A hair coloring process comprising the application of a (poly)carbodiimide compound, a compound comprising at least one carboxylic acid group, and a coloring agent comprising aluminum.

The hair coloring process using a (poly)carbodiimide compound, a carboxylic acid group-containing compound, and aluminum-based coloring agent addresses the issue of insufficient lightening and coverage in existing methods, achieving enhanced coloring results.

FR3137287B1Active Publication Date: 2026-01-02LOREAL SA
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Patent Information

Application Number
FR2022006633
Authority / Receiving Office
FR · FR
Patent Type
Patents
Current Assignee / Owner
Filing Date
2022-06-30
Publication Date
2026-01-02
Estimated Expiration
2042-06-30

AI Technical Summary

Technical Problem

Existing hair coloring methods, particularly on dark hair, fail to achieve satisfactory levels of lightening and coverage, especially with temporary and non-permanent coloring compositions.

Method used

A hair coloring process using a composition comprising a (poly)carbodiimide compound, a compound with a carboxylic acid group, and a coloring agent containing aluminum, which provides improved lightening and coverage on hair.

Benefits of technology

The process achieves visible coloring on all hair types with a very good level of lightening and coverage, enhancing the cosmetic properties of hair coloring.

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Abstract

The present invention relates to a hair coloring process comprising the application to the hair of at least one composition C comprising: - at least one (poly)carbodiimide compound; - at least one compound comprising at least one carboxylic function; and - at least one coloring agent comprising aluminum different from coloring agents comprising at least one aluminosilicate.
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Description

Title of the invention: A hair coloring process comprising the application of a (poly)carbodiimide compound, a compound comprising at least one carboxylic acid group, and a coloring agent comprising aluminum

[0001] The present invention relates to a hair coloring process comprising the application to the hair of a composition C comprising a (poly)carbodiimide compound, a compound comprising at least one carboxylic function, and a coloring agent comprising a particular aluminum. technical field

[0002] In the field of hair keratin fiber coloring, it is already known to color hair keratin fibers by different techniques from direct dyes or pigments for non-permanent colorings or from dye precursors for permanent colorings.

[0003] There are essentially three types of hair coloring processes:

[0004] a) so-called permanent coloring which has the function of bringing about a significant change in the natural color and which uses oxidation dyes which penetrate the hair fiber and form the dye by a process of oxidative condensation;

[0005] b) non-permanent, semi-permanent or direct coloring, which does not implement the oxidative condensation process and resists 4 or 5 shampoos; consists of dyeing the keratin fibers with dyeing compositions containing direct dyes;

[0006] c) Temporary hair coloring that results in a change to the natural hair color that lasts from one shampoo to the next and serves to enhance or correct a previously achieved shade. It can also be considered a "makeup" process.

[0007] Another coloring method involves using pigments. Indeed, applying pigment to the surface of keratin fibers generally produces visible color on dark hair, since the surface pigment masks the fiber's natural color. However, the results obtained using this method do not always provide a satisfactory level of lightening, particularly on dark hair.

[0008] Moreover, temporary hair coloring compositions can also lead to cosmetic properties that do not give complete satisfaction, particularly in terms of coverage.

[0009] There therefore remains a need for a hair coloring process, which It has the advantage of providing a colored coating on hair with a good level of lightening and good coverage.

[0010] Thus, the object of the present invention is to develop a hair coloring process which has the advantage of obtaining a colored coating on the hair with an improved level of lightening and coverage. Description of the invention

[0011] The present invention therefore relates to a hair coloring process comprising the application to the hair of at least one composition C comprising:

[0012] - at least one (poly)carbodiimide compound;

[0013] - at least one compound comprising at least one carboxyl group; and

[0014] - at least one coloring agent comprising aluminum different from the agents colorants comprising at least one aluminosilicate.

[0015] Thanks to the hair coloring process according to the invention, colored coatings are obtained on the hair, allowing visible coloring on all hair types with a very good level of lightening as well as very good coverage.

[0016] The expression "at least one" means one or more.

[0017] Unless otherwise indicated, the boundaries of a range of values ​​are included in that range, particularly in the expressions "between" and "ranging from ... to ... ».

[0018] The invention is not limited to the illustrated examples. The features of the different examples can, in particular, be combined within non-illustrated variants.

[0019] For the purposes of the present invention and, unless otherwise indicated,

[0020] - an "alkyl" radical means a saturated linear or branched radical containing by example of 1 to 20 carbon atoms;

[0021] - an "aminoalkyl" radical means an alkyl radical as defined above, said alkyl radical comprising an NH2 group;

[0022] - a "hydroxyalkyl" radical means an alkyl radical as defined above, said alkyl radical comprising an OH group;

[0023] - an "alkylene" radical designates a divalent saturated hydrocarbon group at C2-C4, linear or branched, such as methylene, ethylene, or propylene;

[0024] - a "cycloalkyl" or "alicycloalkyl" radical designates a hydrocarbon group saturated cyclic mono- or polycyclic, preferably monocyclic, comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 24 carbon atoms, in particular comprising from 3 to 20 carbon atoms, more particularly from 3 to 13 carbon atoms, even more particularly from 3 to 12 carbon atoms, of preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, or norbomyl, in particular cyclopropyl, cyclopentyl, or a cyclohexyl. It being understood that the cycloalkyl radical may be substituted by one or more (Ci-C4)alkyl groups such as methyl; preferably the cycloalkyl radical is then an isobotyl group.

[0025] - a "cycloalkylene" radical designates a divalent cycloalkyl group with "cy cloalkyl” as defined above, preferably in C3-Ci2;

[0026] - an "aryl" radical is an unsaturated and aromatic hydrocarbon cyclic radical, comprising from 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms, mono / bi / or tri / cyclic, fused or not, preferably the aryl group comprises 1 ring of 6 carbon atoms such as phenyl, naphthyl, anthryl, phen-nanthryl and biphenyl, it being understood that the aryl radical may be substituted by one or more (Ci-C4)alkyl groups such as methyl, preferably tolyl, xylyl, or methylnaphthyl, preferably the aryl group represents phenyl;

[0027] - an "arylene" radical is a divalent aryl radical with "aryl" as defined above Previously, preferably arylene represents phenylene;

[0028] - a "heterocyclic" radical designates a mono or poly hydrocarbon radical cyclic, saturated or unsaturated, non-aromatic or aromatic, comprising one or more heteroatoms preferably of 1 to 5 atoms chosen from O, S or N, comprising from 3 to 20 links preferably between 5 and 10 links such as imidazolyl, pyrrolyl and furanyl;

[0029] - a "heterocycloalkylene" radical is a divalent heterocyclic group with "heterocyclic" as defined above;

[0030] - an "aryloxy" radical designates an aryl-oxy radical with "aryl" as defined above previously;

[0031] - an "alkoxy" radical designates an alkyl-oxy radical with "alkyl" as defined previously;

[0032] - an "acyloxy" radical designates an ester radical RC(O)-O- with R an alkyl group as defined previously;

[0033] - a "reactive" group is a group capable of forming a bond covalent with another group, identical or different, by chemical reaction.

[0034] Unless otherwise indicated, when compounds are mentioned in this application, this also includes their optical isomers, their geometric isomers, their tautomers, their salts, alone or in mixtures.

[0035] By "capillary keratin fibers" is meant hair. In other words, the expressions "capillary keratin fibers" and "hair" are equivalent in the remainder of the description.

[0036] For the purposes of the present invention, "hair" means the hair on the head. This term does not refer to body hair, eyebrows, or eyelashes. Polycarbodiimide compound

[0037] Composition C used in the process according to the invention comprises at least one (poly)carbodiimide compound.

[0038] The composition may comprise at least two distinct (poly)carbodiimide compounds, present in mixture in the composition.

[0039] The term "(poly)carbodiimide compound" means a compound comprising one or more carbodiimide group(s), preferably at least two carbodiimide groups, more preferably at least three carbodiimide groups, in particular the number of carbodiimide groups not exceeding 200, preferably 150, more preferably 100.

[0040] The term “carbodiimide group” means a linear divalent triatomic fraction of general formula - (N=C=N) -.

[0041] The (poly)carbodiimide compound(s) according to the invention may optionally comprise in their structure one or more reactive groups other than carbodiimide groups, selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoal-kylsilyl, mercaptoalkylsilyl, norbomenylsilyl, acylpentadienylalkylsilyl, maleimi-doalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide and azacyclopropane.

[0042] The reactive group(s) other than the carbodiimide groups may be pendant or terminal. Preferably, the (poly)carbodiimide compound(s) comprise one or more terminal groups other than the carbodiimide groups, preferably one or more terminal groups selected from the following: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbomenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylmylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide, and azacyclopropane.

[0043] According to a particular embodiment, the (poly)carbodiimide compound is chosen from the compounds of the following formula (I):

[0044] (I), OO

[0045] in which:

[0046] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0047] - Ri and R2 independently represent a grouping chosen from a radical hy a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatoms, a group selected from the following groups: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde-kylsilyl, mercaptoalkylsilyl, norbomenylsilyl, acylpentadienylalkylsilyl, maleimi-doalkylsilyl, sulfonylmylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide, and azacyclopropane, and a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatoms and by one or more groups selected from the following groups alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbomenylsilyl,acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylmylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and azacyclopropane; ,

[0048] - n denotes an integer from 1 to 1000; and

[0049] - A is a monomer selected from the compounds below:

[0050]

[0051] According to another embodiment, the (poly)carbodiimide compound is chosen from the compounds of the following formula (!'):

[0052] (D

[0053] in which:

[0054] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0055] - Yiet Y2 represent, independently, a divalent organic radical chosen from a saturated aliphatic group in C36 at Ci or an aromatic or alkylaromatic group in C6 to C24, the aliphatic or aromatic group optionally comprising one or more non-pending heteroatoms, such as nitrogen atom, oxygen atom, sulfur atom, or combinations thereof;

[0056] - Zi and Z2 represent, independently, a reactive terminal group or a group inert terminal;

[0057] - as an inert terminal group, Zi and Z2 can represent, independently, a saturated aliphatic group, linear or branched or cyclic, in the range of C1 to C50, or an aromatic group in the range of C6 to C18, said aliphatic and aromatic groups optionally comprising from 1 to 10 heteroatoms selected from nitrogen, oxygen, sulfur and their combinations, and the aliphatic or aromatic group may be partially or totally fluorinated; in this variant, Zi and Z2 comprise a CG linking group connecting Zi to Yi and Z2 to Y2, the CG group being a single covalent bond, a saturated C-C bond, an unsaturated covalent C-C bond, an amide group, an ester group, a carbonate group, a thioester group, an ether group, a urethane group, a thiourethane group or a urea group;

[0058] - as a reactive terminal group, Zi and Z2 can be chosen from the alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyal-kylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbomenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide groups such as propyl epoxide or butyl epoxide and azacyclopropane;

[0059] - Q represents an organopolymer or an organo-oligomer comprising re-units competitive groups of saturated, linear, branched, or cyclic aliphatic groups, or of aromatic groups or alkylaromatic groups, coupled by repeating bonds carbonate, ester, ether, amide, urethane or urea or their combinations;

[0060] - A represents a divalent aliphatic, aromatic, alkylaromatic or linear, saturated, branched or cyclic having from 2 to 30 carbon atoms, optionally including one or more non-pending heteroatoms, such as nitrogen atom, oxygen atom, sulfur atom, or combinations thereof, in the aliphatic chain or aromatic chain;

[0061] - r denotes an integer equal to 0 or 1;

[0062] - m denotes an integer from 0 to 1000, preferably equal to 0 or 1;

[0063] - m' designates an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0064] - n denotes an integer from 0 to 1000, preferably equal to 0 or 1, with m+ (m'*n ) > 2.

[0065] Preferably, Zi and Z2 represent, independently, a reactive terminal group, more preferably, Zi and Z2 represent, independently, a group selected from the following groups: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylal-kylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, car-boxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbor-nénylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide, and azacyclopropane.

[0066] Such (poly)carbodihnide compounds are marketed for example by the company Stahl BV, under the name Permutex XR, or under the name RelcaLinklO., under the name Picassian XL and Nisshinbo compounds marketed under the name CARBODILITE with the series V-02, V-02-L2, SV-02, E-02, V-10, SW-12G, E-03A, E-04DG-T, E-05, V-04, V-02B, V-04PF, V-05.

[0067] Preferably, the (poly)carbodiimide compound(s) is / are chosen from the compounds of the following formula (II):

[0069] in which

[0070] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0071] - Ri and R2 independently represent a hydrocarbon radical possibly in interrupted by one or more heteroatom(s);

[0072] - n and z denote an integer from 1 to 20, with n+z > 2 and w denotes a integer ranging from 1 to 3;

[0073] - Li independently represents a divalent aliphatic hydrocarbon radical in Ci - Cig, a C3-Ci5 cycloalkylene radical, a C3-Ci2 heterocycloalkylene group, or a C6-Ci4 arylene group, and mixtures thereof;

[0074] - E independently represents a grouping chosen from:

[0075] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-,

[0076] in which R3 and R4 independently represent a divalent hydrocarbon radical possibly interrupted by one or more heteroatom(s);

[0077] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, possibly interrupted by one or more heteroatom(s);

[0078] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

[0079] The term “hydrocarbon radical” means a saturated or unsaturated, linear or branched radical having from 1 to 300 carbon atoms, preferably from 1 to 250 carbon atoms, more preferably from 1 to 200 carbon atoms. Preferably, the hydrocarbon radical is a linear and saturated radical.

[0080] The hydrocarbon radical may comprise one or more cyclic groups.

[0081] The hydrocarbon radical may be interrupted by one or more heteroatom(s), in particular chosen from O, S or N and / or substituted by one or more cation(s), anion(s), or zwitterion(s) or cationic group(s) such as ammonium, anionic group(s) such as carboxylate, or zwitterionic group(s), and / or comprising a metal ion that can be incorporated in the form of a salt.

[0082] The term "heteroatom(s)" means an oxygen atom O, a sulfur atom S or a nitrogen atom N, as well as halogen atoms such as Cl, F, Br and I. If the heteroatom is included in the chain of the hydrocarbon radical, the heteroatom is preferably chosen from among the oxygen atoms O, sulfur atoms S or nitrogen atoms N.

[0083] Preferably, Xi and X2 independently represent an oxygen atom.

[0084] Preferably, Ri and R2 are chosen independently from dialkylaminoalcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, and mixtures thereof.

[0085] According to a preferred embodiment, Ri and R2 are chosen independently from the following groupings (i) to (iv):

[0086] (i) the compound of the following formula (III):

[0087] R7-OC(O)-C(R8)(H)-(III),

[0088] wherein R7 represents an alkyl group in CrC3, and R8 represents a hydrogen atom or an alkyl group in Ci-C3, preferably R7 is a methyl and R8 is a hydrogen atom or a methyl.

[0089] (ii) the compound of the following formula (IV):

[0090] R9-[0-CH2-C(H)(Rio)]p-(IV),

[0091] wherein R9 represents a Ci-C4 alkyl group, Rio represents a hydrogen atom or a Ci-C4 alkyl group and p denotes an integer from 1 to 3; preferably, R9 is a methyl, ethyl or butyl and R10 is a hydrogen atom or a methyl and p is equal to 1.

[0092] (iii) the compound of the following formula (V):

[0093] (Rh)2N-CH2-C(H)(Ri2)- (V),

[0094] wherein Rn represents an alkyl group in CrC4 and Rn represents a hydrogen atom or an alkyl group in CrC4; preferably Ru is a methyl, ethyl or butyl and Rn is a hydrogen atom or a methyl.

