amine, amide, car
of Ro and Rio is not hydrogen; 50 boxyl, hydroxyl, and carbonyl groups,
R is a non hydrolyzable functional group providing a X is an integer ranging from 1 to 3.
cosmetic effect, and X' is an integer ranging from 1 to 3.
Rs is a non hydrolyzable functional group bearing at least
one function chosen from: amines, carboxylic acids and salts 55 p=0 or 1,
thereof. Sulfonic acids and salts thereof, polyols such as gly p'=0 or 1,
col, polyethers such as polyalkylene ether, and phosphoric p"=0 or 1,
acids and salts thereof. q=0 or 1,
As used herein, the term “functional group providing a
cosmetic effect” means a group derived from an entity chosen 60 wherein at least one of q or q is not equal to Zero,
from reducing agents, oxidizing agents, coloring agents, A., A', and A", which may be identical or different, are
polymers, Surfactants, antibacterial agents, and UV absorb chosen from linear and branched C-Co alkylene divalent
ing filters. radicals, and
In at least one embodiment, the functional group providing R and R's, which may be identical or different, are cho
a cosmetic effect is a group derived from a coloring agent. 65 Sen from hydrogen and linear and branched, Saturated and
According to a third embodiment of the present disclosure, unsaturated hydrocarbon chains, optionally comprising at
the at least one alkoxysilane comprising at least one solubi least one heteroatom, optionally interrupted by or substituted
 US 8,343,238 B1
27 28
with at least one entity chosen from: ether, C-C alcohol and carbonyl groups, and aromatic, heterocyclic, and non
ester, amine, carboxyl, alkoxysilane, C-C aryl, hydroxyl, heterocyclic rings, optionally Substituted with at least one
and carbonyl groups, and aromatic, heterocyclic, and non group chosen from: C-C alcohol ester, amine, amide, car
heterocyclic rings, optionally Substituted with at least one boxyl, alkoxysilane, hydroxyl, carbonyl, and acyl groups,
group chosen from C-C alcohol ester, amine, amide, car r is an integer ranging from 0 to 4,
boxyl, alkoxysilane, hydroxyl, carbonyl, and acyl groups. r=0 or 1, and
As defined above, R. R. R', and R', which may be Rs, which may be identical or different, is chosen from
identical or different, may be chosen from hydrocarbon hydrogen and linear and branched, Saturated and unsaturated
chains. As used herein, the term "hydrocarbon chain” means, hydrocarbon chains, comprising, for example, from 1 to 10
for example, a chain comprising from 1 to 10 carbon atoms. 10 carbon atoms and optionally at least one heteroatom, option
Likewise, R and R's may be chosen from hydrocarbon ally interrupted by or substituted with at least one entity
chains. In Such an embodiment, the hydrocarbon chains may chosen from: ether, C-Co alcohol ester, amine, carboxyl,
comprise from 1 to 10 carbon atoms. alkoxysilane, Co-Co aryl, hydroxyl, and carbonyl groups,
According to one embodiment, the aromatic ring com and aromatic, heterocyclic, and non-heterocyclic rings,
prises from 6 to 30 carbonatoms. In another embodiment, the
15 optionally substituted with at least one group chosen from:
aromatic ring is an optionally Substituted phenyl radical. C-C alcohol ester, amine, amide, carboxyl, alkoxysilane,
hydroxyl, carbonyl, and acyl groups.
In at least one embodiment, in formula (IV) above: As defined above, R2 and Rs, which may be identical or
RR', different, may be chosen from hydrocarbon chains. As used
R22 R22, herein, the term “hydrocarbon chain' is intended to mean a
chain comprising, for example, from 1 to 10 carbon atoms.
Likewise, Re and R-7 may be chosen from hydrocarbon
chains. In this embodiment, the hydrocarbon chains may
q1, and comprise from 1 to 10 carbon atoms.
25 According to another embodiment, the aromatic ring com
According to a further embodiment, the at least one alkox prises from 6 to 30 carbon atoms. In a further embodiment,
ysilane comprising at least one solubilizing functional group the aromatic ring is an optionally Substituted phenyl radical.
used according to the present disclosure may also have at least According to at least one embodiment, the at least one
one of the following characteristics: alkoxysilane comprising at least one solubilizing functional
R. R. R', and R', which may be identical or differ
30 group used in accordance with the present disclosure may
ent, are chosen from C-C alkyl groups; have at least one of the following characteristics:
R is a C-C alkyl group:
A and A', which may be identical or different, are chosen x"=3;
from linear C-C alkylene groups; and/or n'=n"=1:
R2 is hydrogen. 35 r=r'=0; and/or
According to this embodiment, the at least one alkoxysi R and R-7, which may be identical or different, are cho
lane comprising at least one solubilizing functional group Sen from hydrogen and groups chosen from C-C alkyl
may be chosen from compounds of formula (V): groups, C-C hydroxyalkyl groups, and C-C aminoalkyl
groups.
40 According to a further embodiment of the present disclo
(V) Sure, the at least one alkoxysilane comprising at least one
solubilizing functional group present in the composition is
chosen from compounds of formula (VI):
AR (RO)x (Ro)y-Si-(A)-CH=O (VI)
(RO),(Rs) -Si-(E)- o-()5S,(E)-NRR, 45
wherein:
R and Ro, which may be identical or different, are cho
Sen from linear and branched, Saturated and unsaturated
wherein: hydrocarbon chains, optionally comprising at least one het
Ra and Rs, which may be identical or different, are cho 50 eroatom, optionally interrupted by or substituted with at least
Sen from linear and branched, saturated and unsaturated one group chosen from ether, ester, amine, amide, carboxyl,
hydrocarbon chains, optionally comprising at least one het hydroxyl, and carbonyl groups,
eroatom, optionally interrupted by or substituted with at least X=2 or 3,
one group chosen from ether, ester, amine, amide, carboxyl,
hydroxyl, and carbonyl groups, 55 A is chosen from linear and branched C-Co alkylene
x"=2 or 3, divalent radicals, optionally interrupted by or substituted with
y"=3-x", at least one group chosen from C-Clso alcohol ester, amine,
n"=0 or 1, carboxyl, alkoxysilane, Co-Co aryl, hydroxyl, and carbonyl
n"=0 or 1, groups, and
E and E, which may be identical or different, are chosen 60 S=O or 1.
from linear and branched C-C alkylene divalent radicals, As defined above, R and Ro, which may be identical or
Re and R-7, which may be identical or different, are cho different can be chosen from hydrocarbon chains. As used
Sen from hydrogen and linear and branched, Saturated and herein, the term “hydrocarbon chain” means a chain compris
unsaturated hydrocarbon chains, optionally comprising at ing, for example, from 1 to 10 carbon atoms.
least one heteroatom, optionally interrupted by or substituted 65 In another embodiment, the at least one alkoxysilane com
with at least one entity chosen from: ether, C-C alcohol prising at least one solubilizing functional group may have at
ester, amine, carboxyl, alkoxysilane, Co-Co aryl, hydroxyl, least one of the following characteristics:
 US 8,343,238 B1
29 30
Ro and Ro, which may be identical or different, are cho dyes; groups having a reductive effect. Such as thiol groups,
sen from C-C, alkyl groups; Sulphinic acid or Sulphinic salt, it being possible for these
s=1; and alkoxysilanes to carry a solubilizing non-hydrolysable group
A is a linear C-C alkylene group. Such as amino groups, carboxylic acids, Sulphonic acids,
According to this embodiment, the at least one alkoxysi Sulphates, quaternary ammoniums, polyalcohols, polyether
lane comprising at least one solubilizing functional group and phosphates. One possible example includes aminopro
may be chosen from: pyl-N-(4.2-dinitrophenyl)aminopropyldiethoxysilane. Com
triethoxysilylbutyraldehyde, of formula: pounds of this kind are described, for example, in Patent
(CHCH2O). S-(CH2). CH=O 10
Application EP 1216 023.
