A hair coloring process comprising the application of a composition T comprising an amino acid and the application of a (poly)carbodiimide compound and a coloring agent

Abstract

The present invention relates to a hair coloring process comprising: a) applying to the hair at least one composition T comprising at least one agent AA selected from amino acids and their derivatives; then b) applying to the hair at least one composition C comprising: - at least one (poly)carbodiimide compound; and - at least one coloring agent selected from pigments, direct dyes, and mixtures thereof.

Description

Title of the invention: A hair coloring process comprising the application of a composition T comprising an amino acid and the application of a (poly)carbodiimide compound and a coloring agent

[0001] The present invention relates to a hair coloring process comprising the application to the hair of a composition T comprising a particular agent, then the application of a composition C comprising a (poly)carbodihnide compound and a coloring agent. 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 colors on dark hair, since the surface pigment masks the fiber's natural color. However, the colors obtained using this method have the disadvantage of being poorly resistant to shampoos and external agents such as sebum, perspiration, brushing, and / or friction.

[0008] There therefore remains a need for a hair coloring process which has the advantage of obtaining a homogeneous colored coating on the hair, while forming a coating that is resistant to shampoos and various aggressions that hair can withstand things like brushing and / or rubbing without damaging the hair.

[0009] Thus, the aim of the present invention is to develop a hair coloring process which has the advantage of obtaining a homogeneous and smooth colored coating on the hair, while forming a coating that is resistant to shampoos and to the various aggressions that hair can undergo such as brushing and / or rubbing without damaging the hair. Description of the invention

[0010] The present invention therefore relates to a hair coloring process comprising:

[0011] a) the application to the hair of at least one composition T comprising at least one agent AA selected from amino acids and their derivatives; then

[0012] b) the application to the hair of at least one composition C comprising:

[0013] - at least one (poly)carbodiimide compound; and

[0014] - at least one coloring agent selected from pigments, direct colorants, and their mixtures.

[0015] Thanks to the hair coloring process according to the invention, colored coatings are applied to the hair, resulting in a visible color that remains vibrant even after shampooing on all hair types, while preserving the hair's physical qualities. Such a coating can be resistant to external aggressors such as blow-drying and perspiration. In particular, it allows for a homogeneous application.

[0016] For the purposes of the present invention, "residual color after shampooing" means that the color obtained persists after one shampoo, preferably after 5 shampoos.

[0017] The expression "at least one" means one or more.

[0018] Unless otherwise indicated, the bounds of a range of values ​​are included in that range, in particular in the expressions "between" and "ranging from ... to ...".

[0019] The invention is not limited to the illustrated examples. The features of the different examples can, in particular, be combined within non-illustrated variants.

[0020] For the purposes of the present invention and, unless otherwise indicated,

[0021] - an "alkyl" radical designates a saturated linear or branched radical containing by example of 1 to 20 carbon atoms;

[0022] - an "aminoalkyl" radical means an alkyl radical as defined above, said alkyl radical comprising an NH2 group;

[0023] - a "hydroxyalkyl" radical means an alkyl radical as defined above, said alkyl radical comprising an OH group;

[0024] - an "alkylene" radical designates a divalent saturated hydrocarbon group at C2-C4, linear or branched, such as methylene, ethylene, or propylene;

[0025] - 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, 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.

[0026] - a "cycloalkylene" radical designates a divalent cycloalkyl group with "cy cloalkyl” as defined above, preferably in C3-Ci2;

[0027] - 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;

[0028] - an "arylene" radical is a divalent aryl radical with "aryl" as defined above Previously, preferably arylene represents phenylene;

[0029] - 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;

[0030] - a "heterocycloalkylene" radical is a divalent heterocyclic group with "heterocyclic" as defined above;

[0031] - an "aryloxy" radical designates an aryl-oxy radical with "aryl" as defined above previously;

[0032] - an "alkoxy" radical designates an alkyl-oxy radical with "alkyl" as defined previously;

[0033] - an "acyloxy" radical designates an ester radical RC(O)-O- with R an alkyl group as defined previously;

[0034] - a "reactive" group is a group capable of forming a bond covalent with another group, identical or different, by chemical reaction.