[0095] (iv) the compound of the following formula (VI):

[0096] R13-[O-CH2-C(H)(R14)]q- (VI),

[0097] in which Rn represents a CrC4 alkyl group or a phenyl, RM represents a hydrogen atom or a Ci-C4 alkyl group and q denotes an integer from 4 to 30; preferably Rn is a methyl, ethyl or butyl and R[4 is a hydrogen atom or a methyl.

[0098] Preferably, Ri and R2 independently represent a compound of formula (VI) in which Rn represents a CrC4 alkyl group or a phenyl group, preferably a alkyl group in C1-C4, more preferably a methyl, Ru represents a hydrogen atom or an alkyl group in C1-C4, preferably a hydrogen atom and q denotes an integer from 4 to 30.

[0099] According to an alternative embodiment, Ri and R2 are different and one of the radicals Ri or R2 represents a compound of formula (IV) as described above and the other radical Ri or R2 represents a compound of formula (VI) as described above.

[0100] Preferably, in formula (IV), R9 is a methyl, ethyl or butyl and R10 is a hydrogen atom or a methyl and p is equal to 1.

[0101] Preferably, in formula (VI), Rn is a methyl, ethyl or butyl and RM is a hydrogen atom or a methyl and q denotes an integer from 4 to 30.

[0102] According to another alternative embodiment, Ri and R2 are identical and represent a compound of formula (VI) in which Rn represents a CrC4 alkyl group or a phenyl, preferably a CrC4 alkyl group, more preferably a methyl, R[4] represents a hydrogen atom or a CrC4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30.

[0103] Preferably, n denotes an integer from 1 to 20, more preferably from 2 to 20.

[0104] Preferably, z denotes an integer from 1 to 20, more preferably from 2 to 20.

[0105] Preferably, w is equal to 1.

[0106] Preferably, w is equal to 1, n+z denotes an integer from 4 to 10.

[0107] Preferably, Li is chosen from a divalent aliphatic hydrocarbon radical in Ci -Ci8 such as methylene, ethylene, and propylene, a C3-Cn cycloalkylene radical such as cyclopentylene, cycloheptylene, and cyclohexylene, a C3-Ci2 heterocycloalkylene group such as imidazolene, pyrrolene, and furanylene, or a C6-Ci4 arylene group such as phenylene, and mixtures thereof.

[0108] For example, Li can be selected from a radical derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-diisocyanate dodecane, norbornane diisocyanate, 2,4-bis-(8-isocyanateoctyl)-1,3-dioctylcyclobutane, 4,4'-dicylclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate and phenylene diisocyanate and mixtures thereof.

[0109] Preferably, Li is selected from a C3-Ci5 cycloalkylene radical, or a C6-Ci4 arylene group and mixtures thereof, such as the compounds of the following formula (VII):

[0110] [YES]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120] Preferably, L1 is the 4,4-dicyclohexylene methane corresponding to the following formula (VIII): (VIII). According to another embodiment, when L1 is an arylene group at C6-Ci4, Li is not the m-tetramethylxylylene radical represented by the following formula (IX): . (IX). As previously stated, E independently represents a grouping chosen from: - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 independently represent a divalent hydrocarbon radical possibly interrupted by one or more heteroatom(s); - R5 independently represents a covalent bond or a divalent saturated hydrocarbon radical, possibly interrupted by one or more heteroatom(s); and - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s). Preferably, R3 and R4 are chosen independently from a C6 arylene radical - CM such as phenylene, a C3-Ci2 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or CrCi8 branched alkylene radical such as methylene and ethylene, possibly interrupted by one or more heteroatom(s) and mixtures thereof.

[0121] More preferably, R3 and R4 are chosen independently from a linear or CrCi8 branched alkylene radical such as methylene, butylene, propylene, ethylene, optionally interrupted by one or more heteroatom(s).

[0122] Preferably, when R5 is not a covalent bond, R5 is selected from a C6-Ci4 arylene radical such as phenylene, a C3-Ci2 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Ci8 alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0123] Preferably, R6 is selected from a C6-Ci4 arylene radical such as phenylene, a C3-Ci2 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Ci8 alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0124] Preferably, E represents an -O-R3-O- group in which R3 is selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched Ci-Ci8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0125] More preferably, E represents a -O-R3-O- group in which R3 represents a linear or CrCi8 branched alkylene radical such as methylene, butylene, propylene, ethylene, optionally interrupted by one or more heteroatom(s).

[0126] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from alpha-methylstyryl-isocyanates of the following formula (X):

[0127] (X),

[0128] in which R independently represents an alkyl group having from 1 to 24 carbon atoms, a cycloalkyl group having from 3 to 24 carbon atoms or an aryl group having from 6 to 24 carbon atoms, and,

[0129] n denotes an integer from 2 to 100.

[0130] In this embodiment, the term “alkyl group” is as defined above.

[0131] In this embodiment, the term "cycloalkyl group" is as defined above.

[0132] In this embodiment, n can denote an integer from 2 to 50, preferably from 3 to 30, more preferably from 5 to 10.

[0133] According to another particular embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI):

[0134] (XI), ■»»>». H----

[0135] in which R independently represents an alkyl group having from 1 to 24 carbon atoms, a cycloalkyl group having from 3 to 24 carbon atoms, or an aryl group having from 6 to 24 carbon atoms.

[0136] The "alkyl group", the "cycloalkyl group" and the "aryl group" are as defined above.

[0137] According to a preferred embodiment, the (poly)carbodiimide compound is selected from compounds of formula (I) or formula (II) in which:

[0138] - Xi and X2 independently represent an oxygen atom;

[0139] - Ri and R2 are chosen independently from among the dialkylaminoalcohols, the al- esters hydroxycarboxylic acid alkyls and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, more preferably the compound of formula (VI) as described above, in which Rn represents a CrC4 alkyl group or a phenyl group, preferably a CrC4 alkyl group, more preferably a methyl group, RM represents a hydrogen atom or a Ci-C4 alkyl group, preferably a hydrogen atom, and q denotes an integer from 4 to 30

[0140] - n and z, when present, denote an integer from 1 to 20, with n+z > 2 and w is equal to 1;

[0141] - Li, when present, is chosen from an aliphatic hydrocarbon radical divalent in CrCi8, a cycloalkylene radical in C3-Ci5, a heterocycloalkylene group in C3-Ci2, or an arylene group in C6-Ci4, and mixtures thereof, preferably a cycloalkylene radical in C3-Ci5;

[0142] - A, when present, is chosen from an aliphatic hydrocarbon radical CrCi8 divalent, a C3-Ci5 cycloalkylene radical, a heterocy- group C3-Ci2 cloalkylene, or a C6-Ci4 arylene group, and mixtures thereof, preferably a C3-Ci5 cycloalkylene radical;

[0143] - E, when present, independently represents a grouping chosen from:

[0144] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0145] wherein R3 and R4 are independently selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

[0146] - when R5 is not a covalent bond, R5, when present, is chosen from an arylene radical in the C6-Ci4 range, a cycloalkylene radical in the C3-Ci2 range, a linear or branched alkylene radical in the CrCi8 range, possibly interrupted by one or more heteroatoms, and mixtures thereof; and

[0147] - R6, when present, is chosen from a C6-Ci4 arylene radical, a cy radical C3-Ci2 cloalkylene, a linear or CrCi8 branched alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

[0148] Preferably, the (poly)carbodiimide compound is chosen from compounds of formula (II) in which:

[0149] - Xi and X2 independently represent an oxygen atom;

[0150] - Ri and R2 are chosen independently from among the dialkylaminoalcohols, the al- esters hydroxycarboxylic acid alkyls and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, and mixtures thereof;

[0151] - n and z denote an integer from 1 to 20, with n+z > 2 and w is equal to 1;

[0152] - Li is chosen from a divalent aliphatic hydrocarbon radical in CrCi8, a cycloalkylene radical at C3-Ci5, a heterocycloalkylene group at C3-Ci2, or an arylene group at C6-Ci4, and mixtures thereof;

[0153] - E independently represents a grouping chosen from:

[0154] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0155] wherein R3 and R4 are independently selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

[0156] - when R5 is not a covalent bond, R5 is chosen from an arylene radical in C6-Ci4, a C3-Ci2 cycloalkylene radical, a linear or branched Ci-Ci8 alkylene radical, possibly interrupted by one or more heteroatoms, and mixtures thereof; and

[0157] - R6 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched Ci-Ci8 alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

[0158] More preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0159] - Xi and X2 independently represent an oxygen atom;

[0160] - Ri and R2, are independently of (poly)alkylene glycol monoalkyl ethers, in which a hydroxy group has been removed;

[0161] - n and z denote an integer from 1 to 20, with n+z > 2 and w is equal to 1;

[0162] - Li is a C3-Ci5 cycloalkylene radical;

[0163] - E independently represents a grouping chosen from:

[0164] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0165] wherein R3 and R4 are independently selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

[0166] - when R5 is not a covalent bond, R5 is chosen from an arylene radical in C6-Ci4, a C3-Ci2 cycloalkylene radical, a linear or branched Ci-Ci8 alkylene radical, possibly interrupted by one or more heteroatoms, and mixtures thereof; and

[0167] - R6 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched Ci-Ci8 alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

[0168] Even more preferably, the (poly)carbodiimide compound is chosen from compounds of formula (II) in which:

[0169] - Xi and X2 independently represent an oxygen atom;

[0170] - Ri and R2, independently represent the compound of the following formula (VI):

[0171] R13-[O-CH2-C(H)(R14)]q- (VI),

[0172] wherein R13 represents a CrC4 alkyl group or a phenyl, preferably a CrC4 alkyl group, more preferably a methyl, R14 represents a hydrogen atom or a CrC4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30;

[0173] - n and z denote an integer from 2 to 20, with n+z from 4 to 10 and w is equal to 1;

[0174] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cyclo- heptylene, cyclohexylene and 4,4-dicyclohexylene methane; and

[0175] - E represents a grouping -O-R3-O- in which R3 is chosen from a radical arylene in C6-Ci4, a cycloalkylene radical in C3-Ci2, a linear or branched alkylene radical in Ci-Ci8, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

[0176] Even more preferably, the (poly)carbodiimide compound is chosen from compounds of formula (II) in which:

[0177] - Xi and X2 independently represent an oxygen atom;

[0178] - Ri and R2, independently represent the compound of the following formula (VI):

[0179] R13-[O-CH2-C(H)(R14)]q- (VI)

[0180] wherein R13 represents a Ci-C4 alkyl group or a phenyl group, preferably a CrC4 alkyl group, more preferably a methyl group, R14 represents an atom of hydrogen or an alkyl group in CrC4, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;

[0181] - n and z denote an integer from 2 to 20, with n+z from 4 to 10 and w is equal to 1;

[0182] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cyclo- heptylene, cyclohexylene, 4,4-dicyclohexylene, methane, preferably 4,4-Dicyclohexylene methane; and

[0183] - E represents a group- -O-R3-O- in which R3 represents a radical linear or branched CrCi8 alkylene such as methylene, propylene, butylene, ethylene, possibly interrupted by one or more heteroatom(s).

[0184] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of the following formula (XII):

[0185]

[0186] in which L1 is 4,4-dicyclohexylene methane, n and z denote an integer from 2 to 20, with n+z ranging from 4 to 10, E represents an -O-R3-O- group in which R3 represents a linear or Ci-Ci8 branched alkylene radical such as methylene, propylene, butylene ethylene, optionally interrupted by one or more heteroatom(s), and r and s denote an integer from 4 to 30.

[0187] Advantageously, the total amount of the (poly)carbodiimide compound(s) ranges from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, even more preferably from 0.5 to 8%, better from 1 to 6% by weight relative to the total weight of composition C. Compound having at least one carboxylic acid function

[0188] Composition C used in the process according to the invention comprises at least one compound having at least one carboxylic function.

[0189] Preferably, the compound having at least one carboxylic function is chosen from silicone compounds comprising at least one carboxylic group, polyurethanes, acrylic polymers and their mixtures. Polyurethanes and acrylic polymers

[0190] According to a preferred embodiment, composition C comprises at least one compound having at least one carboxylic function selected from polyurethanes, acrylic polymers and their mixtures.

[0191] Preferably, the compound(s) having at least one carboxylic function are in the form of aqueous dispersions of polymer(s) particles selected from polyurethanes, acrylic polymers, and their mixtures.

[0192] Preferably, composition C comprises at least one compound having at least one carboxylic function in the form of aqueous dispersions of polyurethane particles, acrylic polymers, and mixtures thereof.

[0193] The dispersion(s) may be simple dispersions in the aqueous medium of the cosmetic composition. Latexes are a particular example of a dispersion.

[0194] The aqueous dispersion(s) of polymer particles can be chosen from aqueous dispersions of polyurethane particles.

[0195] More particularly, the polyurethane(s) present in the aqueous dispersions used in the present invention are derived from the reaction of

[0196] - a prepolymer of the following formula (A):

[0197] $3 $$ $$

[0198] (A),

[0199] in which

[0200] - Ri represents a divalent radical of a dihydroxylated compound;

[0201] - R2 represents a radical of an aliphatic or cycloaliphatic polyisocyanate;

[0202] - R3 represents a radical of a low molecular weight diol, possibly substituted by one or more ionic groups;

[0203] - n represents an integer from 1 to 5, and

[0204] - m is greater than 1;

[0205] - at least one chain extender according to the following formula (B):

[0206] H2N-R4-NH2 (B),

[0207] wherein R4 represents an alkylene radical or alkylene oxide that is not substituted by one or more ionic or potentially ionic groups; and

[0208] - at least one chain extender according to the following formula (C):

[0209] H2N-R5-NH2 (C),

[0210] in which R5 represents an alkylene radical substituted by one or more ionic or potentially ionic groups.

[0211] Among the dihydroxylated compounds usable according to the present invention, particular examples include compounds having two hydroxyl groups and a number molecular weight of approximately 700 to approximately 16,000, and preferably of approximately 750 to approximately 5,000. Examples of dihydroxylated compounds having a high molecular weight include polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadienes, polyhydroxylated polythioethers, and mixtures thereof. Preferably, the hydroxylated compounds are selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0212] The polyisocyanates usable according to the present invention are in particular chosen from among the organic diisocyanates having a molecular weight of about 112 to 1000, and preferably of about 140 to 400.

[0213] Preferably, the polyisocyanates are chosen from among the diisocyanates and more particularly from those represented by the general formula R2(NCO)2, in which R2 represents a divalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having from 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having from 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having from 6 to 15 carbon atoms.

[0214] Preferably, R2 represents an organic diisocyanate. Examples of organic diisocyanates include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, l,3-bis(isocyanatomethyl)cyclohexane, l,4-bis(isocyanatomethyl)cyclohexane, bis-(4-isocyanato-3-methylcyclohexyl)methane, and isomers of toluene diisocyanate. (TDI) such as toluene 2,4-diisocyanate, toluene 2,6-düsocyanate and mixtures thereof, hydrogenated toluene diisocyanate, diphenylmethane 4,4'-diisocyanate and mixtures with its isomers diphenylmethane 2,4-diisocyanate and possibly diphenylmethane 2,2'-diisocyanate, naphthalene-1,5-diisocyanate, and mixtures thereof.

[0215] Preferably, the diisocyanates are aliphatic and cycloaliphatic diisocyanates, and are most preferably chosen from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate and mixtures thereof.

[0216] By "low molecular weight diol," according to the present invention, we mean a diol having a molecular weight of about 62 to 700, and preferably of 62 to 200. These diols may comprise aliphatic, alicyclic, or aromatic groups. Preferably, they comprise only aliphatic groups.

[0217] Preferably, R3 represents a low molecular weight diol, having more than 20 carbon atoms, more preferably selected from ethylene glycol, diethylene glycol, propane 1,2-diol, propane 1,3-diol, butane 1,4-diol, butylene 1,3-glycol, neopentyl glycol, butyl-ethyl-propane diol, cyclohexane diol, 1,4-cyclohexane dimethanol, hexane 1,6-diol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), and mixtures thereof.