The alkoxysilanes of the present disclosure may be amino
triethoxysilyl undecanal, of formula: aryl alkoxysilanes. Possible examples include but are not
(CHCH2O). S-(CH2) -CH=O limited to the following compounds:
and
3-(m-aminophenoxy)propyltrimethoxysilane, of the for
mula:
triethoxysilyl undecanal, ethylene glycol acetal, of for 15
mula:
(CHCH2O). Si-(CH2)o CH(OCH2)2.
In a further embodiment, the at least one alkoxysilane
comprising at least one solubilizing functional group is cho
sen from compounds of formula (VII):
provided by GELEST,
(VII) p-aminophenyltrimethoxysilane, of formula:
OR 25
M
HN(CH2)-Si-OR HN
OR

wherein the R radicals, which may be identical or different, 30

are chosen from C-C alkyl radicals and n is an integer
ranging from 1 to 6, for example, from 2 to 4. provided by GELEST, and
In at least one embodiment, the at least one alkoxysilane N-(2-aminoethylaminomethyl)phenethyltrimethoxysi
comprising at least one solubilizing functional group present
in the composition of the present disclosure is Y-aminopro 35 lane, of the formula:
pyltriethoxysilane, also known as 3-aminopropyltriethoxysi
lane.
The alkoxysilanes useful in the present disclosure can be
chosen from alkoxysilanes comprising a silicon atom of for (CHO)-Si-(CH2):
mula Ra Six, wherein X is a hydrolysable group such as 40
methoxy, ethoxy or 2-methoxyethoxy, R is a monovalent CH-NH-(CH2)-NH.
organic radical which contains 1 to 12 carbonatoms and may
contain groups such as mercapto, epoxy, acrylyl, methacry
lyl, amino or urea, and n is an integer from 1 to 4, and provided by GELEST.
according to at least one embodiment is 3. Possible examples 45 According to at least one embodiment, the at least one
of useful alkoxysilanes include 3-mercaptopropyltriethox organic silicon compound is N-(2-aminoethylaminomethyl)
ysilane and aminoalkyltrialkoxysilanes such as 3-aminopro phenethyltrimethoxysilane.
pyltriethoxysilane, as described in French Patent Application The alkoxysilanes of the present disclosure may also be
No. FR 2 789 896. silanes having an aldehyde oracetal functional group, Such as
Other useful alkoxysilanes are cited, for example, in Patent 50
the triethoxysilylbutyraldehyde of formula (CHCHO)Si
Application EP 1 216 022, which describes alkoxysilanes (CH2)CHO or the triethoxysilylunedecanol ethylene glycol
comprising at least one hydrocarbon chain containing a non acetal (CHCHO)Si(CH2)CH(OCH), which are pro
basic solubilizing chemical function. In this respect, non vided by GELEST.
limiting mention may be made of the HC1-neutralized sodium The alkoxysilanes may also be silanes containing non
N-(3-trimethoxysilyl)propylethylenediaminetriacetate 55
supplied by GELEST. primary amines. Such as the bis3-(triethoxysilyl)propyl
According to at least one embodiment, the alkoxysilanes amine of the formula (CHCHO), Si(CH)NH(CH)Si
may comprise at least one hydrocarbon chain containing fluo (OCH2CH) provided by Fluorochem, the bis
rine atoms. Possible examples include but are not limited to trimethoxysilylpropylamine of the formula (CHO). Si
the 3,3,3-trifluoropropyltriethoxysilane or tridecafluorooc 60 (CH)NH(CH)SiOCH) provided by Gelest, the bis
tyltriethoxysilane compounds described in Patent Applica methyldiethoxysilylpropylamine of the formula
tion EP 1510 197. (CHCHO)CHSi (CH)NH(CH)SiCH(OCHCH.)
In another embodiment, the useful alkoxysilanes may be provided by Gelest and the bis3-trimethoxysilylpropyleth
alkoxysilanes which carry a group having a cosmetic func ylenediamine of formula (CHO)Si(CH2).NE(CH)NH
tional group, Such as aromatic nitro dyes or anthraquinone, 65 (CH)Si(OCH) provided by Gelest.
napthoduinone, benzoquinone, azo, Xanthene, triaryl In another embodiment the at least one alkoxysilane is a
methane, azine, indoaniline, indophenolic or indoamine trialkoxysilane comprising an amino Substituent.
 US 8,343,238 B1
31 32
The at least one alkoxysilane comprising at least one solu bilizers, acidifying agents, mineral and organic thickeners,
bilizing functional group may be present in the composition antioxidants, hydroxy acids, penetrating agents, fragrances,
for dyeing and reducing curl and/or frizziness of hair from and preserving agents.
about 0.1% to about 10% by weight, preferably from about In the event that Surfactants are employed in the composi
0.25% to about 8% by weight, preferably from about 0.5% to tions of the present invention, said compositions may be used
about 5% by weight, based on the total weight of the compo as a shampoo. Similarly, in the event that one were to decide
sition for dyeing and reducing curl and/or friZZiness of hair. to use the compositions of the invention as a hair conditioner,
Cosmetically Acceptable Carrier various types of conditioning agents can be added to the
As used herein, the term "cosmetically acceptable carrier' composition in order to facilitate this hair treating property.
is known to one of ordinary skill in the art, and may comprise, 10
According to the present invention, there is provided a
for example, water and/or at least one organic solvent. process for altering the appearance of hair, that is, for dyeing
Cosmetically acceptable carriers useful according to vari and reducing the curl and/or frizziness of hair involving the
ous embodiments described herein may, by way of non-lim steps of: (a) providing a composition for dyeing and reducing
iting example, be chosen from water, organic solvents, natu
ral oils, synthetic oils, esters, hydrocarbons, silicones, and 15 curl and/or frizziness of hair, in a cosmetically acceptable
mixtures thereof. Non-limiting examples of cosmetically carrier, containing at least one non-hydroxide base, at least
acceptable carriers include alcohols, such as ethanol, isopro one protein denaturant, at least one oxidative dye precursor, at
pyl alcohol, benzyl alcohol and phenyl ethyl alcohol; glycols least one thickening agent, optionally, at least one alkoxysi
and glycol ethers, such as propylene glycol, hexylene glycol, lane comprising at least one solubilizing functional group;
ethylene glycol monomethyl, monoethyl or monobutyl ether, and optionally, at least one fatty Substance; (b) contacting the
propylene glycol and its ethers, such as propylene glycol hair with the composition for dyeing and reducing curland/or
monomethyl ether, butylene glycol, dipropylene glycol, and frizziness of hair to form treated hair; (c) smoothing the
also diethylene glycol alkyl ethers, such as diethylene glycol treated hair using a combination of heat and means for physi
monoethyl ether and monobutyl ether; hydrocarbons such as cally smoothing hair to form Smoothed hair; (d) optionally,
straight chain hydrocarbons, mineral oil, polybutene, hydro 25 shampooing the Smoothed hair; and (e) rinsing the treated
genated polyisobutene, hydrogenated polydecene, poly hair. The pH of the composition for dyeing and reducing curl
decene, squalene, petrolatum and isoparaffins; and mixtures and/or frizziness of hair is greater than 7 and the pH of the
thereof, to name a few. neutralizing composition is below 7.