[0035] 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.

[0036] 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.

[0037] For the purposes of the present invention, "hair" means the hair on the head. This term does not include body hair, eyebrows, or eyelashes. Composition T

[0038] As indicated above, the process according to the invention comprises a) the application to the hair of at least one composition T comprising at least one agent AA selected from amino acids and their derivatives.

[0039] The term "amino acid derivative" means an amino acid salt or a compound obtained by chemical reaction from an amino acid or a peptide or polypeptide such as polylysine.

[0040] Preferably, the amino acid is selected from natural amino acids, synthetic amino acids in their L, D, or racemic form, and mixtures thereof, and comprises at least one acid function selected from carboxylic, sulfonic, phosphonic, or phosphoric acid functions. Said amino acids may be in acid form or in sal form.

[0041] Said amino acids may be α-amino acids, natural or synthetic, comprising a carbon atom C bearing an amino group, a carboxyl group, a hydrogen atom and a side group which may be a hydrogen atom (case of glycine), any other monovalent organic group or a ring comprising said carbon atom C, the nitrogen atom of said amino group and several additional carbon atoms, preferably 3 to 4 additional carbon atoms.

[0042] The side groups may include alkyl groups (as in the case of alanine, valine, leucine, isoleucine), substituted alkyl groups (as in the case of threonine, serine, methionine, cysteine, asparagine, aspartic acid, glutamic acid, glutamine, arginine and lysine), arylalkyl groups (as in the case of phenylalanine and tryptophan), substituted arylalkyl groups (as in the case of tyrosine), heteroalkyl groups (as in the case of histidine).

[0043] The side group may in particular be a 5-membered ring comprising said carbon atom C, the nitrogen atom of said amino group and 3 additional carbon atoms, such as for proline.

[0044] These α-amino acids are notably listed in Harper et al (1977) Review of

[0045] Physiological Chemistry, 16th edition, Lange Medical Publications, pages 21-24. A synthetic α-amino acid is defined as an α-amino acid that is not incorporated into a protein under mRNA control, such as, for example, a fluorinated α-amino acid like fluoroalanine, trimethylsilylalanine, or an α-amino acid such as:

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054] where ni is an integer from 1 to 6 and n2 is an integer from 1 to 12. Synthetic amino acids are also described in Williams (ed), Synthesis of Optically Active α-Amino Acids, Pergamon Press (1989); Evans et al, J. Amer. Chem. Soc. 112,4011-4030 (1990); Pu et al, J. Amer. Chem. Soc. 56, 1280-1283 (1991); on Williams et al, J. Amer. Chem. Soc., 113,9276-9286 (1991). The AA agent can also be chosen from peptides, polypeptides, including polylysine. For the purposes of this invention, peptide means a polymer of 2 to 9 amino acids, identical or different, linked together by peptide bonds. For the purposes of this invention, polypeptide means a polymer of 10 to 100 amino acids, identical or different, linked together by peptide bonds. Among the peptides and polypeptides, we can mention polylysine, which can be presented in the form of alpha-polylysine (peptide bond on the amine group in the alpha position) or epsilon-polylysine (peptide bond on the amine group in the epsilon position). Advantageously, the amino acid is selected from natural amino acids, synthetic amino acids in their L, D, or racemic form, and comprising at least one acid function selected from carboxylic, sulfonic, phosphonic, or phosphoric acid functions, peptides, polypeptides, and mixtures thereof. Preferably, the AA agent is chosen from amino acids, peptides, and polypeptides. Advantageously, the AA agent is chosen from aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, the glutamine, glycine, histidine, lysine, polylysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine, valine, and mixtures thereof, preferably from lysine, polylysine, glycine, and mixtures thereof.

[0055] Advantageously, agent AA is present in a total content ranging from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 0.75 to 15% by weight, even more preferably from 1 to 10% by weight, better from 1 to 5% by weight relative to the total weight of composition T.