[0218] Low molecular weight diols may optionally include ionic or potentially ionic groups. Examples of low molecular weight diols containing ionic or potentially ionic groups are described in particular in US patent 3,412,054. Such compounds are preferably selected from dimethylol butanoic acid, dimethylol propionic acid, polycaprolactone diols containing a carboxyl group, and mixtures thereof.

[0219] If lower molecular weight diols containing ionic or potentially ionic groups are used, they are preferably used in an amount such that less than 0.30 meq of COOH per gram of polyurethane in the polyurethane dispersion are present.

[0220] The prepolymer is elongated using two families of chain extenders. The first family of chain extenders corresponds to compounds of general formula (B).

[0221] The chain extenders of formula (B) are preferably selected from alkylene diamines, such as hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine; alkylene oxide diamines, such as 3-{2-[2-(3-aminopropoxy)ethoxy]-ethoxy}propylamine (also called dipropylamine diethylene glycol or DPA-DEG, available from Tomah Products, Milton, Wis.), 2-methyl-1,5-pentanediamine (DuPont's Dytec A), hexanediamine, isophoronediamine, 4,4-methylenedi-(cyclohexylamine), DPA series ether-amines available from Tomah Products, Milton, Wis., such as dipropylamine propyleneglycol, dipropylamine dipropyleneglycol, dipropylamine tripropyleneglycol, dipropylamine poly(propylene glycol), dipropylamine ethyleneglycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propanediol, dipropylamine 2-methyl-1,3-propanediol, dipropylamine 1,4-butanediol, dipropylamine 1,3-butanediol, dipropylamine 1,6-hexanediol and dipropylamine cyclohexane-1,4-dimethanol; and mixtures thereof.

[0222] The second family of chain extenders corresponds to compounds of general formula (C). Such compounds preferably have one ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Such compounds may optionally comprise two groups reactive with isocyanate groups and one ionic group or group capable of forming an ionic group.

[0223] The ionic or potentially ionic group may preferably be selected from ternary or quaternary ammonium groups or groups convertible into such groups, a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group. The conversion, at least partial, of the convertible groups into salts of ternary or quaternary ammonium groups may take place before or during mixing with water.

[0224] The chain extenders of formula (C) are preferably chosen from among the diaminosulfonates, such as for example the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid, and mixtures thereof.

[0225] The polyurethane usable according to the present invention may optionally further comprise compounds that are respectively located at the ends of the chains and terminate said chains (chain terminators). Such compounds are described in particular in US patents 7,445,770 and / or US patents 7,452,770.

[0226] Preferably, the aqueous dispersion of polyurethane particles has a viscosity of less than 2000 mPa.s at 23°C, more preferably less than 1500, and even better less than 1000. Even more preferably, the aqueous dispersion of polyurethane has a glass transition temperature of less than 0°C.

[0227] Also preferably, the aqueous polyurethane dispersion has a polyurethane (or active material, or dry matter) content, based on the weight of the dispersion, of 20 to 60% by weight, more preferably 25 to 55% by weight, and even better 30 to 50% by weight. This means that the polyurethane (dry matter) content of the aqueous dispersion is preferably 20% to 60% by weight, more preferably 25% to 55% by weight, and even better 30% to 50% by weight. relative to the total weight of the dispersion.

[0228] Also preferably, the aqueous dispersion of polyurethane particles has a glass transition temperature (Tg) equal to or less than -25°C, preferably less than -35°C, and more preferably less than -40°C.

[0229] Polyurethane particles can have an average diameter of up to about 1000 nm, for example from about 50 nm to about 800 nm, better from about 100 nm to about 500 nm. These particle sizes can be measured with a laser particle size analyzer (for example Brookhaven BI90).

[0230] By way of non-limiting example of aqueous polyurethane dispersions, one may cite those sold under the name Baycusan® by Bayer such as, for example, Baycusan® C1000 (INCI name: polyurethane-34), Baycusan® C1001 (INCI name: po-lyurethane-34), Baycusan® C1003 (INCI name: polyurethane-32), Baycusan® C1004 (INCI name: polyurethane-35) and Baycusan® C1008 (INCI name: polyurethane-48).

[0231] We may also mention aqueous polyurethane dispersions of isophthalic acid / adipic acid copolymer / hexylene glycol / neopentyl glycol / dimethylol acid / isophorone diisocyanate (INCI name: Polyurethane-1, such as Luviset® PUR, BASF), polycarbonate polyurethane, polyurethane and aliphatic polyester aliphatic polyurethane (such as the NEOREZ® series, DSM, such as NEOREZ® R989, NEOREZ® and R-2202).

[0232] According to a preferred embodiment, the aqueous dispersion of polyurethane particles can be selected from aqueous dispersions of particles of compounds with INCI name polyurethane-35 or compounds with INCI name poly-urethane-34.

[0233] Preferably, the compound or compounds having at least one carboxylic function are in the form of aqueous dispersions of acrylic polymer particles, more preferably in the form of aqueous dispersions of film-forming acrylic polymer particles.

[0234] For the purposes of this invention, "polymer" means a compound consisting of the repetition of one or more motifs (these motifs being derived from compounds called monomers). This motif or these motifs are repeated at least twice and preferably at least three times.

[0235] By "film-forming polymer" is meant a polymer capable of forming, either alone or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, in particular on hair, and preferably a cohesive film.

[0236] For the purposes of this invention, "acrylic polymer" means a polymer synthesized from at least one monomer selected from (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide.

[0237] The motif(s) arising from the (meth)acrylic acid monomers of the polymer may (may) possibly be in the form of salt(s), in particular of alkali metal, alkaline earth metal, ammonium or organic base.

[0238] Esters of (meth)acrylic acid (also called (meth)acrylates) are advantageously chosen from alkyl (meth)acrylates, in particular alkyl in C1 to C30, preferably in C1 to C20, better in C1 to C10, aryl (meth)acrylates, in particular aryl in C6 to C10, hydroxyalkyl (meth)acrylates, in particular hydroxyalkyl in C2 to C6.

[0239] Among the alkyl (meth)acrylates, we can mention methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, ethyl-2 hexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate.

[0240] Among the hydroxyalkyl (meth)acrylates, we can mention hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.

[0241] Among the aryl (meth)acrylates, benzyl acrylate and phenyl acrylate can be cited.

[0242] The particularly preferred (meth)acrylic acid esters are alkyl (meth)acrylates, preferably alkyl in C1 to C30, more preferably in C1 to C20, even better in C1 to C10, and even more particularly in C1 to C4.

[0243] According to the present invention, the alkyl group of the esters can be fluorinated, or even perfluorinated, that is to say that part or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

[0244] Examples of (meth)acrylic acid amides include (meth)acrylamides, as well as N-alkyl (meth)acrylamides, particularly alkyl C2 to C12. Among the N-alkyl (meth)acrylamides, examples include N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide and N-undecylacrylamide.

[0245] The acrylic polymer according to the invention can be a homopolymer or a copolymer, advantageously a copolymer, even better a copolymer of (meth)acrylic acid and (meth)acrylic acid esters.

[0246] Preferably, the acrylic polymer(s) according to the invention comprise one or more motifs derived from the following monomers:

[0247] a) (meth)acrylic acid; and

[0248] b) alkyl (meth)acrylate in C1 to C30, more preferably in C1 to C20, even better in C1 to C10, and even more particularly in C1 to C4.

[0249] Preferably, the aqueous dispersion of acrylic polymer particles does not include a surfactant.

[0250] The term “surfactant” means any agent capable of modifying the surface tension between two surfaces.

[0251] Among the acrylic polymers according to the invention, we can mention the copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, in particular the copolymers of methacrylic acid and ethyl acrylate such as the compound sold under the trade name LUVIMER MAE by BASF, or the Polyacrylate-2 crosspolymer compound sold under the trade name FIXATE SUPERHOLD POLYMER by LUBRIZOL, or the Acrylate Copolymer compound sold under the trade name DAITOSOL 3000VP3 by DAITO KASEI KOGYO, or the Acrylate Copolymer compound sold under the trade name DAITOSOL 3000SLPN-PE1 by DAITO KASEI KOGYO.

[0252] The acrylic polymer may optionally comprise one or more additional monomers, other than the (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide monomers.

[0253] As an additional monomer, examples include styrenic monomers, in particular styrene and alpha-methylstyrene, and preferably styrene.

[0254] In particular, the acrylic polymer may be a styrene / (meth)acrylate copolymer, and in particular a polymer selected from copolymers resulting from the polymerization of at least one styrenic monomer and at least one alkyl (meth)acrylate monomer in C1 to C20, preferably in C1 to C10.

[0255] The alkyl (meth)acrylate monomer in C1 to C10 can be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethyl hexyl acrylate.

[0256] As an acrylic polymer, we can cite the styrene / (meth)acrylate(s) copolymers marketed under the name JONCRYL 77 by BASF, under the name YODOSOL GH41F by AKZO NOBEL and under the name SYNTRAN 5760 CG by INTERPOLYMER.

[0257] Preferably, composition C comprises at least an aqueous dispersion of acrylic polymer particles.

[0258] More preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more motifs derived from the following monomers:

[0259] a) (meth)acrylic acid; and

[0260] b) alkyl (meth)acrylate in C1 to C30, more preferably in C1 to C20, even better in C1 to C10, and even more particularly in C1 to C4.

[0261] Preferably, the aqueous dispersion of acrylic polymer particles has an acrylic polymer (or active material, or dry matter) content on the basis of the weight of the dispersion of 20 to 60% by weight, more preferably of 22 to 55% by weight and even better of 25 to 50% by weight. Silicone acrylic copolymer

[0262] According to a particular embodiment, the silicone compound(s) comprising at least one carboxylic group are chosen from silicone acrylic copolymers.

[0263] Thus, according to a particular embodiment, the compound or compounds having at least one carboxylic function are chosen from among silicone acrylic copolymers.

[0264] Preferably, said silicone acrylic copolymer(s) comprise:

[0265] - at least one acrylic, methacrylic, or crotonic motif; and

[0266] - at least one polydimethylsiloxane (PDMS) motif.

[0267] For the purposes of this invention, "polydimethylsiloxanes" (also referred to as PDMS), in accordance with general acceptance, means any linear structure organosilicon polymer or oligomer of variable molecular weight, obtained by polymerization and / or polycondensation of suitably functionalized silanes, and consisting essentially of a repetition of principal motifs in which silicon atoms are linked together by oxygen atoms (Si-O-Si siloxane bond), comprising methyl radicals directly linked via a carbon atom to said silicon atoms.

[0268] The PDMS chains that can be used to obtain the copolymer used according to the invention comprise at least one polymerizable radical group, preferably located on at least one of the ends of the chain, i.e. the PDMS can have for example a polymerizable radical group on each of the two ends of the chain or have a polymerizable radical group on one end of the chain and a terminal trimethylsilyl group on the other end of the chain.

[0269] By polymerizable radical group is meant a radical capable of polymerizing with other polymerizable radical groups or monomers. Preferably, the polydimethylsiloxane motif comprises at least one polymerizable radical group.

[0270] Preferably, the polymerizable radical group comprises at least one vinyl group.

[0271] Preferably, the polydimethylsiloxane (PDMS) motif comprises at least one polymerizable radical group comprising at least one vinyl group, preferably at least two polymerizable radical groups comprising at least one vinyl group, preferably located on at least one end of the chain.

[0272] As indicated above, said or said silicone acrylic copolymers preferably comprise at least one acrylic or methacrylic or crotonic motif, that is to say at least one motif comprising a carboxylic group.

[0273] The term “carboxylic group” means a functional group COOH or COO, the counter-ion of the COO group being able to be chosen from among the alkali metals, the alkaline earth metals, the quaternary ammoniums.

[0274] Preferably, said silicone acrylic copolymer(s) comprise:

[0275] - at least one acrylic or methacrylic or crotonic motif, and at least one motif acrylic ester or methacrylic ester or vinyl ester; and

[0276] - at least one polydimethylsiloxane (PDMS) motif.

[0277] More preferably, the composition comprises one or more silicone acrylic copolymers comprising: - at least one crotonic motif and at least one motif selected from an alkyl crotonate motif, the alkyl radical being a saturated linear or branched radical containing from 1 to 20 carbon atoms; a vinyl acetate motif; a vinyl alkyl ester motif, the alkyl radical being a saturated linear or branched radical containing from 2 to 20 carbon atoms; and mixtures thereof; and - at least one polydimethylsiloxane (PDMS) motif.

[0278] By crotonic motif is meant a motif derived from a crotonic acid monomer or one of its salts.

[0279] By alkyl crotonate motif is meant a motif derived from a crotonic acid ester monomer, having a linear or branched, saturated alkyl radical containing from 1 to 20 carbon atoms.

[0280] By vinyl alkyl ester motif, we mean a motif derived from a vinyl ester monomer having a saturated linear or branched alkyl radical containing from 2 to 20 carbon atoms.

[0281] A vinyl acetate motif is defined as a motif derived from a vinyl acetate monomer.

[0282] In a preferred embodiment, said silicone acrylic copolymer(s) comprise: - at least one crotonic motif, at least one vinylacetate motif and at least one vinyl alkyl ester motif, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms, and - at least one polydimethylsiloxane (PDMS) motif, preferably comprising at least one polymerizable radical group including at least one vinyl group.

[0283] According to a particularly preferred embodiment, said silicone acrylic copolymer(s) comprise: - at least one crotonic motif, at least one vinylacetate motif and at least one vinyl alkyl ester motif, the alkyl radical being a linear or branched, saturated radical containing from 6 to 16 carbon atoms, and

[0284] - at least one polydimethylsiloxane (PDMS) motif comprising at least one group polymerizable radical comprising at least one vinyl group.

[0285] More preferably, the composition comprises one or more silicone acrylic copolymers comprising: - at least one crotonic motif, at least one vinylacetate motif and at least one vinyl alkyl ester motif, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms; and - at least one polydimethylsiloxane (PDMS) motif comprising at least one polymerizable radical group including at least one vinyl group.

[0286] Even more preferably, the composition comprises one or more silicone acrylic copolymers comprising:

[0287] - at least one crotonic motif, at least one vinylacetate motif and at least one motif vinyl alkyl ester, the alkyl radical being a linear or branched, saturated radical containing 6 to 16 carbon atoms; and

[0288] - at least one polydimethylsiloxane (PDMS) motif comprising at least one group polymerizable radical comprising at least one vinyl group.

[0289] Among the silicone acrylic copolymers that can be used in the context of the invention, mention can be made of the compound sold by the company Wacker Chemie AG under the trade name Belsil® PI 101, with the INCI name Crotonic Acid / Vinyl C8-12 Isoalkyl Esters / VA / Bis-Vinyldimethicone Crosspolymer.

[0290] The total quantity of the compound or compounds having at least one carboxylic function is preferably from 0.1 to 30% by weight, more preferably from 0.5 to 20% by weight, better still from 1 to 15% by weight, and even more preferably from 2 to 10% by weight relative to the total weight of composition C.

[0291] The total quantity of the aqueous dispersion(s) of polymer particle(s) selected from polyurethanes, acrylic polymers, and their mixtures is preferably from 0.1 to 40% by weight, more preferably from 0.5 to 30% by weight, better still from 1 to 25% by weight, and even more preferably from 2 to 20% by weight relative to the total weight of composition C.

[0292] According to a particular embodiment, the total quantity of the aqueous dispersion(s) of acrylic polymer particle(s) preferably ranges from 0.1 to 40% by weight, more preferably from 0.5 to 30% by weight, better still from 1 to 25% by weight, and even more preferably from 2 to 20% by weight relative to the total weight of composition C.