The composition for dyeing and reducing curl and/or In commercially available hair straightening or relaxing
frizziness of hair disclosed herein may be, for example, in the 30
compositions, the highly caustic hydroxide compound Such
form of liquids or gels that allow the hair to “stick” together as sodium hydroxide must be used in order to satisfactorily
and hold them in a smooth position during the leave-in time. straighten/relax or reduce the curl of the hair without heat. In
The composition may also be in the form of a thickened cream the present invention, however, the less caustic and the lower
so as to hold the hair as stiff as possible. These creams are concentrations of the non-hydroxide compound can be used
made in the form of “heavy emulsions, particularly, when 35
the at least one fatty substance of the present disclosure is because of the synergy realized by using the composition for
present in the composition, for example, glyceryl Stearate, dyeing and reducing curl and/or frizziness of hair of the
glycol Stearate, self-emulsifying waxes, fatty alcohols, min present disclosure, in combination with heat and an apparatus
eral oil and petrolatum. capable of physically smoothing the hair. Without intending
The composition for dyeing and reducing curl and/or 40 to be bound by theory, it is believed that a synergistic effect in
frizziness of hair has a pH greater than 7, such as from about hair straightening/relaxing or curl reduction is realized due to
7.1 to about 13.5, or such as from about 7.1 to about 13, or an induced Supercontraction and denaturation of hair protein
such as from about 7.5 to about 13. caused by the combination of the disclosed composition for
In various exemplary embodiments, the composition for dyeing and reducing curl and/or frizziness of hair with the
dyeing and reducing curl and/or friZZiness of hair is a ready-to 45 heat and physical Smoothing.
use composition formed by combining, in a cosmetically Moreover, due to the less caustic and the lower concentra
acceptable carrier, an alkaline composition comprising the at tions of the non-hydroxide compound being used, a barrier
least one non-hydroxide base, the at least one protein dena Substance is not required when using the composition for
turant and the at least one thickening agent, with a dye com dyeing and reducing curl and/or frizziness of hair of the
position comprising at least one oxidative dye precursor and 50
present invention. Commercially available hair straightening/
optionally, the at least one thickening agent. The alkaline relaxing products oftentimes require the hair stylist to apply a
composition and the dye composition can each optionally barrier Substance Such as petrolatum to the skin Surrounding
contain the at least one fatty Substance and/or the at least one the scalp and the area around the ears. The barrier substance
alkoxysilane comprising at least one solubilizing functional is used to prevent the skin from becoming irritated if the
group. The alkaline composition has a pH greater than 7. 55
Adjuvants composition contacts the skin and from staining the skin as a
The composition for dyeing and reducing curl and/or result of the dyes in the composition. Thus, a barrier sub
frizziness of hair and the neutralizing composition as dis stance is not necessary when using the process of the present
closed herein may also each comprise at least one adjuvant invention because the concentration and the irritation of the
chosen, for example, from silicones in soluble, dispersed and 60 non-hydroxide compound is much lower.
microdispersed forms, nonionic, anionic, cationic and In preferred embodiments of the present disclosure, the
amphoteric Surfactants, Suspending agents, ceramides, gly composition for dyeing and reducing curl and/or frizziness of
coceramides and pseudoceramides, vitamins and provitamins hair comprises, in a cosmetically acceptable carrier, at least
including panthenol, waxes other than ceramides, glycocera one non-hydroxide base, at least one protein denaturant, at
mides and pseudoceramides, water-soluble and liposoluble, 65 least one oxidative dye precursor, at least one thickening
silicone-based and non-silicone-based Sunscreens, nacreous agent, at least one alkoxysilane comprising at least one solu
agents and opacifiers, sequestering agents, plasticizers, Solu bilizing functional group, and at least one fatty Substance.
 US 8,343,238 B1
33 34
In other preferred embodiments, the composition for dye position for dyeing and reducing curland/or frizziness of hair,
ing and reducing curl and/or frizziness of hair comprises two the color of the treated hair is altered in situ.
protein denaturants, preferably chosen from urea and Oxidizing Agent
hydroxyethyl urea. The at least one oxidizing agent of the present disclosure
The contact time (processing time) of the composition for may be chosen from peroxides, persulfates, perborates, per
dyeing and reducing curl and/or frizziness of hair with the carbonates, peracids, bromates, their salts and mixtures
hair may be up to about 60 minutes, such as up to about 30 thereof. The at least one oxidizing agent may, optionally, be
minutes, such as up to about twenty minutes. The contact tiup water-soluble.
may also be up to about 10 minutes particularly when the Exemplary, non-limiting persulfates include potassium
process of the present disclosure is used as a maintenance 10
persulfate, Sodium persulfate, and ammonium persulfate. In
regimen, i.e., as a follow up procedure to maintain the curl various embodiments, exemplary oxidizing agents may be
pattern or further reduce the curl of the hair. chosen from Sodium perborate and Sodium percarbonate. In
The Smoothing step of the present disclosure, using a com further embodiments, exemplary peracids may be chosen
bination of heat and means for physically smoothing hair to from organic peracids having the general formula (VIII):
form smoothed hair, preferably includes the use of a flat iron 15
or a blow dryer in combination with a comb, a brush, or an
iron. The Smoothing step of the present invention is prefer
ably conducted at a temperature of at least 30°C.; preferably wherein,
at least 50° C.; preferably at least 70° C. The heat in the in formula (VIII), R is chosen from saturated or unsatur
Smoothing step may emanate from any suitable source Such ated, Substituted or unsubstituted, straight or branched chain,
as, for example, a hair dryer or blow dryer or hot/flat iron or alkyl, aryl or alkaryl groups having from 1 to carbonatoms. In
an infrared heat generator/hair dryer in one device (e.g., Roll at least some exemplary embodiments, mixtures of two or
erball brand). more oxidizing agents chosen from persulfates, perborates,
Typically, the lower the amount of non-hydroxide base percarbonates, peracids, perbromates, and salts thereof, may
present in the composition for reducing curl and/or frizziness 25 be chosen.
of hair, the lower the temperature required at the Smoothing In various embodiments, the at least one oxidizing agent is
step. Conversely, the amount of heat applied onto the treated chosen from alkali metal salts of perborates, percarbonates,
hair can depend on the original hair type and/or the degree of perbromates, and persulfates. Such as, for example, ammo
damage to the hair. nium, Sodium, and potassium salts.
The means for physically Smoothing hair can be any appa 30 Preferred persulfates are monopersulfates such as, for
ratus capable of physically Smoothing the hair Such as, for example, potassium persulfate, Sodium persulfate, ammo
example, a hairbrush or comb. In one embodiment, the means nium persulfate, as well as mixtures thereof.
for Smoothing hair also serves as the Source for generating The preferred oxidizing agents in the present invention are
heat Such as, for example, a hot/flat iron. potassium persulfate, sodium persulfate and mixtures
In other embodiments of the present disclosure, the treated 35 thereof.
hair is contacted with a non-volatile oil before before or after Optional peroxides useful herein include, for example,
the Smoothing step. The non-volatile oil may be chosen from hydrogen peroxide, magnesium peroxide, PVP-peroxide,
plant, animal, mineral and synthetic oils. calcium peroxide, and Sodium peroxide.
The smoothed hair may also be contacted with the neutral The at least one oxidizing agent is present in an amount
izing composition of the present disclosure and having a pH 40 Sufficient to generate color in the hair without destroying the
of below about 7 to form neutralized hair, followed by rinsing oxidative dye precursors which have migrated into the hair
with water. The neutralizing composition may be in the form prior to completion of the hair dyeing process to the desired
of a shampoo or a conditioner. colorf shade.