[0056] Composition T may further comprise water, in particular in an amount of at least 70% by weight, preferably at least 80% by weight, and even better at least 85% by weight relative to the total weight of the composition. In particular, it may comprise water in a total amount ranging from 70 to 99% by weight, preferably from 80 to 99% by weight, more preferably from 85 to 99% by weight, and better still from 90 to 99% by weight relative to the total weight of composition T.

[0057] Preferably, the composition T essentially comprises water and one or more AA agents.

[0058] The term "composition essentially comprises a compound" means a composition comprising at least 90% by weight, preferably at least 95% by weight, of said compound in relation to the total weight of the composition.

[0059] More preferably, the composition T comprises only water and one or more AA agents. Additives

[0060] The composition T used in the coloring process according to the invention may contain any adjuvant or additive commonly used.

[0061] Among the additives that may be used are reducing agents, thickening agents, softeners, moisturizing agents, UV filters, peptizers, solubilizers, perfumes, vitamins, polymers other than those previously described, in particular other than silicones, preservatives, oils, waxes and mixtures thereof. Polycarbodiimide compound

[0062] Composition C used in the process according to the invention comprises at least one (poly)carbodiimide compound.

[0063] The composition may comprise at least two distinct (poly)carbodiimide compounds, present in mixture in the composition.

[0064] 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 par in particular the number of carbodiimide groups does not exceed 200, preferably 150, more preferably 100.

[0065] The term “carbodiimide group” means a divalent linear triatomic fraction of general formula - (N=C=N)

[0066] 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.

[0067] 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.

[0068] According to a particular embodiment, the (poly)carbodiimide compound is chosen from the compounds of the following formula (I): OQ A laughed. Ri—XL "N—A——A4—hT H l JH

[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 grouping chosen from a radical hy a drocarbon, preferably alkyl, optionally interrupted by one or more heteroatoms, a group selected from the following: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbomenylsilyl, acylpentadienylalkylsilyl, 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 heteroatom(s) and by one or more groups selected from the following groups: al-koxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylal-kylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hy-droxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpent-tadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, cro-tonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide, and azacyclopropane;

[0072] - n denotes an integer from 1 to 1000; and

[0073] - A is a monomer selected from the compounds below:

[0074] According to another embodiment, the (poly)carbodiimide compound is chosen from the compounds of the following formula (!'): (D

[0075] in which:

[0076] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0077] - 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;

[0078] - Zi and Z2 represent, independently, a reactive terminal group or a group inert terminal;

[0079] - as an inert terminal group, Zi and Z2 can represent, independently, a saturated aliphatic group, linear or branched or cyclic, in the C1 to C50 range, or an aromatic group in the C6 to C8 range, 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;

[0080] - 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;

[0081] - Q represents an organopolymer or an organo-oligomer comprising re-units competitive of saturated aliphatic groups, linear or branched or cyclic, or of aromatic groups or alkylaromatic groups, coupled by repeating bonds carbonate, ester, ether, amide, urethane or urea or their combinations;

[0082] - 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;

[0083] - r denotes an integer equal to 0 or 1;

[0084] - m denotes an integer from 0 to 1000, preferably equal to 0 or 1;

[0085] - m' designates an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0086] - n denotes an integer from 0 to 1000, preferably equal to 0 or 1, with m+ (m'*n ) > 2.

[0087] 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.

[0088] Such (poly)carbodiimide 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.

[0089] Preferably, the (poly)carbodiimide compound(s) is / are chosen from the compounds of the following formula (II): V (n),

[0090] in which

[0091] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0092] - Ri and R2 independently represent a hydrocarbon radical possibly in interrupted by one or more heteroatom(s);

[0093] - n and z denote an integer from 1 to 20, with n+z > 2 and w denotes a integer ranging from 1 to 3;

[0094] - 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;

[0095] - E independently represents a grouping chosen from:

[0096] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-,

[0097] in which R3 and R4 independently represent a divalent hydrocarbon radical possibly interrupted by one or more heteroatom(s);

[0098] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, possibly interrupted by one or more heteroatom(s);

[0099] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

[0100] 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.