[0293] Advantageously, the total quantity of silicone acrylic copolymer(s) ranges from 0.1 to 30% by weight, more preferably from 0.5 to 20% by weight, better still from 1 to 15% by weight, and even more preferably from 2 to 10% by weight relative to the total weight of composition C. Coloring agent containing aluminum

[0294] Composition C used in the process according to the invention comprises at least one colouring agent comprising aluminium other than colouring agents comprising at least one aluminosilicate.

[0295] Preferably, the coloring agent or agents comprising aluminum according to the invention are chosen from pigments comprising aluminum other than pigments comprising at least one aluminosilicate.

[0296] By "pigment" is meant a pigment that imparts color to keratinous materials. Its solubility in water at 25 °C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

[0297] The aluminum pigments according to the invention may comprise a substrate and optionally one or more layers that can be disposed on the substrate.

[0298] The substrate can be chosen from aluminium and aluminium oxides.

[0299] In particular, the substrate can be chosen from lamellar aluminium flakes and lamellar aluminium oxide flakes.

[0300] The substrate can be passivated, for example by anodizing.

[0301] The substrate can be coated with one or more layers.

[0302] Preferably, the substrate is coated with a layer B.

[0303] A layer A may be present between the substrate and layer B.

[0304] A layer C disposed on layer B may also be present.

[0305] Layers A, B and C may be made of materials that can be applied in the form of films and permanently to the substrate.

[0306] Layers A, B and C may partially or even totally cover the surface of the substrate.

[0307] For example, the upper face and / or the lower face of the substrate surface may be totally covered by at least one of the layers A, B and C, while the lateral faces of the substrate surface are not covered.

[0308] Layer A may be made of at least one material selected from metal oxides and / or metal oxide hydrates with a low refractive index.

[0309] For the purposes of this invention, "low refractive index material" means a material having a refractive index of 1.8 or less, preferably 1.6 or less.

[0310] Advantageously, layer A comprises at least 95% by weight, preferably at least 99% by weight, of metal oxides and / or metal oxide hydrates with a low refractive index relative to the total weight of the material constituting layer A.

[0311] Low refractive index metal oxides and / or metal oxide hydrates may be selected from silicon (di)oxide, hydrated silicon oxide, aluminium oxide, hydrated aluminium oxide, boron oxide, germanium oxide, manganese oxide, magnesium oxide and mixtures thereof, preferably from silicon dioxide.

[0312] Layer A may have a thickness ranging from 1 to 100 nm, preferably from 5 to 50 nm, more preferably from 5 to 20 nm.

[0313] Advantageously, layer B consists of at least one high refractive index metal oxide.

[0314] For the purposes of this invention, "high refractive index material" means a material having a refractive index greater than or equal to 1.9, preferably greater than or equal to 2.0, more preferably greater than or equal to 2.4.

[0315] High refractive index metal oxides can be selected from light-absorbing metal oxides, such as ferric oxide, cobalt(II) oxide, chromium(III) oxide, titanium(III) oxide, vanadium(V) oxide, and mixtures thereof.

[0316] High refractive index metal oxides can also be selected from colorless oxides, such as titanium dioxide and / or zirconium oxide.

[0317] Layer B may have a thickness of at least 50 nm, preferably from 50 to 400 nm, more preferably from 50 to 300 nm.

[0318] Advantageously, layer C can be made of at least one material selected from metal oxides and / or metal oxide hydrates.

[0319] Metal oxides and / or metal oxide hydrates may be selected from silicon (di)oxide, hydrated silicon oxide, aluminium oxide, hydrated aluminium oxide, zinc oxide, tin oxide, titanium dioxide, zirconium oxide, iron (III) oxide, chromium oxide and mixtures thereof, preferably from silicon dioxide.

[0320] The C layer may have a thickness ranging from 10 to 500 nm, preferably ranging from 50 to 300 nm.

[0321] Preferably, the substrate is coated with a layer B only.

[0322] Preferably, the substrate is coated with a layer comprising at least one oxide metallic with a high refractive index, most preferably chosen from light-absorbing metallic oxides, such as ferric oxide, cobalt(II) oxide, chromium(III) oxide, titanium(III) oxide, vanadium(V) oxide, and mixtures thereof

[0323] Advantageously, the colouring agent comprising aluminium according to the invention has a thickness ranging from 70 to 500 nm, preferably ranging from 100 to 400 nm.

[0324] According to a preferred embodiment, organic compounds such as silanes can be added to the outermost layer, i.e. to layer A, or to layer B or to layer C.

[0325] Preferably, the aluminum pigment(s) according to the invention are coated with a layer comprising organic compounds such as silanes.

[0326] Preferably, the organic compounds can be selected from methacryloxy- propenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane, 3- methoxy-propyltris(methoxyacryloxypropyl) silane, 3-methacryloxypropyltrimethoxysilane, methacryloxypropyltris (propoxy) silane, 3-methacryloxypropyl (butoxy)silane, 3-acryloxypropyltris(methoxyethoxy)silane, 3-acryloxypropyltris(butoxyethoxy)silane, 3-acryloxypropyltris(butoxy)silane, vi-nyltrimethoxysilane, vinyltriethoxysilane, vinylethyldichlorosilane, vinylmethyldiacetoxysilane, vinylmethyldichlorosilane, vinylmethyldiethoxysilane, vi-nyltriacetoxysilane, vinyltrichlorosilane, phenylvinyldiethoxysilane or phenyl-lallyldichlorosilane.

[0327] As an example of a coloring agent comprising aluminum according to the invention, one can cite that sold under the trade name STARBRITE REVEAL AQ 4172PA sold by the company Siberline.

[0328] The pigments can be dispersed within the composition by means of a dispersing agent.

[0329] The dispersing agent serves to protect the dispersed particles from agglomeration or flocculation. This dispersing agent may be a surfactant, an oligomer, a polymer, or a mixture of several of these, possessing one or more functionalities with a strong affinity for the surface of the particles to be dispersed. In particular, they may adhere physically or chemically to the surface of the pigments. These dispersants also have at least one functional group that is compatible with or soluble in the continuous medium.In particular, esters of 12-hydroxystearic acid are used, especially C8 to C20 fatty acids and polyols such as glycerol, diglycerin, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750g / mol such as that sold under the name Solsperse 21 000 by Avecia, polyglyceryl-2 dipolyhydroxystearate (name CTFA) sold under the reference Dehymyls PGPH by Henkel or polyhydroxystearic acid such as that sold under the reference Arlacel P100 by Uniqema and their mixtures.

[0330] As another dispersant that can be used in the compositions of the invention, we can mention quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17 000 sold by Avecia, poly dimethylsiloxane / oxypropylene mixtures such as those sold by Dow Corning under the references DC2-5185, DC2-5225 C.

[0331] According to a particular embodiment of the invention, the dispersing agent is present with organic or inorganic pigments in submicron-sized particulate form.

[0332] By "sub-micron" or in English "sub-micron" is meant pigments of which the particle size was micronized by micronization method and whose average particle size is less than one micrometer (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm.

[0333] According to one embodiment, the dispersing agent and the pigment(s) are present in quantity (dispersing agent: pigment), according to a weight ratio, between 1:4 and 4:1, particularly between 1.5:3.5 and 3.5:1 or better between 1.75:3 and 3:1.

[0334] The dispersing agent(s) may therefore have a silicone skeleton, such as silicone polyether and amino-silicone dispersants. Suitable dispersing agents include:

[0335] - amino-silicones i.e. silicones comprising one or more amino groups such than those marketed under the names and references: BYK LPX 21879, by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, marketed by Genesee Polymers,

[0336] - silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik,

[0337] - polydimethylsiloxane (PDMS) silicones with carboxylic groups such as X- 22162 and X-22370 by Shin-Etsu, silicone epoxy such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695, by Genesee Polymers, or Tego ® RC 1401, Tego ® RC 1403, Tego ® RC 1412, by Evonik.

[0338] According to a particular embodiment, the dispersing agent(s) are of the amino-silicone type and are cationic.

[0339] The aluminum-containing colorant(s) according to the invention may be present in a total quantity from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight relative to the total weight of composition C. Preferably, the aluminum-containing colorant(s) according to the invention are chosen from aluminum-containing pigments other than pigments containing at least one aluminosilicate.

[0340] The aluminum pigment(s) other than pigments comprising at least one aluminosilicate may be present in a total quantity from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, better from 0.5 to 10% by weight relative to the total weight of composition C.

[0341] Composition C used in the process according to the invention may further comprise one or more pigments other than the aluminum pigments according to the invention.

[0342] Said pigments which may be used are in particular chosen from among the organic and / or mineral pigments known in the art, in particular those which are described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.

[0343] They may be natural, of natural origin, or not.

[0344] These pigments may be in the form of a powder or pigment paste. They may be coated or uncoated.

[0345] Said pigments may for example be chosen from mineral pigments, organic pigments, lacquers, special effect pigments such as mother-of-pearl or glitter, and mixtures thereof.

[0346] Said pigment may be a mineral pigment. By mineral pigment is meant any pigment that meets the definition in the Ullmann Encyclopedia in the chapter on inorganic pigments. Examples of mineral pigments useful in the present invention include iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium dioxide.

[0347] Said pigment may be an organic pigment. By "organic pigment" is meant any pigment that meets the definition in the Ullmann encyclopedia in the chapter on organic pigment.

[0348] The organic pigment may in particular be selected from the following compounds: nitroso, nitro, azo, xanthene, pyrene, quinoline, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complex type, isoindolinone, isoindoline, qui-nacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane, quinophthalone.

[0349] In particular, the white or colored organic pigments may be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments coded in the Color Index under references Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments coded in the Color Index under references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments coded in the Color Index under references Cl 61565, 61570, 74260, the orange pigments coded in the Color Index under reference CI 11725, 45370, 71105, the red pigments coded in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole, phenolic derivatives as described in patent FR 2 679 771.

[0350] By way of example, one can also cite organic pigment pastes such as the products sold by the company HOECHST under the name:

[0351] - COSMENYL YELLOW IOG: Pigment YELLOW 3 (Cl 11710);

[0352] - COSMENYL YELLOW G: Pigment YELLOW 1 (Cl 11680);

[0353] - ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);

[0354] - COSMENYL RED R: Pigment RED 4 (Cl 12085);

[0355] - CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);

[0356] - VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);

[0357] - COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);

[0358] - COSMENYL GREEN GG: Pigment GREEN 7 (Cl 74260);

[0359] - COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

[0360] Said pigments may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments may be composed in particular of particles comprising an inorganic core, at least one binder ensuring the fixation of organic pigments on the core, and at least one organic pigment covering at least partially the core.

[0361] The organic pigment can also be a lacquer. By lacquer, we mean colorants adsorbed onto insoluble particles, the whole thus obtained remaining insoluble during use.

[0362] The inorganic substrates on which the dyes are adsorbed are, for example, silica, calcium sodium borosilicate or calcium aluminium borosilicate.

[0363] Among the colorants, we can mention carminic acid. We can also mention the colorants known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).

[0364] As examples of lacquers, we can cite the product known under the following name: D & C Red 7 (CI 15 850 :1).

[0365] Said pigment may also be a special effects pigment. Special effects pigments are defined as pigments that generally create a non-uniform and changing colored appearance (characterized by a certain shade, vibrancy, and clarity) depending on the viewing conditions (light, temperature, viewing angles, etc.). They are thus distinguished from colored pigments that provide a uniform opaque, semi-transparent, or conventionally transparent tint.

[0366] There are several types of special effect pigments, those with a low refractive index such as fluorescent or photochromic pigments, and those with a higher refractive index such as mother-of-pearl, interference pigments or glitter.

[0367] Examples of special effect pigments include pearlescent pigments such as titanium-coated mica or bismuth oxychloride, colored pearlescent pigments such as titanium-coated mica and iron oxides, iron oxide-coated mica, titanium-coated mica, particularly ferric blue or chromium oxide, and titanium-coated mica with an organic pigment as defined above. previously, as well as pearlescent pigments based on bismuth oxychloride. Examples of pearlescent pigments include Cellini pearlescent pigments marketed by BASF (Mica-TiO2-lake), Prestige marketed by Eckart (Mica-TiO2), Prestige Bronze marketed by Eckart (Mica-Fe2O3), and Colorona marketed by Merck (Mica-TiO2-Fe2O3).

[0368] We can also mention gold-colored mother-of-pearl, notably marketed by BASF under the names Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); bronze mother-of-pearl, notably marketed by MERCK under the names Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super Bronze (Cloisonne); orange mother-of-pearl, notably marketed by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by MERCK under the names Passion Orange (Colorona) and Matte Orange (17449) (Microna); brown-tinted mother-of-pearl, notably marketed by BASF under the names Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); copper-tinted mother-of-pearl, notably marketed by BASF under the name Copper 340A (Timica);red-tinted mother-of-pearl, notably marketed by MERCK under the name Sienna fine (17386) (Colorona); yellow-tinted mother-of-pearl, notably marketed by BASF under the name Yellow (4502) (Chromalite); red-tinted mother-of-pearl with a gold sheen, notably marketed by BASF under the name Sunstone G012 (Gemtone); pink mother-of-pearl, notably marketed by BASF under the name Tan opale G005 (Gemtone);black mother-of-pearl with a gold sheen, notably marketed by BASF under the name Nu antique bronze 240 AB (Timica); blue mother-of-pearl, notably marketed by MERCK under the name Matte blue (17433) (Microna); white mother-of-pearl with a silver sheen, notably marketed by MERCK under the name Xirona Silver; and orange-pink-green-gold mother-of-pearl, notably marketed by MERCK under the name Indian summer (Xirona), and their mixtures.

[0369] As further examples of nacres, we can also mention particles comprising a borosilicate substrate coated with titanium oxide.

[0370] Particles with a glass substrate coated with titanium oxide are notably sold under the name METASHINE MC1080RY by the company TOYAL.

[0371] Finally, as examples of mother-of-pearl, polyethylene terephthalate flakes can also be cited, particularly those marketed by Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver flakes). Multilayer pigments based on synthetic substrates such as silica, calcium sodium borosilicate or calcium aluminium borosilicate.

[0372] Special effect pigments may also be selected from reflective particles, that is to say, in particular, particles whose size, structure, including the thickness of the layer(s) that constitute them and their physical and chemical nature, and surface condition, enable them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create, on the surface of the composition or mixture, when applied to the makeup support, highlights visible to the naked eye, that is to say, brighter points that contrast with their surroundings by appearing to shine.

[0373] Reflective particles can be selected so as not to significantly alter the coloring effect generated by the coloring agents associated with them, and more particularly so as to optimize this effect in terms of color rendering. They may, in particular, have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or reflection.

[0374] These particles can have various shapes, including being platelet-shaped or globular, particularly spherical.

[0375] Reflective particles, whatever their shape, may or may not have a multilayer structure and, in the case of a multilayer structure, for example at least one layer of uniform thickness, in particular of a reflective material.

[0376] When reflective particles do not have a multilayer structure, they can be composed, for example, of metal oxides, with the exception of aluminum oxides, in particular titanium or iron oxides obtained by synthesis.

[0377] When reflective particles have a multilayer structure, they may, for example, comprise a natural or synthetic substrate, in particular a synthetic substrate at least partially coated by at least one layer of a reflective material, in particular at least one metal or metallic material other than aluminum. The substrate may be monomaterial, multimaterial, organic and / or inorganic.

[0378] More specifically, it may be selected from glasses, ceramics, graphite, metal oxides, with the exception of aluminium oxides, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica and mixtures thereof, this list not being exhaustive.

[0379] The reflective material may include a layer of metal or a metallic material.