In some embodiments of the present disclosure, the com Preferably, the at least one oxidizing agent is provided in
position for dyeing and reducing curl and/or frizziness of hair 45 the neutralizing composition comprising a cosmetically
may be rinsed out from the hair before contacting the treated acceptable carrier as described above.
hair with the neutralizing composition. In general, the at least one oxidizing agent will be present
Neutralizing Composition in the neutralizing composition of the present disclosure in an
A neutralizing composition may also be applied onto the amount of at least 1% by weight, based on the total weight of
hair after it has been Smoothened using a combination of heat 50 the neutralizing composition.
and means for physically smoothing hair. The neutralizing According to a preferred embodiment, the at least one
composition can comprise a cosmetically acceptable carrier oxidizing agent is present in the neutralizing composition of
chosen from water, organic solvents, and mixtures thereof. the present disclosure in an amount ranging from about 1% by
Suitable examples of cosmetically acceptable carriers include weight to about 80% by weight, preferably from about 5% by
those described above. 55 weight to about 75% by weight, based on the total weight of
The cosmetically acceptable carrier may, for example, be the neutralizing composition.
present in the neutralizing composition of the present disclo The pH of the neutralizing composition can be from about
sure in an amount ranging from about 0.5% to about 85% by 1 to about 6.5, such as from about 2 to about 6, or such as from
weight, such as from about 2% to about 80% by weight, about 2 to about 5, or such as at about 3, or at about 4, or at
preferably from about 5 to about 70% by weight, based on the 60 about 4.8, or at about 5, and it may be adjusted to the desired
total weight of the neutralizing composition. value using pH adjusting agents that are well known in the art
The neutralizing composition preferably comprises at least in the dyeing of keratin fibers.
one oxidizing agent. According to a preferred embodiment of the invention, the
The neutralizing composition may also comprise one or neutralizing composition is Substantially anhydrous.
more of the adjuvants listed above. 65 The term “substantially anhydrous' means that the neutral
When the neutralizing composition comprising at least one izing composition is either completely free of water or con
oxidizing agent is applied onto the hair treated with the com tains no appreciable amount of water, preferably no more than
 US 8,343,238 B1
35 36
1% by weight, and more preferably no more than 0.5% by sition containing at least one Surfactant, such as a shampoo,
weight, based on the weight of the neutralizing composition. with a oxidizer composition containing at least one oxidizing
According to a particularly preferred embodiment of the agent. Preferably, the oxidizer composition containing the at
invention, the neutralizing composition is totally anhydrous, least one oxidizing agent is an anhydrous composition.
that is to say it does not contain water at all. In one embodiment of the present disclosure, an anhydrous
When the neutralizing composition is Substantially anhy oxidizer composition and a shampoo composition are pro
drous or totally anhydrous, the cosmetically acceptable car vided and are combined immediately prior to use, to form the
rier is chosen from organic solvents. neutralizing composition wherein the oxidizer composition
10
The neutralizing composition of the present disclosure contains at least one oxidizing agent chosen from persulfates,
may also contain at least one fatty Substance and/or at least perborates, percarbonates, bromates, peroxides, their salts,
one thickening agent as described above. and mixtures thereof and the shampoo composition contains
In some embodiments of the present disclosure, the neu a cosmetically acceptable carrier and at least 4% by weight,
tralizing composition will additionally contain an oxidizing 15
agent chosen from peroxides and its salts. Peroxides useful based on the total weight of the shampoo composition, of at
herein include, for example, hydrogen peroxide, magnesium least one surfactant chosen from anionic, amphoteric, non
peroxide, PVP-peroxide, calcium peroxide, and sodium per ionic, Zwitterionic, cationic Surfactants, and mixtures thereof.
oxide. The resulting neutralizing composition contains from about
The neutralizing composition may be in the form of a 1% to about 80% by weight of the oxidizing agent, based on
powder, gel, liquid, foam, lotion, cream, mousse, and emul the total weight of the neutralizing composition. Optionally,
Sion.
It should be noted that the use of a catalyst during the the hair may also first be contacted with a pre-alkalizing
oxidation of the oxidative dye precursor Such as, for example, composition having a pH of from about 8.0 to about 12.0 to
25
cupric or ferrous salt, is not necessary in order to achieve a form pre-alkalized hair prior to application of the dyeing and
desired colorf shade. curl/frizziness reducing composition. This pre-alkalizing
Thus, according to a preferred embodiment of the present step renders the process for reducing the curland/or friZZiness
disclosure, the composition for dyeing and reducing curl of hair more efficient and less time-consuming.
and/or frizziness of hair and the neutralizing composition of 30
the present disclosure are substantially free of an oxidation The pre-alkalizing step comprises contacting the hair with
catalyst, i.e., Such catalyst is present in a less than catalyti a pre-alkalizing composition which may be provided in any
cally effective amount in the hair treatment and neutralizing suitable form. Examples thereof include, but are not limited
compositions.
35 to, a shampoo, a conditioner oran alkaline Solution in general.
As used herein, “oxidation catalyst” refers to transition In a particularly preferred embodiment, the alkaline compo
metal cations that can aid in the oxidation of certain dye
precursors, such as cupric and ferrous ions. sition is in the form of a shampoo which would facilitate both
According to a particularly preferred embodiment, the the pre-alkalizing and cleaning of the hair at the same time.
composition for dyeing and reducing curl and/or frizziness of 40 Thus, in one embodiment of the present invention, there is
hair and the neutralizing composition are each totally free of provided a process for dyeing and reducing curl and/or friZZi
cupric ions and of ferrous ions. ness of hair that includes first pre-alkalizing or treating the
According to a particularly preferred embodiment, the hair with the alkaline composition before contacting the hair
composition for dyeing and reducing curl and/or frizziness of
hair and the neutralizing composition do not contain hydro 45
with the dyeing and curl/frizziness reducing composition to
gen peroxide. form treated hair. Preferably, the alkaline composition is
According to some embodiments, when the oxidative dye rinsed from the hair and the hair is dried, blown dry, prior to
precursor employed in the composition for dyeing and reduc contacting the hair with the dyeing and curl/frizziness reduc
ing curl and/or frizziness of hair is an auto-oxidizable com ing composition.
pound, i.e., the color development occurs in the presence of 50
The pH of the pre-alkalizing composition can range from
air, the neutralizing composition may not require an oxidizing above 7 to about 12, such as from about 7.5 to 12, or such as
agent as described above. from about 7.5 to about 10 or such as from about 8 to about 12
According to other embodiments, the composition for dye or such as from about 8 to about 10.
ing and reducing curl and/or frizziness of hair and/or neutral 55 Due to the less caustic and the lower concentrations of the
izing composition do not contain more than about 2.5% by non-hydroxide compound being used, a barrier Substance is
weight of aqueous ammonia based on the total weight of the not required when using the composition for dyeing and
composition for dyeing and reducing curl and/or frizziness of reducing curl and/or frizziness of hair. Commercially avail
hair and/or neutralizing composition.
able hair relaxing products oftentimes require the hair stylist
The neutralizing composition is applied onto the hair for a 60 to apply a barrier Substance Such as petrolatum to the skin
period of time sufficient to neutralize the pH on the hair and/or Surrounding the Scalp and the area around the ears. The barrier
develop color, in situ, to form colored hair. In general, the Substance is used to prevent the skin from becoming irritated
neutralizing composition is applied onto the hair for a period if the hair relaxing product contacts the skin. Thus, a barrier
of from 1 to t 20 minutes, such as from 1 to 10 minutes, for Substance is not necessary when using the process of the
example from 1 to 5 minutes. 65 present invention because the concentration and therefore,
In various exemplary embodiments, the neutralizing com the degree of irritation of the non-hydroxide compound, are
position is formed by combining a surfactant-based compo much lower.