[0101] The hydrocarbon radical may comprise one or more cyclic groups.

[0102] 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 which may be incorporated in the form of a salt.

[0103] 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.

[0104] Preferably, Xi and X2 independently represent an oxygen atom.

[0105] 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.

[0106] According to a preferred embodiment, Ri and R2 are chosen independently from the following groupings (i) to (iv):

[0107] (i) the compound of the following formula (III):

[0108] R7-OC(O)-C(R8)(H)-(III),

[0109] wherein R7 represents a Ci-C3 alkyl group, and R8 represents a hydrogen atom or a Ci-C3 alkyl group, preferably R7 is a methyl and R8 is a hydrogen atom or a methyl.

[0110] (ii) the compound of the following formula (IV):

[0111] R9-[0-CH2-C(H)(Rio)]p-(IV),

[0112] 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.

[0113] (iii) the compound of the following formula (V):

[0114] (Rn)2N-CH2-C(H)(R12)-(V),

[0115] wherein Rn represents an alkyl group in CrC4 and R12 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.

[0116] (iv) the compound of the following formula (VI):

[0117] R13-[O-CH2-C(H)(R14)]q- (VI),

[0118] wherein Rn represents a CrC4 alkyl group or a phenyl, RM represents a hydrogen atom or a CrC4 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.

[0119] Preferably, Ri and R2 independently represent a compound of formula (VI) in which Rn represents a CrC4 alkyl group or a phenyl, preferably a Ci-C4 alkyl group, more preferably a methyl, R[4] represents a hydrogen atom or a Ci-C4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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, Ru represents a hydrogen atom or a CrC4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30.

[0124] Preferably, n denotes an integer from 1 to 20, more preferably from 2 to 20.

[0125] Preferably, z denotes an integer from 1 to 20, more preferably from 2 to 20.

[0126] Preferably, w is equal to 1.

[0127] Preferably, w is equal to 1, n+z denotes an integer from 4 to 10.

[0128] Preferably, Li is selected from a divalent aliphatic hydrocarbon radical in Ci-Ci8 such as methylene, ethylene, and propylene, a cycloalkylene radical in C3-C15 such as cyclopentylene, cycloheptylene, and cyclohexylene, a heterocycloalkylene group in C3-Ci2 such as imidazolene, pyrrolene, and furanylene, or an arylene group in C6-Ci4 such as phenylene, and mixtures thereof.

[0129] 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.

[0130] 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):

[0131] Preferably, L1 is the 4,4-dicyclohexylene methane corresponding to the following formula (VIII): (VIII).

[0132] 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).

[0133] As stated previously, E independently represents a grouping chosen from:

[0134] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0135] in which R3 and R4 independently represent a divalent hydrocarbon radical possibly interrupted by one or more heteroatom(s);

[0136] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, possibly interrupted by one or more heteroatom(s); and

[0137] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

[0138] Preferably, R3 and R4 are chosen independently from a C6-CM arylene radical 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, optionally interrupted by one or more heteroatom(s) and mixtures thereof.

[0139] 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).

[0140] 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.

[0141] 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 CrCi8 alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0142] 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 CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0143] 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, possibly interrupted by one or more heteroatom(s).

[0144] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from alpha-methylstyryl-isocyanates of the following formula (X): (X),

[0145] 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,

[0146] n denotes an integer from 2 to 100.

[0147] In this embodiment, the term “alkyl group” is as defined above.

[0148] In this embodiment, the term "cycloalkyl group" is as defined above.

[0149] In this embodiment, n can denote an integer from 2 to 50, preferably from 3 to 30, more preferably from 5 to 10.

[0150] According to another particular embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI):

[0151] 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.

[0152] The "alkyl group", the "cycloalkyl group" and the "aryl group" are as defined above.