[0380] Reflective particles are described in particular in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0381] Again, as an example of reflective particles comprising a substrate Mineral coated with a layer of metal, we can also mention particles containing a borosilicate substrate coated with silver.

[0382] Silver-coated glass substrate particles in the form of wafers are sold under the name MICROGLASS METASHINE REFSX 2025 PS by the company TOYAL. Nickel / chromium / molybdenum alloy-coated glass substrate particles are sold under the names CRYSTAL STAR GF 550, GF 2525 by the same company.

[0383] Particles comprising a metallic substrate such as silver, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, titanium may also be used, said substrate being coated with at least one layer of at least one metallic oxide such as titanium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

[0384] One can cite as an example the bronze or copper powders coated with SiO2 marketed under the name VISIONAIRE by the company ECKART.

[0385] Other examples include non-substrate interference pigments such as liquid crystals (Wacker's Helicones HC) and interference holographic glitter (Spectratek's Geometry Pigments or Spectra f / x). Special effect pigments also include fluorescent pigments, whether daylight fluorescent or ultraviolet fluorescent, phosphorescent pigments, photochromic pigments, thermochromic pigments, and quantum dots, marketed, for example, by Quantum Dots Corporation.

[0386] The variety of pigments that can be used in the present invention makes it possible to obtain a rich palette of colors, as well as particular optical effects such as metallic, interference effects.

[0387] The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 µm, preferably between 20 nm and 80 µm, and more preferably between 30 nm and 50 µm.

[0388] The pigments can be dispersed in the composition by means of a dispersing agent, as described above.

[0389] Furthermore, said pigments can be surface-treated with an organic agent.

[0390] Thus, the surface-treated pigments useful within the scope of the invention are pigments that have undergone, totally or partially, a surface treatment of a chemical, electronic, electrochemical, mechanochemical, or mechanical nature, with an organic agent such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, pp. 53-64, before being dispersed in the composition according to the invention. These organic agents may, for example, be chosen from waxes, such as carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate motifs; alkanoamines; silicone compounds, for example silicones, in particular polydimethylsiloxanes; fluorinated organic compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.

[0391] The surface-treated pigments useful in the composition may also have been treated by a mixture of these compounds and / or have undergone several surface treatments.

[0392] The surface-treated pigments useful in the context of the present invention can be prepared using surface treatment techniques well known to those skilled in the art or found as such in the commercial market.

[0393] Preferably, the surface-treated pigments are covered by an organic layer.

[0394] The organic agent with which the pigments are treated can be deposited on the pigments by solvent evaporation, chemical reaction between the molecules of the surfactant or creation of a covalent bond between the surfactant and the pigments.

[0395] Surface treatment can thus be achieved, for example, by a chemical reaction of a surfactant with the surface of the pigments and the creation of a covalent bond between the surfactant and the pigments or fillers. This method is described in particular in US patent 4,578,266.

[0396] Preferably, an organic agent covalently linked to the pigments will be used.

[0397] The surface treatment agent may represent from 0.1 to 50% by weight of the total weight of the pigment treated on the surface, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 20% by weight of the total weight of the pigment treated on the surface.

[0398] Preferably, the surface treatments of the pigments are chosen from the following treatments:

[0399] - a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW;

[0400] - a Methicone treatment such as the SI surface treatment marketed by LCW;

[0401] - a Dimethicone treatment such as the Covasil 3.05 com- surface treatment marketed by LCW;

[0402] - a Dimethicone / Trimethylsiloxysilicate treatment as the surface treatment Covasil 4.05 marketed by LCW;

[0403] - a Magnesium Myristate treatment such as the MM com surface treatment marketed by LCW;

[0404] - an Aluminium Dimyristate treatment such as the MI com surface treatment marketed by Miyoshi;

[0405] - a Perfluoropolymethylisopropyl ether treatment as a surface treatment FHC marketed by LCW;

[0406] - an Isostearyl Sebacate treatment such as the commercially available HS surface treatment by Miyoshi;

[0407] - a Perfluoroalkyl Phosphate treatment as a PF surface treatment marketed by Daito;

[0408] - an acrylate / dimethicone copolymer and perfluoalkyl phosphate treatment such as the FSA surface treatment marketed by Daito;

[0409] - a Polymethylhydrogen siloxane / Perfluoroalkyl Phosphate treatment such as the FS01 surface treatment marketed by Daito;

[0410] - an Acrylate / Dimethicone Copolymer treatment as the surface treatment ASC marketed by Daito;

[0411] - an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito;

[0412] - an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito;

[0413] - a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito.

[0414] Preferably, said pigments may be selected from mineral, mixed mineral-organic or organic pigments.

[0415] In one embodiment of the invention, said pigments are organic pigments, preferably organic pigments surface-treated with an organic agent selected from silicone compounds. In another embodiment of the invention, said pigments are mineral pigments.

[0416] According to a particular embodiment, composition C used in the process according to the invention comprises at least one pigment comprising aluminum other than pigments comprising at least one aluminosilicate and at least one pigment other than pigments comprising aluminum according to the invention. Direct colorant

[0417] Composition C used in the process according to the invention may further comprise one or more direct dye(s) different from the agents colorants containing aluminum as previously described.

[0418] By "direct dye" we mean natural and / or synthetic dyes, different from oxidation dyes. These are dyes that will diffuse superficially onto the fiber.

[0419] They can be ionic or non-ionic, preferably cationic or non-ionic.

[0420] Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in mixtures.

[0421] Direct dyes are preferably cationic direct dyes. Examples include the hydrazono cationic dyes of formulas (XIII) and (XIV), and the azo cationic dyes (XV) and (XVI) below:

[0422] (XIII),

[0423] (XIV), Her-C <Ra)=N-N(Rb)-M Q [°424] [°425] Ar^-Ar”. Q- <XVI)’

[0426] formulas (XIII) to (XVI) in which:

[0427] - Het+ represents a cationic heteroaryl radical, preferentially with a ca charge endocyclic tionic such as imidazolium, indolium, or pyridinium, possibly preferentially substituted by at least one (Ci-C8)alkyl group such as methyl;

[0428] - Ar+ represents an aryl radical, such as phenyl or naphthyl, with a cationic charge exocyclic preferentially ammonium particularly tri(Ci-C8)alkyl-ammonium such as trimethylammonium;

[0429] - Ar represents an aryl group, in particular phenyl, possibly substituted, preferably by one or more electron-donating groups such as i) (CrC8)alkyl possibly substituted, ii) (CrC8)alkoxy possibly substituted, iii) (di)(Ci-C8)(alkyl)amino possibly substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) N-(Ci-C8)alkyl-N-aryl(Ci-C8)alkylamino possibly substituted or else Ar represents a julolidine group;

[0430] - Ar” represents a (hetero)aryl group possibly substituted such that phenyl or pyrazolyl, possibly substituted, preferably by one or more (CrC8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (CrC8) groups

[0431]

[0432]

[0433]

[0434]

[0435]

[0436]

[0437]

[0438]

[0439]

[0440]

[0441]

[0442]

[0443] )alkoxy or phenyl; - Ra and Rb, identical or different, representing a hydrogen atom or a (CrC8)alkyl group possibly substituted, preferably by a hydroxyl group; or the substituent Ra with a substituent of Het+ and / or Rb with a substituent of Ar together form with the atoms which bear them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (CrC4)alkyl group possibly substituted by a hydroxyl group; - Q- represents an organic or mineral anionic counter-ion such as a halide or an alkyl sulfate. In particular, one may cite the endocyclic cationic direct dyes of azo and hydrazono of formula (XIII) to (XVI) as defined above; more particularly, the endocyclic cationic direct dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP-714954; preferably the following direct dyes: Formulas (XVII) and (XVIII) in which: - R1 represents an (Ci-C4)alkyl group such as methyl; - R2 and R3, whether identical or different, represent a hydrogen atom or an (Ci-C4)alkyl group such as methyl; and - R4 represents a hydrogen atom or an electron-donating group such as (Ci-C8)alkyl possibly substituted, (CrC8)alkoxy possibly substituted, (di)(CrC8)(alkyl)amino possibly substituted on the alkyl group(s) by a hydroxyl group; particularly R4 is a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferably CH, - Q- is an anionic counter ion as defined previously, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl. In particular, colorants of formula (XV) and (XVI) are chosen from the Basic

[0444]

[0445]

[0446]

[0447] Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives with Q' an anionic counter ion as defined above, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl. Direct dyes can be selected from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly called "acid" direct dyes because of their affinity for alkali substances. Anionic direct dyes are defined as any direct dye having in its structure at least one CO2R or SO3R substituent, where R designates a hydrogen atom or a cation from a metal or an amine, or an ammonium ion. Anionic dyes can be selected from acidic nitro direct dyes, acidic azo dyes, acidic azinic dyes, acidic triarylmethanic dyes, acidic indoamine dyes, acidic anthraquinone dyes, indigoids, and acidic natural dyes. Examples of acid dyes useful to the invention include dyes with the following formulas: (XIX), (XIX'), (XX), (XX'), (XXI), (XXI'), (XXII), (XXII'), (XXIII), (XXIV), (XXV) and (XXVI): a. Diaryl anionic azo dyes of formula (XIX) or (XIX'):

[0448]

[0449]

[0450]

[0451]

[0452]

[0453]

[0454] formulas (XIX) and (XIX') in which: - R7, R8, R9, Rio, R'7, R's, R'9 and R'i0, whether identical or different, represent a hydrogen atom or a group chosen from: - alkyl; - alkoxy, alkylthio; - hydroxy, mercapto; - nitro, nitroso;

[0455] - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing atony of hydrogen, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

[0456] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0457] - (O)CO—, M+ with M+ as defined above;

[0458] - R”-S(O)2-, with R” representing a hydrogen atom, an alkyl group, a aryl group, (di)(alkyl)amino, aryl(alkyl)amino; preferably a phenylamino or phenyl group;

[0459] - R'”-S(O)2-X'- with R”' representing an alkyl group, possibly aryl substituted, X' as defined previously;

[0460] - (di)(alkyl)amino;

[0461] - aryl(alkyl)amino optionally substituted by one or more selected groups among i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+ and iv) alkoxy with M+ as defined previously;

[0462] - heteroaryl possibly substituted; preferably a benzo- group thiazolyl;

[0463] - cycloalkyl, in particular cyclohexyl;

[0464] - Ar-N=N- with Ar representing a possibly substituted aryl group; pre differentially a phenyl possibly substituted by one or more alkyl groups, (O)2S(O-)-, M+ or phenylamino;

[0465] - or two contiguous groups R7 with R8 or R8 with R9 or R9 with R10 together form a fused group benzo A'; and R'7 with R'8 or R'8 with R'9 or R'9 with R'1O together form a fused group benzo B'; with A' and B' possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; vüi) R°-X'-C(X)-; ix) R°-X'-C(X)-X”-; x) Ar-N=N- and xi) aryl(alkyl)amino possibly substituted; with M+, R°, X, X', X” and Ar as defined above;

[0466] - W represents a sigma bond, an oxygen atom, a sulfur atom, or a radical divalent i) -NR- with R as defined above, or ii) methylene -C(Ra)(Rb)- with Ra and Rb identical or different, representing a hydrogen atom or an aryl group, or Ra and Rb together with the carbon atom bearing them form a spiro cycloalkyl; preferably W represents a sulfur atom or Ra and Rb together form a cyclohexyl;

[0467] it being understood that formulas (XIX) and (XIX') comprise at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical (O)CO-, M+ on one of the rings A, A', B, B' or C; preferably sodium sulfonate.

[0468] A titre d’exemple de colorants de formule (XIX) on peut citer : Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2 ; Food yellow 3 ou sunset yellow;

[0469] et à titre d’exemple de colorants de formule (XIX’) on peut citer : Acid Red 111, Acid Red 134, Acid yellow 38 ;

[0470] b) les colorants azo anioniques pyrrazolone de formule (XX) et (XX’) :

[0472]

[0473] formulas (XX) and (XX') in which:

[0474] - Ru, Rn and Rn, whether identical or different, represent a hydrogen atom, halogen, an alkyl group or -(O)2S(O-), M+ with M+ as defined previously;

[0475] - RM represents a hydrogen atom, an alkyl group or a group - C(O)O-, M+ with M+ as defined previously;

[0476] - Rb represents a hydrogen atom;

[0477] - Ri6 represents an oxo group in which case R'i6 is absent, or else R[5 with R[6 together form a double bond;

[0478] - Rn and Ri8, whether identical or different, represent a hydrogen atom, or a group chosen from:

[0479] - (O)2S(O-)-, M+ with M+ as defined above;

[0480] - Ar-OS(O)2- with Ar representing an aryl group possibly substituted; preferably a phenyl possibly substituted by one or more alkyl groups;

[0481] - R19 and R20 together form either a double bond or a benzo D' group, possibly substituted;

[0482] - R' i6, R' 19 and R'2O, identical or different, represent a hydrogen atom or a alkyl group, or hydroxy;

[0483] - R2i represents a hydrogen atom, an alkyl group, or alkoxy;

[0484] - Ra and Rb, whether identical or different, are as defined above, preferably Ra represents a hydrogen atom and Rb represents an aryl group;

[0485] - Y represents either a hydroxy group or an oxo group;

[0486] - - * * » represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group;

[0487] it being understood that the formulas (XX) and (XX') comprise at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical -C(O)O-, M+ on one of the rings D or E; preferably sodium sulfonate;

[0488] Examples of colorants of formula (XX) include: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and examples of colorants of formula (XX') include: Acid Yellow 17;

[0489] c) the anthraquinone dyes of formula (XXI) and (XXI'):

[0490] (XXI),

[0491] (XXI'),

[0492] formulas (XXI) and (XXI') in which:

[0493] - R22, R23, R24, R25, R26 and R27, whether identical or different, represent an atom of hydrogen, halogen, or a group chosen from:

[0494] - alkyl;

[0495] - hydroxy, mercapto;

[0496] - alkoxy, alkylthio;

[0497] - aryloxy or arylthio possibly substituted, preferably substituted by a or several groups chosen from alkyl and (O)2S(O-)-, M+ with M+ as defined previously;

[0498] - aryl(alkyl)amino optionally substituted by one or more selected groups among alkyl and (O)2S(O-)-, M+ with M+ as defined previously;

[0499] - (di)(alkyl)amino;

[0500] - (di)(hydroxyalkyl)amino

[0501] - (O)2S(O-)-, M+ with M+ as defined above;

[0502] - Z' represents a hydrogen atom or an NR28R29 group with R2s and R29, identical or different, represent a hydrogen atom or a group chosen from:

[0503] - alkyl;

[0504] - polyhydroxyalkyl such as hydroxyethyl;

[0505] - aryl possibly substituted by one or more particularly i) groups alkyl such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O-)-, M+ with M+ as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R°, X, X' and X” as defined previously, preferably R° represents an alkyl group;

[0506] - cycloakyl, in particular cyclohexyl;

[0507] - Z represents a group chosen from hydroxy and NR'28R'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined previously;

[0508] it being understood that formulas (XXI) and (XXI') comprise at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical -C(O)O-, M+; preferably sodium sulfonate;

[0509] Examples of colorants of formula (XXI) include: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT violet No. 2; and examples of colorants of formula (XXI') include: Acid Black 48;

[0510] d) Nitrated dyes of formula (XXII), (XXII'):

[0513] formulas (XXII) and (XXII') in which:

[0514] - R30, R31 and R32, whether identical or different, represent a hydrogen atom, halogen, or a group selected from:

[0515] - alkyl;

[0516] - alkoxy possibly substituted by one or more hydroxy groups, alkylthio possibly substituted by one or more hydroxy groups;

[0517] - hydroxy, mercapto;

[0518] - nitro, nitroso;

[0519] - polyhalogenoalkyl;

[0520] - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X' ' - with R° ; X, X' and X” as defined previously;

[0521] - (O)2S(O-)-, M+ with M+ as defined above;

[0522] - (O)CO—, M+ with M+ as defined above;

[0523] - (di)(alkyl)amino;

[0524] - (di)(hydroxyalkyl)amino;

[0525] - heterocycloalkyl such as piperidino, piperazino or morpholino; particularly R 30, R31 and R32 represent a hydrogen atom;

[0526] - Rc and Rd, whether identical or different, represent a hydrogen atom or a alkyl group;

[0527] - W is as defined above; W particularly represents a grouping -NH-;

[0528] - ALK represents a linear or branched divalent alkylene group, in Ci-C6; particularly ALK represents a grouping -CH2-CH2-;

[0529] - n is equal to 1 or 2;

[0530] - p represents an integer between 1 and 5 inclusive;

[0531] - q represents an integer between 1 and 4 inclusive;

[0532] - u is equal to 0 or 1;

[0533] - when n equals 1, J represents a nitro or nitroso group; particularly nitro;

[0534] - when n equals 2, J represents an oxygen atom, a sulfur atom, or a divalent radical -S(0)m- with m representing an integer 1 or 2; preferably J represents a radical -SO2-;

[0535] - M' represents a hydrogen atom or a cationic counter-ion;

[0536] - .... .... present or absent represents a benzo group possibly replaced by one or more R30 groups as defined above,

[0537] it being understood that formulas (XXII) and (XXII') comprise at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical -C(O)O-, M+; preferably sodium sulfonate.