 US 8,343,238 B1
37 38
The present invention will be better understood from the The Swatches were then washed and dried. The permed hair
examples which follow, all of which are intended for illustra was used as a control to validate that the hair fibers were
tive purposes only, and are not meant to unduly limit the scope colored according to the desired shade.
of the invention in any way. Natural wavy hair as used herein refers to curly hair (curl
type III) whose degree of curl is in between straight hair and
EXAMPLES kinky hair which has very tight curls (curl type V).
It was found that the process above dyed the Swatches with
Example 1 the desired color/shade and significantly reduced the curl on
the natural wavy hair.
10
Dyeing and Curl Reduction with the Inventive Hair Example 2
Treatment Formula (Clear Gel Composition)
Retention of Color and Retention of Curl Reduction
Study
15
test formula The color fading and curl reducing properties of the com
ngredient % by weight position in Example 1 were studied on three different types of
SODIUMSULFITE 0.4
hair: permed, African American (kinky hair with very tight
ASCORBIC ACID O.3 curls), and natural wavy hair. The Swatches were treated
DISODIUM EDTA O.1 according to the procedure above. The permed hair was used
XANTHAN GUM 2 as a control to validate that the hair fibers were colored
MONOETHANOLAMINE 1
PENTASODIUMPENTETATE 2 according to the desired shade. It was found that the curl on
SODIUMMETASILICATE 2 the African American hair was significantly reduced and the
CETEARYLALCOHOL (and) 3 natural wavy hair was straightened.
DIPALMITOYLETHYL
HYDROXYETHYLMONIUMMETHOSULFATE
25 Each Swatch was then subjected to 5 cycles of shampooing,
COCO-GLUCOSIDE 2
with each cycle involving treating each Swatch with 5 grams
RESORCINOL O6 of shampoo and rinsing with water.
-PHENYLENEDLAMINE O.S8 After the five cycles of shampooing and rinsing, it was
UREA 10 found that the color on the swatches did not fade and in fact
HYDROXYETHYLUREA 2
WATE Q.S.
30 appeared darker (probably due to a continued color develop
ment). In addition, the curl on the African American hair was
Surfactant-based composition (shampoo) still significantly reduced or loosened, and the wavy hair
Ingredient % by weight
remained straight.
SODIUMLAURETHSULFATE 13.85 35 Example 3
DISODIUM COCOAMPHODLACETATE 10
AMMONIUM HYDROXIDE 3.2 Lift Study
TARTARICACID O.1
CITRICACID 4
FRAGRANCE O.3 The level of lightening (lift) of the color of hair was studied
POLYQUATERNIUM-10 O.8 40 on Swatches of four different types of hair: permed,
SALICYLIC ACID O45 unpermed, Asian hair (natural dark color) and natural wavy
BENZOIC ACID O45 hair (medium brown shade) using three inventive composi
HEXYLENE GLYCOL 1
ETHYLEHEXYLMETHOXYCINNAMATE O.OS tion for dyeing and reducing curl and/or frizziness of hairs
PEG-60 HYDROGENATED CASTOR OIL O.S and a control formula. The Swatches were treated according
TOCOPHERYLACETATE O.OS 45 to the procedure in Example 1.
WATER Q.S.
Oxidizing composition
Ingredient % by weight Test Test Test
formula. A formula B formula C
50 % by % by % by
SODIUMPERSULFATE 75
EDTA 1 Ingredients weight weight weight
SILICA 2.3
SODIUMSULFITE 0.4 0.4 0.4
ZEA MAYS (CORN) STARCH 2O ASCORBIC ACID O.3 O.3 O.3
HYDROGENATED POLYDECENE 1.7
DISODIUM EDTA O.1 O.1 O.1
55 XANTHAN GUM 2 2 2
MONOETHANOLAMINE 1 1 1
Two hair swatches, each a different type of hair permed, PENTASODIUMPENTETATE 2 2 2
and natural wavy (loose curls) were treated according to the SODIUMMETASILICATE 2
following procedure: ARGININE 5
Thirty (30) grams of the composition above was applied to SODIUM HYDROXIDE 2.1
each hair Swatch. The composition was left on the Swatches 60 CETEARYLALCOHOL (and) 3 3 3
DIPALMITOYLETHYL
for 50 minutes, after which heat (using a flat iron) was applied HYDROXYETHYLMONIUM
to the treated hair to straighten/reduce the curl of the hair. The METHOSULFATE
Swatches were then treated with a neutralizing composition COCO-GLUCOSIDE
UREA
2
10
2
10
2
10
formed by combining the shampoo composition and the oxi HYDROXYETHYLUREA 2 2 2
dizing composition (92%:8% by weight). The pH of the neu 65 WATE Q.S. Q.S. Q.S.
tralizing composition was at about 4.8. The neutralizing com
position was allowed to remain on the Swatches for 5 minutes.
 US 8,343,238 B1
39 40
The test formulas lifted the color of the natural wavy hair The hair was treated according to the procedure in Example 1.
by one level as compared to 3 levels of lift caused by a
standard permanent oxidative dye formula containing 7.41%
ammonium hydroxide (aqueous ammonia) in the same type Test formula G
of hair. On the other hand, the test formulas did not noticeably Ingredients % by weight
lift the color of the Asian hair while 2 levels of lift were
WATER Q.S.
observed using the standard dye formula. The standard dye XANTHAN GUM 2
formula was able to lift color to a higher level in the same type TRIETHANOLAMINE O.2
of hair because it contained 18% sodium hydroxide, whereas ETHANOLAMINE
10 HEXYLENE GLYCOL
1
2
the test formulas contained no or very little amount of sodium UREA 10
hydroxide (not more than about 2.1% by weight). HYDROXYETHYLUREA 5
Significant reductions in curl were observed for the African AMINOPROPYL TRIETHOXYSILANE (APTES) 1
DISODIUM EDTA O.2
American and the natural wavy hair treated with the test ASCORBIC ACID O.3
formulas. It was also observed that the various hair types 15 SODIUMSULFITE 0.4
treated with test formula C, which contained arginine, felt n-AMINOPEHENOL O.25
more conditioned to the touch as compared to the hair treated 1-HYDROXYETHYL 4,5-DIAMINO PYRAZOLE
SULFATE (provides the red color)
O.S
with the other test formulas and with the control formula.

Example 4 With respect to conditioning, it was observed that the hair

treated with the test formula G containing APTES imparted
Study on Thickening Agents more conditioning to the hair compared to test formula F in
Example 4 which did not contain APTES.
The effect of the presence of thickening agents was tested In addition, it was observed that the hair was effectively
as shown below. 25 colored a red color.
Example 6
Test Test Test
formula D formula E formula F
Curl Reduction/Straightening Study, Color
ngredients % by weight % by weight % by weight Deposition Study and Rinsing Study Involving an
Additional Rinsing Step Before the Application of
WATER
TRIETHANOLAMINE
Q.S.
O.1
Q.S.
O.2
Q.S.
O.2
the Neutralizing Composition onto the Hair
ETHANOLAMINE 1 1 1
HEXYLENE GLYCOL 2 2 2 The inventive formulas below were tested against a stan
UREA 10 10 10 35 dard permanent oxidative dye formulas (standard dye formu
HYDROXYETHYLUREA
DISODIUM EDTA
5
O.2
5
O.2
5
O.2
las) containing high amounts of ammonium hydroxide (aque
ASCORBIC ACID O.3 O.3 O.3 ous ammonia) on Swatches of two types of hair: permed and
SODIUMSULFITE 0.4 0.4 0.4 natural wavy hair. For the tests, 2 grams of product per gram
-PHENYLENEDLAMINE O.S4 O.S4 O.S4 of hair were used. The swatches were treated with the test
b-AMINOPEHENOL O.62 O.62 O.62
(and) SODIUM
40 formulas for 20 minutes then heat was applied to the Swatches
METABISULFITE (4 passes with the flat iron).