[0153] According to a preferred embodiment, the (poly)carbodiimide compound is selected from compounds of formula (I) or formula (II) in which:

[0154] - Xi and X2 independently represent an oxygen atom;

[0155] - Ri and R2 are chosen independently from among the dialkylaminoalcohols, the al- esters hydroxycarboxylic acid alkyls and monoalkyl ethers of (poly)alkylene glycol, wherein a hydroxyl group has been removed, and mixtures thereof, preferably, monoalkyl ethers of (poly)alkylene glycol, wherein a hydroxyl group has been removed, more preferably, the compound of formula (VI) as described above, wherein Rn represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, RM represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q denotes an integer from 4 to 30

[0156] - n and z, when present, denote an integer from 1 to 20, with n+z > 2 and w is equal to 1;

[0157] - 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;

[0158] - A, when present, is chosen from an aliphatic hydrocarbon radical divalent in Ci-Ci8, 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;

[0159] - E, when present, independently represents a grouping chosen from:

[0160] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0161] 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;

[0162] - 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

[0163] - 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.

[0164] Preferably, the (poly)carbodiimide compound is chosen from compounds of formula (II) in which:

[0165] - Xi and X2 independently represent an oxygen atom;

[0166] - 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;

[0167] - n and z denote an integer from 1 to 20, with n+z > 2 and w is equal to 1;

[0168] - 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;

[0169] - E independently represents a grouping chosen from:

[0170] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0171] 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;

[0172] - 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

[0173] - 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.

[0174] More preferably, the (poly)carbodiimide compound is chosen from compounds of formula (II) in which:

[0175] - Xi and X2 independently represent an oxygen atom;

[0176] - Ri and R2, are independently of (poly)alkylene glycol monoalkyl ethers, in which a hydroxy group has been removed;

[0177] - n and z denote an integer from 1 to 20, with n+z > 2 and w is equal to 1;

[0178] - Li is a C3-Ci5 cycloalkylene radical;

[0179] - E independently represents a grouping chosen from:

[0180] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0181] 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;

[0182] - 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

[0183] - 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.

[0184] Even more preferably, the (poly)carbodihnide compound is chosen from compounds of formula (II) in which:

[0185] - Xi and X2 independently represent an oxygen atom;

[0186] - Ri and R2, independently represent the compound of the following formula (VI):

[0187] R13-[O-CH2-C(H)(R14)]q- (VI),

[0188] in which Rn represents a Ci-C4 alkyl group or a phenyl, preferably a CrC4 alkyl group, more preferably a methyl, RM represents a hydrogen atom or a CrC4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30;

[0189] - n and z denote an integer from 1 to 20, with n+z ranging from 4 to 10 and w is equal to 1;

[0190] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cyclo- heptylene, cyclohexylene and 4,4-dicyclohexylene methane; and

[0191] - 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 CrCi8, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

[0192] Even more preferably, the (poly)carbodiimide compound is chosen from compounds of formula (II) in which:

[0193] - Xi and X2 independently represent an oxygen atom;

[0194] - Ri and R2, independently represent the compound of the following formula (VI):

[0195] R13-[O-CH2-C(H)(R14)]q- (VI)

[0196] wherein R[3 represents a Ci-C4 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;

[0197] - n and z denote an integer from 1 to 20, with n+z from 4 to 10 and w is equal to 1;

[0198] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cyclo- heptylene, cyclohexylene, 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and

[0199] - E represents a group- -O-R3-O- in which R3 represents a radical linear or CrCi8 branched alkylene such as methylene, propylene, butylene ethylene, possibly interrupted by one or more heteroatom(s).

[0200] According to a preferred embodiment, the (poly)carbodiimide compound is a compound with the following formula (XII):

[0201] in which L1 is 4,4-dicyclohexylene methane, n and z denote an integer from 1 to 20, with n+z ranging from 4 to 10, E represents an -O-R3-O- group in which R3 represents a linear or CrCi8 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.