[0538] By way of example of colorants of formula (XXII) the following may be cited: Acid Brown 13; Acid Orange 3; by way of example of colorants of formula (XXII') the following may be cited: Acid Yellow 1, Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2(4'-N,N(2'-hydroxyethyl)amino-2'-nitro)aniline ethanesulfonic acid, 4-[3-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C yellow 7;

[0539] e) triarylmethane dyes of formula (XXIII):

[0540] (XXIII),

[0541] formula (XXIII) in which:

[0542] - R33, R34, R35 and R36, whether identical or different, represent a hydrogen atom or a group chosen from alkyl, possibly substituted aryl and possibly substituted arylalkyl; particularly an alkyl and benzyl group possibly substituted by an (O)mS(O-)-, M+ group with M+ and m as defined above;

[0543] - R37, R38, R39, R4o, R4i, R42, R43 and R^, identical or different, represent an atom of hydrogen or a group chosen from:

[0544] - alkyl;

[0545] - alkoxy, alkylthio;

[0546] - (di)(alkyl)amino;

[0547] - hydroxy, mercapto;

[0548] - nitro, nitroso;

[0549] - R°-C(X)-X'-, R°-X' -C(X)-, R°-X'-C(X)-X' ' - with R° representing an atom of hydrogen, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

[0550] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0551] - (O)CO—, M+ with M+ as defined above;

[0552] - or two contiguous groups R4| with R42 or R42 with R43 or R43 with R^ together form a fused benzo group: I'; with I' possibly substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2 S(O-)-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X”-; with M+, R°, X, X', X” as defined above;

[0553] particularly R37 to R40 represent a hydrogen atom, and R4[ to R44, identical or different, represent a hydroxyl group or (O)2S(O-)-, M+; and when R43 with R^ together form a benzo group, it is preferentially substituted by a grouping (O)2S(O-)- ;

[0554] provided that at least one of the rings G, H, I or I' comprises at least one sulfonate radical (O)2S(O-)- or one carboxylate radical -C(O)O-; preferably sulfonate.

[0555] Examples of colorants of formula (XXIII) include: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50.

[0556] f) xanthene-derived dyes of formula (XXIV):

[0558] formula (XXIV) in which:

[0559] - R45, R46, R47 and R48, whether identical or different, represent a hydrogen atom or an atom of halogen;

[0560] - R49. R50, R51 and R52, whether identical or different, represent a hydrogen atom, halogen, or a group selected from:

[0561] - alkyl;

[0562] - alkoxy, alkylthio;

[0563] - hydroxy, mercapto;

[0564] - nitro, nitroso;

[0565] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0566] - (O)CO—, M+ with M+ as defined above;

[0567] particularly R49, R50, R51 and R52 represent a hydrogen or halogen atom

[0568] - G represents an oxygen atom, a sulfur atom, or an NRe group with Re such that defined previously; in particular G represents an oxygen atom;

[0569] - L represents an O-, M+ alkoxide; an S-, M+ thioalkoxide or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined previously; M+ is particularly sodium or potassium;

[0570] - L' represents an oxygen atom, a sulfur atom, or an ammonium group: N+RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an alkyl group, possibly substituted aryl; L' particularly represents an oxygen atom or a phenylamino group possibly substituted by one or more alkyl groups or (O)mS(O-)-, M+ with m and M+ as defined previously;

[0571] - Q and Q', identical or different, represent an oxygen or sulfur atom; in particular Q and Q' represent an oxygen atom;

[0572] - M+ is as defined previously.

[0573] As an example of colorants of formula (XXIV) we can cite: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[0574] g) dyes derived from indole of formula (XXV):

[0575] (XXV),

[0576] formula (XXV) in which:

[0577] - R53, R54, R55, R56, R57, R58, R59 and R60, whether identical or different, represent an atom of hydrogen or a group chosen from:

[0578] - alkyl;

[0579] - alkoxy, alkylthio;

[0580] - hydroxy, mercapto;

[0581] - nitro, nitroso;

[0582] - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing an atom of hydrogen, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

[0583] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0584] - (O)CO—, M+ with M+ as defined above;

[0585] - G represents an oxygen atom, a sulfur atom, or an NRe group with Re such that defined previously; in particular G represents an oxygen atom;

[0586] - Ri and Rh, whether identical or different, represent a hydrogen atom or a alkyl group;

[0587] it being understood that the formula (XXV) comprises at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical -C(O)O-, M+; preferably sodium sulfonate.

[0588]

[0589]

[0590] Examples of colorants with formula (XXV) include: Acid Blue 74; h) quinoline-derived colorants with formula (XXVI):

[0591] formula (XXVI) in which:

[0592] - R6i represents a hydrogen atom, a halogen atom or an alkyl group;

[0593] - R62, R63, and RM, whether identical or different, represent a hydrogen atom or a group (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counter-ion;

[0594] or R6[ with R62, or R6[ with R64, together form a benzo group possibly substituted by one or more (O)2S(O-)- groups, M+ with M+ representing a hydrogen atom or a cationic counter-ion;

[0595] it being understood that formula (XXVI) comprises at least one sulfonate radical (O)2 S(O-)-, M+ preferably sodium sulfonate.

[0596] Examples of colorants of formula (XXVI) include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0597] Among the natural direct dyes that can be used according to the invention are lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine, and orceins. Extracts or decoctions containing these natural dyes, and in particular henna-based poultices or extracts, can also be used.

[0598] Preferably, the direct dyes are chosen from among the anionic direct dyes.

[0599] The direct colorant(s) may be present in a total quantity ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight relative to the total weight of composition C. Non-carboxylic anionic thickening agent

[0600] Composition C used in the process according to the invention may further comprise at least one non-carboxylic anionic thickening agent.

[0601] For the purposes of the present invention, "non-carboxylic agent" means an agent that does not include a carboxylic acid (-COOH) or carboxylate (-COO) function.

[0602] For the purposes of this invention, a thickening agent is defined as a compound which increases the viscosity of a composition into which it is introduced at a concentration of 0.05% by weight relative to the total weight of the composition, by at least 20 cps, preferably by at least 50 cps, at room temperature (25°C), at atmospheric pressure and at a shear rate of 1 s⁻¹ (the viscosity can be measured using a cone / plate viscometer, Haake R600 rheometer or similar).

[0603] Preferably, the non-carboxylic anionic thickening agent(s) are chosen from non-carboxylic anionic polymers, more preferably from anionic polymers with sulfonic group(s).

[0604] For the purposes of this invention, anionic polymer means a polymer comprising one or more anionic or anionizable groups and not comprising any cationic or cationizable group.

[0605] Advantageously, the non-carboxylic anionic thickening agent(s) are chosen from anionic polymers comprising at least one monomer with ethylenic unsaturation and a sulfonic group, in free form or partially or totally neutralized.

[0606] These polymers can be crosslinked or non-crosslinked. They are preferably crosslinked.

[0607] These polymers may be associative or non-associative, preferably non-associative.

[0608] It is recalled that "associative polymers" are polymers capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

[0609] Their chemical structure includes more particularly at least one hydrophilic zone and at least one hydrophobic zone.

[0610] By "hydrophobic group" is meant a hydrocarbon chain radical or polymer, saturated or unsaturated, linear or branched, comprising at least 8 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms and more preferably 18 to 30 carbon atoms.

[0611] Preferably, the hydrocarbon group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, or decyl alcohol. It may also refer to a hydrocarbon polymer such as, for example, polybutadiene.

[0612] Monomers with ethylenic unsaturation and a sulfonic group are selected in particular from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci-C22)alkylsulfonic acids, N-(Ci-C22)alkyl(meth)acrylamido-(Ci-C22)alkylsulfonic acids such as undecyl-acrylamido-methane-sulfonic acid and their partially or totally neutralized forms.

[0613] More preferably, (meth)acrylamido(Ci-C22) alkylsul- acids will be used funic acids such as, for example, acrylamido-methane-sulfonic acid, acrylamido-ethane-sulfonic acid, acrylamido-propane-sulfonic acid, 2-acrylamido-2-methylpropane-sulfonic acid, methacrylamido-2-methylpropane-sulfonic acid, 2-acrylamido-n-butane-sulfonic acid, 2-acrylamido-2,4,4-trimethylpentane-sulfonic acid, 2-methacrylamido-dodecyl-sulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptane-sulfonic acid, as well as their partially or totally neutralized forms.

[0614] In particular, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or totally neutralized forms will be used.

[0615] Among the copolymers of 2-acrylamido-2-methylpropane sulfonic acid, mention may be made of crosslinked copolymers of 2-acrylamido-2-methylpropane sulfonic acid and partially or totally neutralized acrylamide, and in particular mention may be made of the product described in Example 1 of document EP 503 853 and reference may be made to this document for information relating to these polymers.

[0616] We can also mention copolymers of 2-acrylamido-2-methylpropane sulfonic acid or its salts and hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT 10 by the company SEPPIC (INCI name: hydroxyethyl-lacrylate / sodium acryloyldimethyl taurate copolymer).

[0617] Associative AMPS polymers may, in particular, be selected from statistically associative AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine, and such as those described in patent application WO 00 / 31154 (forming an integral part of the content of the description). These polymers may also contain other ethylenically unsaturated hydrophilic monomers selected, for example, from derivatives of (meth)acrylic acids, such as their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, or mixtures of these compounds.

[0618] Preferred polymers of this family are chosen from among associative copolymers of AMPS and at least one hydrophobic monomer with ethylenic unsaturation.

[0619] These same copolymers may further contain one or more ethylenically unsaturated monomers without a fatty chain such as (meth)acrylic acid derivatives, in particular their esters obtained with monoalcohols or mono- or poly-alkylene glycols, (meth)acrylamides, vinylpyrrolidone, or mixtures of these compounds.

[0620] These copolymers are described in particular in patent application EP-A-750899, US patent 5089578 and in the following publications by Yotaro Morishima:

[0621] - “Self-assembly amphiphilic polyelectrolytes and their nanostructures - Chinese Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336. » ;

[0622] - “Miscelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, Vol. 33, No. 10 (2000), 3694-3704”;

[0623] - “Solution properties of miscelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte: known effects on rheological behavior - Langmuir, Vol. 16, No. 12, (2000) 5324-5332”;

[0624] - “Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers - Polym. Preprint, Div. Polym. Chem., 40(2), (1999), 220-221”.

[0625] Among these polymers, we can mention:

[0626] - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS motifs and 40 to 85% by weight of (C8-Ci6)alkyl(meth)acrylamide or (C8-Ci6)alkyl(meth)acrylate motifs relative to the polymer, such as those described in application EP-A750 899;

[0627] - terpolymers comprising from 10 to 90 mol% of acrylamide motifs, from 0.1 to 10 mole percent of AMPS motifs and 5 to 80 mole percent of n-(C6-Ci8)alkylacrylamide motifs, such as those described in US patent 5089578.

[0628] We can also mention copolymers of totally neutralized AMPS and dodecyl methacrylate as well as copolymers of uncrosslinked and crosslinked AMPS and n-dodecylmethacrylamide, such as those described in the articles by Morishima cited above.

[0629] Preferably, the non-carboxylic anionic thickening agent(s) are selected from the sodium 2-acrylamido-2-methylpropane-sulfonate / hydroxyethylacrylate copolymer, marketed by SEPPIC (INCI name: hydroxyethyl-lacrylate / sodium acryloyldimethyl taurate copolymer).

[0630] Advantageously, the total amount of the non-carboxylic anionic thickening agent(s) ranges from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight, better from 0.1 to 5% by weight, and better still from 0.1 to 3% by weight, relative to the total weight of composition C. Associative polymers

[0631] Composition C according to the invention may further comprise at least one associative polymer different from the compound having at least one carboxylic function and different from the non-carboxylic anionic thickening agent as defined above.

[0632] It is recalled that "associative polymers" are polymers capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

[0633] Their chemical structure includes more particularly at least one hy- zone Drosophila and at least one hydrophobic area.

[0634] By "hydrophobic group" is meant a hydrocarbon chain radical or polymer, saturated or unsaturated, linear or branched, comprising at least 10 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms and more preferably 18 to 30 carbon atoms.

[0635] Preferably, the hydrocarbon group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, or decyl alcohol. It may also refer to a hydrocarbon polymer such as, for example, polybutadiene.

[0636] Associative polymers can be of non-ionic, anionic, cationic or amphoteric nature.

[0637] Preferably, the associative polymer(s) are chosen from anionic associative polymers.

[0638] Among the anionic-type associative polymers, we can mention:

[0639] - (a) those comprising at least one hydrophilic motif, and at least one ether motif of fatty chain allyl, more particularly those whose hydrophilic motif is made up of an unsaturated ethylenic anionic monomer, more particularly still of a vinylic carboxylic acid and especially of an acrylic acid or a methacrylic acid or mixtures thereof.

[0640] Among these anionic associative polymers, polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, 5 to 60% by weight of lower alkyl (meth)acrylates, 2 to 50% by weight of fatty chain allyl ether, and 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylene monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

[0641] Among these, crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 OE) stearyl alcohol ether (Steareth 10) are particularly preferred, especially those sold by the company CIBA under the names SALCARE SC80® and SALCARE SC90® which are aqueous emulsions at 30% of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40 / 50 / 10).

[0642] - (b) those comprising i) at least one hydrophilic motif of the carboxylic acid type unsaturated olefinic, and ii) at least one hydrophobic motif of the alkyl (C10-C30) ester type of unsaturated carboxylic acid.

[0643] Alkyl (C10-C30) esters of unsaturated carboxylic acids useful to the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and the corresponding methacrylates ponders, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

[0644] Anionic polymers of this type are described and prepared, for example, according to US patents 3,915,921 and 4,509,949.

[0645] Among this type of anionic associative polymers, more particularly those made up of 95 to 60% by weight of acrylic acid (hydrophilic motif), 4 to 40% by weight of C10-C30 alkyl acrylate (hydrophobic motif), and 0 to 6% by weight of polymerizable crosslinking monomer will be used, or those made up of 98 to 96% by weight of acrylic acid (hydrophilic motif), 1 to 4% by weight of C10-C30 alkyl acrylate (hydrophobic motif), and 0.1 to 0.6% by weight of polymerizable crosslinking monomer such as those described above.