2-METHYL-5- O.8 O.8 O.8 In order to investigate the effects of rinsing the hair with
HYDROXYETHYLAMINOP water before and after applying the neutralizing composition,
HENOL one of the Swatches was rinsed before and another was rinsed
4-AMINO-2- O.86 O.86 O.86
HYDROXYTOLUENE
45 after the application. The neutralizing composition was left
6-HYDROXYINDOLE O.O6 O.O6 O.O6 on the hair for 2 minutes for test formulas H and I, and 5
CARBOMER O.2 minutes for test formulas J and K. The swatches were then
(THICKENINGAGENT)
XANTHAN GUM 2
hung to dry.
(THICKENINGAGENT) 50

It was observed that the dyes in test formula D which did Test
Test
formula
not contain a thickening agent precipitated to the bottom for Test Test formula J K
lack of viscosity and solubility in the base while the gel formula H formula I Brown Brown
structure intest formula E which contained a thickening agent 55 Red shade Red shade shade shade
comprising a charged compound, carbomer, fell apart as soon % By % By % By % By
Ingredients weight weight weight weight
as the dyes were added to the gel. On the other hand, the gel
structure of test Formula F, which contained Xanthan gum, a WATER
XANTHAN GUM 2
QS QS
2
QS
2
QS
2
nonionic thickening agent, remained stable when the dyes TRIETHANOLAMINE O.2 O.2 O.2 O.2
were added. 60 MONOETHANOLAMINE
1 1 1 1
HEXYLENE GLYCOL 2 2 2 2
Example 5 UREA 10 10 10 10
AMINOPROPYL 1 1
TRIETHOXYSILANE
Study on Red Shades DISODIUM EDTA O.2 O.2 O.2 O.2
65 ASCORBIC ACID O.3 O.3 O.3 O.3
The next test was to study the effect of APTES and to SODIUMSULFITE 0.4 0.4 0.4 0.4
determine whether hair can be effectively colored a red shade.
 US 8,343,238 B1
41
-continued -continued
Test AE
Test formula (difference
between treated
Test Test formula J K Treatment of and untreated
formula H formula I Brown Brown hair L* a: b: hair)
Red shade Red shade shade shade
Neutralization
% By % By % By % By Test formula I 33.53 22.34 2.1 37.42
Ingredients weight weight weight weight withoutrinsing
10 before
n-AMINOPEHENOL O.25 O.25 O.6 O.6 Neutralization
1-HYDROXYETHYL O.S O.S
contained oxidative dyes ammonium thiolactate, pentasodim pentetate, propylene glycol,
4,5-DIAMINO glycol distearate, fatty alcohols, fatty acid, cationic agents, silica dimethylsilylate, thick
PYRAZOLE SULFATE ening agent, nonionic surfactants, 1.15% by weight monoethanolamine, 18% by weight
aqueous ammonia and water
1,4-DIAMINO- O.S8 O.S8 15
BENZENE The a values among the hair swatches treated with the
standard hair color for red shade and the test formulas Hand
I were comparable and were significantly greater than the a
value for the untreated Swatch. This indicates that the test
Example 6a formulas were able to effect a color change on the hair. In
addition, the hair treated with the test formulas demonstrated
significant overall color changes, AE, between the untreated
Color Deposition Study for Red Shades and Rinsing and the treated hair. Although the hair treated with the stan
Step Study Involving an Additional Rinsing Step dard hair color exhibited a higher color change, this could be
Before the Application of the Neutralizing 25 attributed to the presence of 18% ammonium hydroxide
Composition onto the Hair (aqueous ammonia) in the formula. These results indicate
good color deposit using the test formulas and that the hair
The color of the hair swatches treated with test formulas H swatches were effectively dyed a red shade even without the
and I and hair swatches treated with a standard dye formula presence of aqueous ammonia. These results were also visu
30
for red shades containing 18% ammonium hydroxide (aque ally observed.
ous ammonia) was measured using a Minolta CM2002 colo As for the effect of rinsing, the comparable overall color
rimeter in the L*a*b* system. In the L*a*b* system, the 3 changes or differences between the hair treated with the test
parameters denote, respectively, the intensity or lightness of formulas and the untreated hair indicate that the additional
the color (L*), the value of the color on a green/red axis (a) step of rinsing before applying the neutralizing composition
35
and the value of the color on a blue/yellow axis (b). Accord onto the smoothed hair did not affect the degree of color
ing to this system, the greater the value of L, the lighter or less deposit on the hair treated with the test formulas. These
intense the color. Conversely, the lower the value of L, the results were also visually observed. Therefore, the hair may
darker or more intense the color. Also, according to this be rinsed before applying the neutralizing composition with
system, the overall color change, AE, can be calculated from 40
out compromising the color development on the hair.
the AL, AA, and AB values. The hair used as a control was In addition, the swatches treated with the formulas contain
90% grey permed hair. ing the alkoxysilane felt more conditioned to the touch.
Colorimetric Results Example 6b
45 Color Deposition Study for Brown Shades and
Rinsing Step Study (Rinsing Employed Before
AE Application of the Neutralizing Composition Versus
(difference after Application of the Neutralizing Composition
between treated
Treatment of and untreated
hair L* b: hair) 50 A colorimetric study comparing test formulas J and K
No treatment- 62.3 1.16 13.24 above with a standard permanent oxidative dye formula (stan
untreated dard dye formula) for brown shade containing 10% ammo
Swatch; 90% nium hydroxide (aqueous ammonia). The colorimetric mea
permed gray hair Surements were made as described above.
(control) 55 Colorimetric Results
standard dye 22.55 2O 9.5 44.15
ormula for red
shade
Test formula H 41.45 16.13 3.52 27.45
with rinsing AE
before (treated versus
60
Neutralization Treatment L* b* untreated hair)
Test formula H 32.62 20.69 1.85 37.31
withoutrinsing untreated Swatch; 62.3 1.16 13.24
before 90% permed gray
Neutralization hair (control)
Test formula I 37.17 19.33 2.18 32.92 standard dye 32.19 2.99 9.88 30.35
with rinsing 65 formula for brown
before shade
 US 8,343,238 B1
43 44
-continued type. Two hair Swatches were assigned as test Swatches and
one Swatch was assigned as a control (no treatment).
AE
(treated versus Step 1: The test and control hair swatches were cleansed
Treatment L* a: b* untreated hair)
5
with a shampoo (0.52grams shampoo per Swatch) and simul
Test formula J 2O.S4 3.36 2.47 43.18 taneously washed with tap water for 2 minutes at 30° C. and
with rinsing combed in order to detangle the hair. The test hair swatches
before
Neutralization
were then blow dried and pulled straight at the same time.