[0202] 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. Coloring agent

[0203] Composition C used in the process according to the invention comprises one or more coloring agent(s) selected from pigments, direct colorants, and mixtures thereof.

[0204] Preferably, the composition C used in the process according to the invention comprises one or more pigments.

[0205] The term "pigment" means all pigments that impart color to keratinous materials. Their solubility in water at 25 °C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

[0206] The pigments that may be used are chosen in particular from among the organic and / or mineral pigments known to the technique, in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in the Encyclopedia of Ullmann industrial chemistry.

[0207] They may be natural, of natural origin, or not.

[0208] These pigments may be in the form of a powder or pigment paste. They may be coated or uncoated.

[0209] Pigments can, for example, be chosen from mineral pigments, organic pigments, lacquers, special effect pigments such as mother-of-pearl or glitter, and mixtures thereof.

[0210] The pigment may be a mineral pigment. By mineral pigment, we mean 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 oxide.

[0211] The 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.

[0212] 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.

[0213] 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.

[0214] By way of example, one can also cite organic pigment pastes such as the products sold by the company HOECHST under the name:

[0215] - COSMENYL YELLOW IOG: Pigment YELLOW 3 (Cl 11710);

[0216] - COSMENYL YELLOW G: Pigment YELLOW 1 (Cl 11680);

[0217] - ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);

[0218] - COSMENYL RED R: Pigment RED 4 (Cl 12085);

[0219] - CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);

[0220] - VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);

[0221] - COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);

[0222] - COSMENYL GREEN GG: Pigment GREEN 7 (Cl 74260);

[0223] - COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

[0224] The pigments according to the invention can also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments can 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.

[0225] The organic pigment can also be a lake. By lake, we mean colorants adsorbed onto insoluble particles, the whole thus obtained remaining insoluble during use.

[0226] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

[0227] 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).

[0228] As examples of lacquers, we can cite the product known under the following name: D & C Red 7 (CI 15 850 :1).

[0229] The pigment can 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 distinct from colored pigments that provide a uniform opaque, semi-transparent, or conventionally transparent tint.

[0230] 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.

[0231] Examples of special effect pigments include pearlescent pigments such as titanium-coated mica or bismuth oxychloride, colored pearlescent pigments such as titanium- and iron oxide-coated mica, iron oxide-coated mica, and titanium-coated mica, particularly ferric blue or oxide Chromium, mica coated with titanium and an organic pigment as defined previously, and pearlescent pigments based on bismuth oxychloride. Examples of pearlescent pigments include Cellini pearlescent pigments marketed by BASF (Mica-TiO2-lacquer), Prestige marketed by Eckart (Mica-TiO2), Prestige Bronze marketed by Eckart (Mica-Fe2O3), and Colorona marketed by Merck (Mica-TiO2-Fe2O3).

[0232] 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.

[0233] As further examples of nacres, we can also mention particles comprising a borosilicate substrate coated with titanium oxide.

[0234] Particles with a glass substrate coated with titanium oxide are notably sold under the name METASHINE MC1080RY by the company TOYAL.

[0235] Finally, as examples of mother-of-pearl, one can also cite polyethylene terephthalate flakes, in particular those marketed by Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver flakes). One can also consider multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate, and aluminum.

[0236] Special effect pigments may also be selected from reflective particles, that is to say, 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.

[0237] 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.

[0238] These particles can have various shapes, including platelet or globular, particularly spherical.

[0239] 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.

[0240] When reflective particles do not have a multilayer structure, they can be composed, for example, of metal oxides, in particular titanium or iron oxides obtained by synthesis.

[0241] 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. The substrate may be monomaterial, multimaterial, organic and / or inorganic.

[0242] More specifically, it may be selected from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica and mixtures thereof, this list not being exhaustive.

[0243] The reflective material may include a layer of metal or a metallic material.

[0244] Reflective particles are described in particular in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0245] 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.

[0246] 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.