[0646] Among the aforementioned polymers, the products sold by GOODRICH under the trade names PEMULEN TRI®, PEMULEN TR2®, CARBOPOL 1382®, and even more preferably PEMULEN TRI®, and the product sold by SEPPIC under the name COATEX SX®, are particularly preferred according to the present invention.

[0647] We can also mention the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer marketed under the name Acrylidone LM by the ISP Company.

[0648] - (c) C30-C38 maleic anhydride / α-olefin / alkyl maleate terpolymers such that the product (maleic anhydride / C30-C38 α-olefin / isopropyl maleate copolymer) sold under the name PERFORMA V 1608® by the company NEWPHASE TECHNOLOGIES.

[0649] - (d) acrylic terpolymers comprising:

[0650] i) about 20 to 70% by weight of an unsaturated α,[3-monoethylenic [α],

[0651] ii) about 20 to 80% by weight of a non-surfactant α,[3-monoethylenic] unsaturation monomer other than [α],

[0652] iii) approximately 0.5 to 60% by weight of a non-ionic monourethane which is the reaction product of a monohydric surfactant with a monoethylenic unsaturation monoisocyanate,

[0653] such as those described in patent application EP-A-0173109 and more particularly that described in Example 3, namely, a methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate terpolymer of ethoxylated behenyl alcohol (40 OE) in 25% aqueous dispersion.

[0654] - (e) copolymers comprising among their monomers a carboxylic acid with saturation α,[3-monoethylenic and an ester of carboxylic acid with unsaturation α,[3-monoethylenic and an oxyalkylated fatty alcohol.

[0655] Preferably these compounds also comprise as a monomer an ester of α,p-monoethylenic unsaturated carboxylic acid and C1-C4 alcohol.

[0656] As an example of this type of compound, we can cite ACULYN 22® sold by the company ROHM and HAAS, which is a methacrylic acid / ethyl acrylate / oxyalkylened stearyl methacrylate terpolymer, as well as ACULYN 88 also sold by the company ROHM and HAAS.

[0657] Advantageously, the associative polymer(s), different from compounds having at least one carboxylic function and different from the non-carboxylic anionic thickening agents previously described, are chosen from acrylic associative polymers, more preferably carboxylic acrylic associative polymers.

[0658] In a particularly preferred manner, the associative polymer(s), different from compounds having at least one carboxylic function and different from the previously described non-carboxylic anionic thickening agents, are chosen from copolymers comprising among their monomers an α,[3-monoethylenic unsaturation carboxylic acid and an ester of an α,[3-monoethylenic unsaturation carboxylic acid and an oxyalkylated fatty alcohol.

[0659] Advantageously, the total quantity of the associative polymer(s) different from the compound(s) having at least one carboxylic function and different from the non-carboxylic anionic thickening agent(s) as defined above ranges from 0.05 to 15% by weight, preferably from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight, and even more preferably from 0.1 to 1% by weight relative to the total weight of composition C. Organic solvents

[0660] Composition C according to the invention may comprise one or more organic solvents.

[0661] Examples of organic solvents include lower Ci-C4 alkanols such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols, in particular aromatic monoalcohols such as benzyl alcohol, phenoxyethanol, and mixtures thereof.

[0662] Organic solvents may be present in a total quantity of between 0.01 and 60% by weight, preferably between 0.05 and 50% by weight and more preferably inclusively between 0.1 and 45% by weight relative to the total weight of composition C.

[0663] Composition C used in the process according to the invention may be aqueous. The water content may range from 1 to 90% by weight, preferably from 10 to 80% by weight, more preferably from 20 to 75% by weight relative to the total weight of composition C. Additives

[0664] Composition C used in the process according to the invention may contain any adjuvant or additive usually used.

[0665] Among the additives that may be contained in the composition, we can mention reducing agents, softeners, antifoaming agents, moisturizing agents, UV filters, peptizers, perfumes, anionic, cationic, non-ionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers previously described, preservatives, silicones, oils, waxes other than silicones in wax form, and mixtures thereof.

[0666] The composition C used in the process according to the invention may be in particular in the form of a suspension, dispersion, gel, emulsion, in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion, or multiple (W / O / W or polyol / O / W or O / O / O), in the form of a cream, foam, stick, dispersion of vesicles in particular of ionic or non-ionic lipids, bi-phase or multi-phase lotion.

[0667] A person skilled in the art will be able to choose the appropriate pharmaceutical form, as well as its method of preparation, on the basis of their general knowledge, taking into account on the one hand the nature of the constituents used, in particular their solubility in the support, and on the other hand the application envisaged for the composition. Protocol

[0668] Composition C described above can be used on dry or wet hair, as well as on all types of hair, light or dark, natural or colored, permed, bleached or straightened.

[0669] According to a particular embodiment of the invention, the hair is washed before application of composition C.

[0670] Preferably, a washing, rinsing, wringing or drying step is carried out after the application of composition C to the hair.

[0671] More preferably, a drying step is implemented after the application of composition C to the hair.

[0672] Application to the hair can be carried out by any conventional means, in particular by means of a comb, a brush, a sponge or the fingers.

[0673] The application of composition C to the hair is generally carried out at room temperature (between 15 and 25 °C).

[0674] After applying composition C to the hair, one may wait between 1 minute and 6 hours, in particular between 1 minute and 2 hours, more particularly between 1 minute and 1 hour, more preferably between 1 minute and 30 minutes, before for example a washing, rinsing, spinning and / or drying stage.

[0675] After application of composition C, the hair may be left to dry or dried, for example at a temperature of 30 °C or higher.

[0676] The process according to the invention can thus include a step of applying heat to the hair using a heating tool.

[0677] The heat application step of the process of the invention can be carried out using a helmet, a hair dryer, a straightener or curling iron, a climazon...

[0678] Preferably, the heat application step of the process of the invention is carried out using a hair dryer.

[0679] When the process of the invention implements a step of applying heat to the hair, the step of applying heat to the hair takes place after the application of composition C to the hair.

[0680] During the heat application step on the hair, a mechanical action on the strands can be exerted such as combing, brushing, passing with fingers.

[0681] When the step of applying heat to the hair is carried out using a helmet or a hair dryer, the temperature is preferably between 30 and 110°C, preferably between 50 and 90°C.

[0682] When the step of applying heat to the hair is carried out using a straightening iron, the temperature is preferably between 110 and 220°C, preferably between 140 and 200°C.

[0683] In a particular embodiment, the process of the invention implements a step (c1) of applying heat using a helmet, a hair dryer or a climazon, preferably a hair dryer and a step (c2) of applying heat using a straightening or curling iron, preferably a straightening iron.

[0684] Step (cl) can be performed before step (c2).

[0685] During step (cl), also called the drying step, the hair can be dried, for example, at a temperature of 30°C or higher. In one particular embodiment, this temperature is higher than 40°C. In another particular embodiment, this temperature is higher than 45°C and lower than 110°C.

[0686] Preferably, if the hair is dried, it is dried not only with heat but also with an airflow. This airflow during drying helps to improve the individualization of the coating.

[0687] During drying, mechanical action on the strands can be exerted such as combing, brushing, passing with fingers.

[0688] During step (c2), the passage of the straightening or curling iron, preferably the straightening iron, may be carried out at a temperature ranging from 110 to 220°C, preferably between 140 and 200°C.

[0689] After the heating step, a shaping step can be implemented with For example, with a hair straightener, the temperature for the styling stage can be between 110 and 220°C, preferably between 140 and 200°C.

[0690] Preferably, the invention is a hair coloring process comprising the following steps: (i) the application to the hair of at least one composition C comprising:

[0691] - at least one (poly)carbodiimide compound as described above;

[0692] - at least one compound having at least one carboxylic function as described above previously; and

[0693] - at least one coloring agent comprising aluminum other than the agents colorants comprising at least one aluminosilicate as described above; then ii) optionally a processing time of said composition C on the hair of 1 to 30 minutes, preferably 1 to 20 minutes; then iii) optionally a step of washing, rinsing, wringing and / or drying said hair.

[0694] Preferably, composition C further comprises at least one non-carboxylic anionic thickening agent as described above.

[0695] Preferably, composition C further comprises at least one associative polymer as described above, different from the compound having at least one carboxylic function and different from the non-carboxylic anionic thickening agent as defined above.

[0696] Advantageously, the step of applying composition C to the hair is repeated several times.

[0697] According to a preferred embodiment, the coloring process according to the invention is a hair coloring process consisting of extemporaneously mixing at least two compositions A and B at the time of use to obtain a composition C and applying composition C to the hair, with: - composition A comprising at least one (poly)carbodiimide compound as described above; - composition B comprising at least one compound having at least one carboxylic function as described above,

[0698] composition A and / or composition B comprising at least one colouring agent comprising aluminium other than colouring agents comprising at least one aluminosilicate as described above. Composition A and / or composition B may optionally include at least one non-carboxylic anionic thickening agent as described above and / or at least one associative polymer as described above, different from the compound having at least one carboxylic function and different from the non-carboxylic anionic thickening agent as defined above.

[0699] Preferably, composition B comprises at least one colouring agent comprising aluminium other than colouring agents comprising at least one aluminosilicate as described above.

[0700] Preferably, composition A does not include at least one colouring agent comprising aluminium other than colouring agents comprising at least one aluminosilicate as described above.

[0701] According to this embodiment, compositions A and B are mixed preferably less than 15 minutes before application to the hair, more preferably less than 10 minutes before application, better less than 5 minutes before application.

[0702] The weight ratio between composition A and composition B is preferably from 0.1 to 10, preferably from 0.2 to 5, better from 0.5 to 2, or even from 0.6 to 1.5. In a particular embodiment, the weight ratio between composition A and composition B is equal to 1.

[0703] According to a particular embodiment, the hair coloring process according to the invention is a hair coloring process consisting of mixing at least two compositions A and B extemporaneously at the time of use to obtain a composition C, and applying composition C to the hair, with: - composition A comprising at least one (poly)carbodiimide compound as described above; and - composition B comprising at least one compound having at least one carboxylic function as described above, and at least one colouring agent comprising aluminium other than colouring agents comprising at least one aluminosilicate as described previously; Composition A and / or composition B optionally comprising at least one non-carboxylic anionic thickening agent as described above and / or at least one associative polymer as described above, different from the compound having at least one carboxylic function and different from the non-carboxylic anionic thickening agent as defined above.

[0704] Advantageously, composition A and / or composition B comprises (include) at least one non-carboxylic anionic thickening agent as described above, at least one associative polymer as described above, different from the compound having at least one carboxylic function and different from the non-carboxylic anionic thickening agent as defined above.

[0705] The total amount of the (poly)carbodiimide compound(s) preferably ranges from 0.01 to 40% by weight, more preferably from 0.1 to 30% by weight, better from 0.5 to 20% by weight, even more preferably from 1 to 12% by weight relative to the total weight of composition A.

[0706] The total quantity of the compound(s) having at least one carboxylic function will preferably from 0.2 to 60% by weight, more preferably from 1 to 40% by weight, better still from 1 to 30% by weight, and even more preferably from 2 to 20% by weight relative to the total weight of composition B.

[0707] The total quantity of the aqueous dispersion(s) of polymer particle(s) selected from polyurethanes, acrylic polymers, and their mixtures is preferably from 0.2 to 60% by weight, more preferably from 1 to 50% by weight, better still from 1 to 40% by weight, and even more preferably from 2 to 30% by weight relative to the total weight of composition B.

[0708] According to a particular embodiment, the total quantity of the aqueous dispersion(s) of acrylic polymer particle(s) preferably ranges from 0.2 to 60% by weight, more preferably from 1 to 50% by weight, better still from 1 to 40% by weight, and even more preferably from 2 to 30% by weight relative to the total weight of composition B. Multi-compartment device (kit)

[0709] The present invention also relates to a hair coloring device comprising several compartments containing: - in a first compartment, a composition A comprising: a) at least one (poly)carbodiimide compound as described above,

[0710] - in a second compartment, a composition B comprising: b) at least one compound comprising at least one carboxyl group as described above,

[0711] Composition A and / or Composition B comprising: c) at least one colouring agent comprising aluminium other than colouring agents comprising at least one aluminosilicate.

[0712] The present invention will now be described more specifically by means of examples, which are in no way limiting of the scope of the invention. However, the examples allow for the support of specific features, variants, and preferred embodiments of the invention. EXAMPLES

[0713] The (poly)carbodihnide(s) of the invention are accessible by synthetic methods known to those skilled in the art, from commercial products or from reagents synthesizable according to chemical reactions also known to those skilled in the art. Examples include the book *Sciences of Synthesis - Houben - Weyl Methods of Molecular Transformations*, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D-70469 Stuttgart, or US patent 4,284,730 or Canadian application CA 2,509,861.

[0714] More particularly the process for preparing (poly)carbodiimides of the invention implements in a first step a diisocyanate reagent (1): O=C=N-Li-N=C=O (1), formula (1) in which Li is as defined previously which reacts in the presence of a carboimidation catalyst (2) such as those described in US 4,284,730, in particular phosphorus catalysts especially chosen from among phospholene oxides and phospholene sulfoxides, diaza and oxazaphospholanes, preferably under an inert atmosphere (nitrogen or Argon), and in particular in a polar solvent preferably aprotic such as THF, glyme, diglyme, 1,4-dioxane, and DMF, at a temperature between room temperature and solvent reflux, preferably around 140 °C; to give rise to the carbodiimide diisocyanate compound (3): O=C=N-L1-(N=C=N-L1)nN=C=O (3), formula (3) in which Li and n are as defined above. Benzoyl halogen such as benzoyl chloride may be added to deactivate the catalyst.

[0715] To obtain "symmetrical" (poly)carbodiimides, in the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq) of nucleophilic reagent Ri-XrH, then with 0.5 eq of HEH reagent with Rb Xi and E as defined above, to give the "symmetrical" compound according to the invention (4): [Ri-X1-C(O)-NH-L1-(N=C=N-L1)n-NH-C(O)]2-E (4), formula (4) in which Rb Xb Lh n, and E are such as defined previously. According to one variant to obtain compound (4) from (3) it is possible to first add 0.5 eq. of HEH reagent, then 1 eq. of Ri-XrH reagent.

[0716] To obtain "asymmetric" (poly)carbodiimides, in the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq) of nucleophilic reagent Ri-XrH and then 1 eq of HEH reagent with Rb Xi and E as defined above, to give compound (5): R1-X1-C(O)-NH-L1-(N=C=N-L1)n-NH-C(O)-EH (5), formula (5) in which Rb Xb Lh n, and E are such as defined previously.

[0717] According to one variant for obtaining compound (5) from (3) it is possible to add first 1 eq. of reagent Ri-XrH, then 0.5 eq. of reagent HEH.

[0718] In a third step, compound (5) reacts with 1 eq. of compound (6) R2-X2-C(O)-NH-Li-(N=C=N-Li)zN=C=O (6), said compound (6) is prepared beforehand from compound (3'): O=C=N-L1-(N=C=N-L1)ZN=C=O (3'),

[0719] formula (3') in which Li and z are as defined previously which reacts with 1 eq of nucleophilic reagent R2-X2-H with Lb R2, X2, and z as defined previously, to give rise to the asymmetric compound (7): R1-X1-C(O)-NH-L1-(N=C=N-L1)n-NH-C(O)-EC(O)-NH-L1--(N=C=N-L1)z-NH-C(O) -X2-R2 (7),

[0720] Formula (7) in which Rb Xb Lb R2, X2, n, z and E are as defined previously.