Test formula J 20.1 1.57 2.46 43.56 Step 2: Each test hair swatch was treated with about 4
withoutrinsing 10 grams of the invention's composition for dyeing and reducing
before
Neutralization curl and/or frizziness of hair (inventive formula K in example
Test formula K 20.58 2.72 1.78 43.29 6 above). The composition was combed through the hair and
with rinsing allowed to remain on the test hair Swatches for about 20
before minutes at 45° C. Each treated test hair Swatch was then
Neutralization 15
Test formula K 18 1.74 1.29 45.89 Smoothened by passing a titanium flat iron 3 times through
withoutrinsing each Swatch, 5 seconds per pass, at 370°F.
before
Neutralization Step 3—Each test Swatch was treated with about 1.3 grams
of the invention's neutralizing composition (1:1 ratio of neu
contained oxidative dyes, ammonium thiolactate, sodium sulfiteimetabisulfite, silica dim tralizing composition to weight of hair Swatch) by combing it
ethylsilylate, propylene glycol, glycerin, fatty alcohols, fatty acids, alkoxylated fatty amine,
thickening agents, cationic agents, chelants, amphoteric surfactants, 6% by weight steara
mide and monoethanolamine, 1.21% by weightmonoethanolamine, 10% by weightaqueous through the hair. The neutralizing composition was allowed to
ammonia and water remain on the hair for about 5 minutes.
The L values (more representative parameter for the brown The test and control hair swatches were then cleansed with
shade to determine adequate color deposit) among the hair a shampoo (0.52 grams shampoo per Swatch) and simulta
swatches treated with the standard dye formula and the test 25
neously washed with tap water for 2 minutes at 30° C. and
formulas J and K were comparable and were lighter than the combed in order to detangle the hair. The swatches were
L value for the untreated swatch. This indicates that the test combed 3 times before hanging to airdry. After drying, digital
formulas were able to effect a color change on the hair. In photographs of the test and control hair Swatches were taken
addition, the hair treated with the test formulas demonstrated against a ruler in order to compare the length and width of the
significant overall color changes, AE, between the untreated 30
Swatches with the control swatch.
and the treated hair while the hair treated with the standard
dye formula, which contained 10% ammonium hydroxide, In order to determine the durability of the curl and/or frizz
exhibited less color change. These results indicate good color reduction effect and the artificial color on the hair, one test
deposit using the test formulas and that the hair Swatches were hair Swatch and one control Swatch were each shampooed/
effectively dyed a brown shade even without the presence of 35 washed/combed for 10 cycles, with hanging to air dry in
aqueous ammonia. These results were also visually observed. between each cycle. Digital photographs of the Swatches
As for the effect of rinsing, the comparable overall color were taken every 2 cycles.
changes even with the rinsing step before applying the neu
tralizing composition indicate that this additional step does The photographs of the hair swatches showed that the test
not affect the degree of color deposit on the hair treated with 40
hair Swatches appeared longer and significantly more straight
the test formulas. These results were also visually observed. than the control Swatch. In addition, the test hair swatches
Therefore, the hair may also be rinsed before applying the were significantly less frizzy as seen from the smaller width
neutralizing composition without compromising the color of the test hair swatch as compared to the width of the control
development on the hair. Swatch.
Study on curl and frizziness reduction using test formula K 45
on the natural wavy hair according to the procedure in Example 8
Example 1
Anti-Frizz Study
Width at Width at Width at Width at 50
Length Length 7 cm: * 7 cm:8: 10 cm3 * 10 cm3*
before after before after before after
treatinent treatinent treatinent treatinent treatinent treatinent
Width of
14.5 16.25 3 2.5 5.5 3.5 Swatch at Width at
55 midpoint of the end of
Width was measured across the swatch to determine reduction infrizz or volume of the hair Length of length of the Swatch,
**measured at the specified distance from the root end Treatment Swatch, cm Swatch, cm Cl
Untreated natural 16 3.1 6.8
The results in the table above show that the natural wavy wavy hair
hair was longer and the frizz or volume of the hair was Hair treated with 17 2.1 4.4
reduced after the hair was treated with the test formula. 60 test formula K

Example 7
The measurements above of the length of the hair swatches
Curl Reduction and Frizz Control Study show that the Swatch treated with the test formula was longer
65 compared to the untreated hair which indicates that the hair
Hair Swatches: Bleached hair swatches (~1.3 g of hairper was straightened. In addition, the width of the treated
swatch) were prepared from samples of Natural wavy hair Swatches at midpoint and at the ends are less than that of the
 US 8,343,238 B1
45 46
untreated swatch which indicates that the treated hair was less It is to be understood that the foregoing describes preferred
frizzy or spread out compared to the untreated hair. embodiments of the invention and that modifications may be
made therein without departing from the spirit or scope of the
Example 9 invention as set forth in the claims.
Test Formula Containing a Fatty Substance (Mineral What is claimed is:
Oil) 1. A process for altering the appearance of hair, the process
comprising:
(a) providing a composition for dyeing and reducing curl
10 and/or frizziness of hair, said comprising, in a cosmeti
INCIUS 87928 MX cally acceptable carrier:
(i) at least one non-hydroxide base;
UREA 10
DISODIUM EDTA O.2
(ii) at least one protein denaturant different from (a)(i);
MONOETHANOLAMINE 4.4 (iii) at least one oxidative dye precursor,
SODIUMSULFITE 0.4 15 (iv) at least one thickening agent;
HYDROXYETHYLUREA 5 (v) optionally, at least one alkoxysilane comprising at
n-AMINOPEHENOL
1-HYDROXYETHYL 4,5-DLAMINO
O.25 least one solubilizing functional group; and
PYRAZOLE SULFATE O.S (vi) optionally, at least one fatty Substance;
MINERAL OIL 60 (b) contacting the hair with the composition in (a) to form
CETEARYLALCOHOL 2.5 treated hair;
CARBOMER 0.4 (c) Smoothing the treated hair using a combination of heat
AMINOPROPYLTRIETHOXYSILANE 1
WATER 11.05 and means for physically smoothing hair to form
SODIUM CETEARYL SULFATE 2 Smoothed hair;
STEARETH-2O 2 (d) optionally, shampooing the Smoothed hair; and
ASCORBIC ACID O.3 25 (e) rinsing the treated hair.
2. The process of claim 1, wherein the composition for
dyeing and reducing curl and/or frizziness of hair is a ready
Example 10 to-use composition.
3. The process of claim 1, wherein (a)(i) is chosen from an
Study on Retention of Curl Reduction and 30 alkylamine, alkyleneamine, alkanolamine, aminomethylpro
Frizz/Volume Reduction or Control on Natural Wavy panol, basic amino acids and mixtures thereof.
Hair and Retention of Color on Permed Hair after 4. The process of claim 1, wherein (a)(i) is chosen from
Multiple Washings ethylenediamine, monoethanolamine, triethanolamine, and
mixtures thereof.
35 5. The process of claim 1, wherein (a)(i) is chosen from
arginine, lysine, histidine and mixtures thereof.
Length before treatment, cm 13 6. The process of claim 1, wherein (a)(i) is chosen from an
Length after 10 washes, cm 14 alkali metal phosphate, an alkali metal carbonate, and mix
Length after 20 washes, cm 15.5 tures thereof.
Width at 7 cm before treatment 2.5
Width at 7 cm after 10 washes 2
40 7. The process of claim 1, wherein (a)(i) is employed in an
Width at 7 cm after 20 washes 2.5 amount of from about 0.1% to about 50% by weight, based on
Width at 10 cm * before 4 the weight of the composition in (a).
treatinent
Width at 10 cm after 10 washes 2
8. The process of claim 1, wherein (a)(i) is employed in an
Width at 10 cm after 20 washes 3.5 amount of from about 1% to about 5% by weight, based on the
45 weight of the composition in (a).
Width was measured across the swatch to determine reduction infrizz or volume of the hair 9. The process of claim 1, wherein (a)(ii) is chosen from
**measured at the specified distance from the root end urea, guanidine, urea derivatives and/or salts, guanidine
Natural wavy hair and permed hair were treated with the derivatives and/or salts, and mixtures thereof.
test formula Kaccording to the procedure in Example 1. The 10. The process of claim 1, wherein (a)(ii) is chosen from
hair was then Subjected to 20 shampoo/rinse cycles (washes) urea, hydroxyethyl urea and mixtures thereof.