[0721] It is also possible to react 1 molar equivalent of compound O=C=N-Li -(N=C=N-Li)zN=C=O (3') with 1 / w molar equivalent of HEH, then 1 eq. of nucleophilic reagent R2-X2-H to lead to compound (8): H-[EC(O)-NH-L1-(N=C=N-L1)z]w-NH-C(O)-X2-R2(8),

[0722] formula (8) in which Lb R2, X2, z and E are as defined previously, and w is an integer from 1 to 3, more preferably w = 1.

[0723] This latter compound (8) can then react with 1 eq of compound (4'): Ri-Xi-C(O)-NH-Li-(N=C=N-Li)nN=C=O (4'), (said compound (4') being able to be synthesized by reaction of 0.5 eq. of nucleophilic reagent Ri-XrH with 1 equivalent of compound (3)), to lead to the (poly)carbodihnide of the invention (9): Ri-X1-C(O)-NH-L1-(N=C=N-L1)n-NH-C(O)-[EC(O)-NH-L1-(N=C=N-L1)z]w-NH C(O)-X2-R2 (9), formula (9) in which Lb Rb Xb R2, X2, n, z, w, and E are such as defined previously.

[0724] (Poly)carbodiimide compounds, as well as all reaction intermediates and reactants, can be purified with conventional methods known to those skilled in the art, such as extraction with water and water-immiscible organic solvent, precipitation, centrifugation, filtration, and / or chromatography.

[0725] Example 1: Process for the synthesis of the (poly)carbodiimide compound

[0726] In a 500 mL three-necked flask equipped with a thermometer, a stirrer and a reflux tube, 50 g of dicyclohexylmethane 4,4'-diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-l-phenyl-lH-phosphole 1-oxide were introduced under stirring.

[0727] The reaction medium was heated to 140°C under nitrogen for 4 hours, following the reaction by infrared spectroscopy through the absorption of isocyanate functions between 2200 and 2300 cm1, then cooled to 120°C.

[0728] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol is introduced into the reaction medium while stirring. The temperature of 120°C is maintained until the complete disappearance of the isocyanate groups, monitored by infrared spectroscopy at 2200-2300 cm1, and then cooled to room temperature.

[0729] After cooling to room temperature, the reaction mixture is poured dropwise under vigorous stirring into a 500 mL glass beaker containing 85 g of distilled water to produce the desired product in the form of a translucent yellow liquid. Example 2

[0730] Compositions A, B1 and B2 as described in Table 1 below have been prepared: quantities are expressed in g of raw material as is / 100g, unless otherwise stated.

[0731] [Tables 1] Composition A Polycarbodihnide (1) 17.5 Hydroxyethyl acrylate / sodium acryloyl-dimethyl taurate copolymer (2) 3 Ethanol 20 Water q.s. 100

[0732] (1) synthesized according to the synthesis process described in Example 1 (at 40% of material active in water), (2) sold by the company SEPPIC under the name SEPINOV EMT10 (with 90% active material).

[0733] ​​[Tables2] Compositions B1 B2 Acrylates copolymer (3) 29.2 29.2 Acrylates / Steareth-20 methacrylate copolymer (4) 2.2 2.2 Synthetic Fluorphlogopite (and) Titanium dioxide (and) Tin oxide <5' 6 ma - Colouring agent comprising aluminium according to the invention (6) - 6 ma Amodimethicone 8.8 8.8 Dimethicone 10.2 10.2 Ethanol 3.8 3.8 Preservative(s) qs qs Water Qsp 100 Qsp 100

[0734] (3) sold by the company DAITO KASEI KOGYO under the trade name DAITOSOL 3000SLPN-PE1 (aqueous dispersion with 30% active ingredient),

[0735] (4) sold by the company ROHM and HAAS under the trade name ACULYN 22® (methacrylic acid / ethyl acrylate / oxyalkylated stearyl methacrylate terpolymer with 30% active ingredient),

[0736] (5) sold by ECKART under the trade name SYNCRYSTAL SOFT SILVER,

[0737] (6) sold by the company Siberline under the trade name Starbrite Reveal AQ 4172PA.

[0738] Two mixtures are then carried out. Composition A was mixed with each of compositions B1 and B2 at a mass ratio of 50 / 50 to obtain two compositions Cl and C2.

[0739] Thus, the process using composition Cl is a comparative process. The process using composition C2 is a process according to the invention. Protocol

[0740] Each of the compositions Cl and C2 is applied to strands of natural hair HT 4 (level 4), or to strands of dry natural hair 90% white (BN90), at a rate of 0.8g of composition per gram of strand. The hair strands are then blow-dried on medium heat while combing.

[0741] The hair strands are then stored at ambient temperature and humidity for 24 hours.

[0742] Lightening and coverage measurements were then carried out. These measurements were performed using a Minolta CM3600A Spectrophotometer (illuminant D65, angle 10°, specular component included). Color is defined according to the CIE L*a*b* system, in which L* represents color intensity, a* indicates the green / red color axis, and b* the blue / yellow color axis. Evaluation of lightening

[0743] The lightening is highlighted using the L* component. The higher the L* value, the lighter the color appears.

[0744] For these measurements, HT 4 (tone height 4) natural hair strands were used.

[0745] The results are summarized in Table 3 below.

[0746] [Tables3] Process implementing the composition Cl (comparative) C2 (invention) L* 29.8 56.0

[0747] It is clear that the hair strands treated with the process according to the invention have an L* value approximately twice as high as that of the hair strands treated with a comparative process.

[0748] Thus, the process according to the invention makes it possible to obtain a significantly lighter color. In other words, the colored coating obtained with the process according to the invention exhibits an improved level of lightening. Coverage assessment

[0749] The coverage of a composition is represented by the color difference AE obtained between strands of natural hair HT (tone height) 4 (dark hair), and strands of natural hair that are 90% white (very light hair), after coloring. The smaller the color difference AE, the better the coverage.

[0750] Thus, to determine coverage, the compositions used are applied to a strand of natural HT 4 hair and to a strand of natural hair that is 90% white. The higher the coverage of the composition, the closer the color results are on the strand of natural HT 4 hair and on the strand of natural hair that is 90% white.

[0751] The results are summarized in Table 4 below.

[0752] [Tables4] L* a* b* AE* Cl (HT 4 wick) 29.8 1.6 -0.9 41.1 Cl (BN90 wick) 68.0 0.5 14.2 C2 (HT 4 wick) 56.0 -0.1 0.1 4.6 C2 (BN90 wick) 60.4 -0.7 1.1

[0753] It is clear that a greater difference in colour is obtained between the BN90 and HT4 hair strands when treated with the comparative process than when treated with the process according to the invention.

[0754] Moreover, the ratio between the AE color differences (41.1 / 4.6) is approximately equal to 9. Thus, the process according to the invention makes it possible to obtain a coverage 9 times greater than that with the comparative process.

[0755] Consequently, the coloured coating obtained with the process according to the invention has significantly improved coverage.

Claims

Claims

1. A hair coloring process comprising applying to the hair at least one composition C comprising: - at least one (poly)carbodiimide compound; - at least one compound comprising at least one carboxylic acid function; and - at least one coloring agent comprising aluminum other than coloring agents comprising at least one aluminosilicate.

2. A process according to claim 1, characterized in that the (poly)carbodiimide compound(s) is / are selected from compounds of the following formula (I): X1 - A1 - Al1 - R2 - H1 AH in which: - X1 and X2 independently represent an oxygen atom O, a sulfur atom S, or an NH3 group; - R1 and R2 independently represent a group selected from a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatoms, or a group selected from alkoxysilyl groups.hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoal-kylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylal-kylsilyl, maleimidoalkylsilyl, sulfonylmylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide, and azacyclopropane, and a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatoms and by one or more groups selected from the alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl groups, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylmylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide,and azacyclopropane; - n denotes an integer from 1 to 1000; and - A is a monomer chosen from the compounds below:

3. A process according to claim 1, characterized in that the (poly)carbodiimide compound(s) is / are selected from the compounds of the following formula (II): (II), in which - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group; - Ri and R2 independently represent a hydrocarbon radical possibly interrupted by one or more heteroatom(s); - n and z denote an integer from 1 to 20, with n+z > 2, and w denotes an integer from 1 to 3; - Li independently represents a divalent aliphatic hydrocarbon radical in CrCi8, a cycloalkylene radical in C3-Ci5, a heterocycloalkylene group in C3-Ci2, or an arylene group in C6-Ci4, and mixtures thereof; - E independently represents a group chosen from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-, in which R3 and R4 independently represent a divalent hydrocarbon radical possibly interrupted by one or more heteroatoms; - R5 independently represents a covalent bond or a divalent saturated hydrocarbon radical, possibly interrupted by one or more heteroatoms; - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

4. A process according to claim 3, characterized in that the (poly)carbodiimide compound(s) is / are selected from compounds of formula (II) in which: - Xi and X2 independently represent an oxygen atom; - Ri and R2 are selected independently from dialkylaminoalcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, and mixtures thereof; - n and z denote an integer from 1 to 20, with n+z > 2 and w equals 1; - L1 is selected from a divalent aliphatic hydrocarbon radical in C1-C18, a cycloalkylene radical in C3-C15, a heterocycloalkylene group in C3-C12, or an arylene group in C6-C14, and mixtures thereof; - E independently represents a grouping chosen from: - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;in which R3 and R4 are chosen independently from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched Ci-Ci8 alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof; - when R5 is not a covalent bond, R5 is chosen from a; a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly interrupted by one or more heteroatoms, and mixtures thereof; and - R6 is chosen from a C6-Ci4 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

5. A process according to claim 3 or 4, characterized in that the (poly)carbodiimide compound(s) is / are selected from the compounds of formula (II) in which: - Xi and X2 independently represent an oxygen atom; - Ri and R2 are independently monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed; - n and z denote an integer from 1 to 20, with n+z > 2 and w is equal to 1; - Li is a C3-C15 cycloalkylene radical; - E independently represents a grouping chosen from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a C6-Ci4 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof; - when R5 is not a covalent bond, R5 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly interrupted by one or more heteroatoms, and mixtures thereof; and - R6 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

6. A method according to any one of claims 3 to 5, characterized in that the (poly)carbodiimide compound(s) is / are selected from the compounds of formula (II) in which: - Xi and X2 independently represent an oxygen atom; - Ri and R2 independently represent the compound with the following formula (VI): R13-[O-CH2-C(H)(R14)]q- (VI), in which Rn represents a C1-C4 alkyl group or a phenyl group, preferably an alkyl group in C1-C4, more preferably a methyl, RM represents a hydrogen atom or an alkyl group in Ci-C4, preferably a hydrogen atom and q denotes an integer from 4 to 30; - n and z denote an integer ranging from 2 to 20, with n+z ranging from 4 to 10 and w is equal to 1; - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, and - E represents an -O-R3-O- group in which R3 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

7. A method according to any one of claims 3 to 6, characterized in that the (poly)carbodiimide compound(s) is / are selected from the compounds of formula (II) in which: - Xi and X2 independently represent an oxygen atom; - Ri and R2 independently represent the compound with the following formula (VI): R13-[O-CH2-C(H)(R14)]q- (VI), in which Rn represents a Ci-C4 alkyl group or a phenyl, preferably a CrC4 alkyl group, more preferably a methyl, R14 represents a hydrogen atom or a CrC4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30; - n and z denote an integer ranging from 2 to 20, with n+z ranging from 4 to 10, and w is equal to 1; - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and - E represents a group- -O-R3-O- in which R3 represents a linear or CrCi8 branched alkylene radical such as methylene, propylene, butylene, ethylene, possibly interrupted by one or more heteroatom(s).

8. A process according to any one of claims 3 to 7, characterized in that the (poly)carbodiimide compound(s) is / are selected from the compounds of the following formula (XII): (XII), in which Li is 4,4-dicyclohexylene methane, n and z denote an integer from 2 to 20, with n+z ranging from 4 to 10, E represents a -O-R3-O- group in which R3 represents a linear or Ci-Ci8 branched alkylene radical such as methylene, propylene, butylene ethylene, possibly interrupted by one or more heteroatom(s), and r and s denote an integer from 4 to 30.

9. A process according to any one of the preceding claims, characterized in that the total amount of the (poly)carbodiimide compound(s) ranges from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, even more preferably from 0.5 to 8% by weight, better from 1 to 6% by weight relative to the total weight of composition C.

10. A method according to any one of the preceding claims, characterized in that the coloring agent or agents comprising aluminum are selected from pigments comprising aluminum other than pigments comprising at least one aluminosilicate.

11. A method according to claim 10, characterized in that the pigment(s) comprising aluminum, other than pigments comprising at least one aluminosilicate, comprise a substrate and optionally one or more layers that can be disposed on the substrate.

12. A method according to claim 11, characterized in that the substrate is chosen from aluminium and aluminium oxides.

13. A method according to claim 11 or 12, characterized in that the substrate is coated with a layer comprising at least one high refractive index metal oxide, more preferably chosen from light-absorbing metal oxides such as ferric oxide, cobalt(II) oxide, chromium(III) oxide, titanium(III) oxide, vanadium(V) oxide, and mixtures thereof.

14. A method according to any one of claims 11 to 13, characterized in that the aluminum pigment(s) other than pigments comprising at least one aluminosilicate are coated with a layer comprising organic compounds such as silanes.

15. A process according to any one of the preceding claims, characterized in that the total quantity of colorant(s) comprising aluminum other than colorants comprising at least one aluminosilicate ranges from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight relative to the total weight of composition C

16. A process according to any one of the preceding claims, characterized in that the compound(s) comprising at least one carboxylic function are selected from silicone compounds comprising at least one carboxylic group, polyurethanes, acrylic polymers and mixtures thereof.

17. A process according to any one of the preceding claims, characterized in that the compound(s) having at least one carboxylic function are in the form of aqueous dispersions of polymer particle(s) selected from polyurethanes, acrylic polymers and their mixtures, preferably in the form of aqueous dispersions of acrylic polymer particles, more preferably in the form of aqueous dispersions of film-forming acrylic polymer particles.

18. A process according to the preceding claim, characterized in that the acrylic polymer(s) comprise one or more motifs derived from the following monomers: a) (meth)acrylic acid; and b) alkyl (meth)acrylate in C1 to C30, more preferably in C1 to C20, even better in C1 to C10, and even more particularly in C1 to C4.

19. A method according to any one of claims 1 to 16, characterized in that the total quantity of compound(s) comprising at least one carboxylic function ranges from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 15% by weight, better from 2 to 10% by weight relative to the total weight of composition C.

20. A process according to claim 17 or 18, characterized in that the total quantity of the aqueous dispersion(s) of polymer particle(s) selected from polyurethanes, acrylic polymers, and mixtures thereof ranges from 0.1 to 40% by weight, more preferably from 0.5 to 30% by weight, even better from 1 to 25% by weight, and even more preferably from 2 to 20% by weight relative to the total weight of composition C.

21. A method according to any one of claims 1 to 18, characterized in that it consists of extemporaneously mixing at the time of use at least two compositions A and B to obtain a composition C and applying composition C to the hair, with: - composition A comprising at least one (poly)carbodiimide compound as defined in any one of claims 1 to 8; - composition B comprising at least one compound having at least one carboxylic function as defined in any one of claims 1 and 16 to 18, composition A and / or composition B comprising at least one colorant comprising aluminum other than colorants comprising at least one aluminosilicate as defined in any one of claims 1 and 10 to 14.

22. A hair coloring device comprising several compartments containing: - in a first compartment, a composition A comprising: a) at least one (poly)carbodiimide compound as defined in any one of claims 1 to 8, - in a second compartment, a composition B comprising: b) at least one compound comprising at least one carboxylic function as defined in any one of claims 1 and 16 to 18, composition A and / or composition B comprising: c) at least one coloring agent comprising aluminum other than coloring agents comprising at least one aluminosilicate as defined in any one of claims 1 and 10 to 14.