50

which corresponds to a period of about 4 to about 6 weeks that 11. The process of claim 1, wherein (a)(ii) is employed in
a consumer would wait until the next coloration/hair treat an amount of from about 0.1% to about 50% by weight, based
ment. on the weight of the composition in (a).
The length and width measurements in the table above 12. The process of claim 1, wherein (a)(ii) is employed in
show that treatment on the natural wavy hair provided excel 55 an amount of from about 2% to about 20% by weight, based
lent retention of curl reduction (the hair did not revert to its on the weight of the composition in (a).
original curl length) and good frizz/volume control even after 13. The process of claim 1, wherein (a)(ii) is chosen from
the 10" and 20" washes. At the 10" wash, the widths along urea, hydroxyethyl urea and mixtures thereof.
the length of the swatch were still less than the widths before 14. The process of claim 1, wherein (a)(ii) comprises at
the treatment. At the 20" wash, the widths along the length of 60 least two protein denaturants present in a ratio by weight
the Swatch were comparable to or less than the widths before ranging from about 10:1 to about 1:10.
the treatment. This indicates long lasting retention of curl 15. The process of claim 1, wherein (a)(iii) is chosen from
reduction and frizz/volume control even after multiple wash oxidation bases and couplers, and mixtures thereof.
ing cycles. 16. The process of claim 1, wherein (a)(iii) is chosen from
From a visual assessment of the color of the permed hair, it 65 ortho- and para-phenylenediamine oxidation bases, double
was observed that the treatment resulted in excellent color bases, ortho- and para-aminophenols, heterocyclic bases, as
retention even after the 10" and 20" wash cycles. well as salts of addition of these compounds with an acid and
 US 8,343,238 B1
47 48
meta-aminophenol, meta-phenylenediamine, meta-diphenol, 36. The process of claim 30, wherein the neutralizing com
naphthol couplers, heterocyclic couplers and acid salts position comprises, in a cosmetically acceptable carrier, at
thereof. least one surfactant chosen from anionic, amphoteric, non
17. The process of claim 1, wherein (a)(iv) is chosen from ionic and cationic Surfactants.
gums, waxes, silica gels, polysaccharides, clays, silicas, fatty 37. The process of claim 30, wherein the pH of the neu
acid soaps, fatty acid alkanolamides, poly(acrylic acid)S. tralizing composition is from about 1 to about 6.
esters of polyethylene glycol, crosslinked copolymers of 38. The process of claim 30, wherein the smoothed hair is
acrylamide and of a monomer selected from the group con rinsed prior to contacting the Smoothed hair with the neutral
sisting of ammonium acrylate, 2-acrylamido-2-methylpro izing composition.
panesulfonic acid and methacryloyloxyethyltrimethy 10 39. The process of claim 1, wherein the composition in (a)
lammonium chloride, polyurethanes, and crosslinked methyl is Substantially free of formaldehyde-generating compounds.
vinyl ether-maleic acid copolymers. 40. The process of claim 1, wherein the composition in (a)
18. The process of claim 1, wherein (a)(iv) is chosen from does not contain more than about 2.5% by weight of aqueous
Xanthan gum and guar gum. ammonia based on the total weight of the composition in (a).
19. The process of claim 1, wherein (a)(iv) is present in an 15 41. The process of claim 1, wherein the composition in (a)
amount of from about 1% to about 10% by weight, based on comprises an alkaline composition containing, in a cosmeti
the weight of the composition in (a). cally acceptable carrier, at least one non-hydroxide base and
20. The process of claim 1, wherein (a)(v) is 3-aminopro at least one protein denaturant different from the at least one
pyltriethoxysilane. non-hydroxide base.
21. The process of claim 1, wherein (a)(v) is employed in 42. The process of claim 1, wherein the composition in (a)
an amount of from about 1% to about 10% by weight, based comprises a dye composition containing, in a cosmetically
on the weight of the composition in (a). acceptable carrier, at least one oxidative dye precursor.
22. The process of claim 1, wherein (a)(vi) is chosen from 43. A kit for dyeing and reducing the curl and/or frizziness
lower alkanes, fatty alcohols, fatty acids, esters offatty acids, of hair, the kit comprising:
esters of fatty alcohol, non-silicone oils, non-silicone waxes 25 1) a first unit containing, in a cosmetically acceptable car
and silicones. rier:
23. The process of claim 1, wherein (a)(vi) is present in an (a) at least one non-hydroxide base;
amount of at least about 10% by weight, based on the weight (b) at least one protein denaturant different from (a):
of the composition in (a). (c) at least one dye chosen from oxidative dye precur
24. The process of claim 1, wherein the composition in (a) 30 sors; and
further comprises at least one direct dye. (d) at least one thickening agent;
25. The process of claim 1, wherein (b) is performed for (e) optionally, at least one alkoxysilane comprising at
less than about 60 minutes. least one solubilizing functional group; and
26. The process of claim 1, wherein the means for physi (f) optionally, at least one fatty Substance; and
cally Smoothing hair in (c) is chosen from a brush, a comb, 35 2) a second unit containing:
and an iron. (a) at least one oxidizing agent chosen from persulfates,
27. The process of claim 1, wherein (c) is performed using perborates, percarbonates, peroxyacids, bromates,
a hot/flat iron at a temperature of at least about 70° C. peroxides, their salts and mixtures thereof, and
28. The process of claim 1, wherein the treated hair is (b) optionally, at least one fatty Substance.
rinsed or washed after step (b). 40 44. The kit of claim 43, further comprising a third unit
29. The process of claim 1, wherein the process further containing, in a cosmetically acceptable carrier, at least one
comprises contacting the hair with a conditioning agent cho anionic Surfactant.
Sen from plant oils, synthetic oils, silicones, esters, humec 45. A composition for dyeing and reducing curl and/or
tants, conditioning polymers, and cationic agents prior to (c) frizziness of hair, said composition comprising, in a cosmeti
or (d) or (e) or after step (e). 45 cally acceptable carrier:
30. The process of claim 1, further comprising contacting (a) from about 1 to about 5% by weight of at least one
the Smoothed hair with a neutralizing composition after step non-hydroxide base chosen from monoethanolamine
(c) to form neutralized hair wherein the neutralizing compo and triethanolamine;
sition has a pH of below about 7. (b) from about 2 to about 20% by weight of a protein
31. The process of claim 30, wherein the neutralizing com 50 denaturant comprising urea and hydroxyethylurea
position comprises at least one oxidizing agent chosen from present in a ratio by weight ranging from about 5:1 to
persulfates, perborates, percarbonates, peroxyacids, bro about 2:1;
mates, peroxides, their salts and mixtures thereof. (c) at least one dye chosen from oxidative dye precursors;
32. The process of claim 30, wherein the neutralizing com (d) at least one thickening agent chosen from Xanthan gum
position comprises at least one oxidizing agent chosen from 55 and guar gum,
persulfate salts and mixtures thereof. (e) from about 1 to about 10% by weight of at least one
33. The process of claim 32, wherein the at least one alkoxysilane comprising at least one solubilizing func
oxidizing agentis presentinanamount of at least about 1% by tional group; and
weight, based on the weight of the neutralizing composition. (f) at least one fatty substance in an amount of at least 10%
34. The process of claim 32, wherein the neutralizing com 60 by weight;
position is applied onto the smoothed hair in order to alter the wherein all weights are based on the weight of the composi
color of the hair in situ. tion.
35. The process of claim 31, wherein the neutralizing com
position is Substantially anhydrous.