[0247] Particles comprising a metallic substrate such as silver, aluminum, 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, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

[0248] An example can be cited as aluminium, bronze or copper powders coated with SiO2 marketed under the name VISIONAIRE by the company ECKART.

[0249] 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.

[0250] 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.

[0251] 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.

[0252] The pigments can be dispersed in the composition by means of a dispersing agent.

[0253] 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, bearing one or more functionalities having 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 in particular and fatty acids in C8 to C20 and polyols such as glycerol, diglycerin, such as poly(12-hydroxystearic acid) stearate with a molecular weight of about 750g / mol such as that sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxy stearate (name CTFA) sold under the reference Dehymyls PGPH by the company Henkel or polyhydroxystearic acid such as that sold under the reference Arlacel P100 by the company Uniqema and their mixtures.

[0254] 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.

[0255] The pigments used in the composition can be surface treated with an organic agent.

[0256] Thus, the pigments previously treated on the surface useful within the framework of the invention are pigments which have undergone totally or partially a surface treatment of a chemical, electronic, electro-chemical, mechano-chemical 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 be chosen, for example, 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 aluminum salts of fatty acids, such as aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, such as polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanoamines; silicone compounds, such as silicones, in particular polydimethylsiloxanes; fluorinated organic compounds, such as perfluoroalkyl ethers; Fluoro-silicon compounds.

[0257] 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.

[0258] 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.

[0259] Preferably, the surface-treated pigments are covered by an organic layer.

[0260] 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.

[0261] 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.

[0262] Preferably, an organic agent covalently linked to the pigments will be used.

[0263] 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.

[0264] Preferably, the surface treatments of the pigments are chosen from the following treatments:

[0265] - a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW;

[0266] - a Methicone treatment such as the SI surface treatment marketed by LCW;

[0267] - a Dimethicone treatment such as the Covasil 3.05 com surface treatment marketed by LCW;

[0268] - a Dimethicone / Trimethylsiloxysilicate treatment as the surface treatment Covasil 4.05 marketed by LCW;

[0269] - a Magnesium Myristate treatment such as the MM com surface treatment marketed by LCW;

[0270] - an Aluminium Dimyristate treatment such as the MI com surface treatment marketed by Miyoshi;

[0271] - a Perfluoropolymethylisopropyl ether treatment as a surface treatment FHC marketed by LCW;

[0272] - an Isostearyl Sebacate treatment such as the commercially available HS surface treatment by Miyoshi;

[0273] - a Perfluoroalkyl Phosphate treatment as a PF surface treatment marketed by Daito;

[0274] - an acrylate / dimethicone copolymer and perfluoalkyl phosphate treatment such as the FSA surface treatment marketed by Daito;

[0275] - a Polymethylhydrogen siloxane / Perfluoroalkyl Phosphate treatment such as the FS01 surface treatment marketed by Daito;

[0276] - an Acrylate / Dimethicone Copolymer treatment as the surface treatment ASC marketed by Daito;

[0277] - an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito;

[0278] - an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito;

[0279] - a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito.

[0280] According to a particular embodiment of the invention, the dispersing agent is present with organic or inorganic pigments in submicron-sized particulate form.

[0281] By "sub-micronic" or in English "sub-micronic" is meant pigments whose particle size has been 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.

[0282] 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.

[0283] The dispersing agent(s) may therefore have a silicone skeleton, such as silicone polyether and amino-silicone dispersants. Suitable dispersing agents include:

[0284] - 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 les polymers,

[0285] - silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik,

[0286] - 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.

[0287] According to a particular embodiment, the dispersing agent(s) are of the amino-silicone type and are cationic.

[0288] Preferably, the pigment(s) is / are chosen from mineral, mixed mineral-organic or organic pigments.

[0289] In one embodiment of the invention, the pigment(s) are organic pigments, preferably organic pigments surface-treated with an organic agent selected from silicone compounds. In another embodiment of the invention, the pigment(s) are mineral pigments.

[0290] Preferably, the pigment(s) are chosen from iron oxides, in particular red, brown, or black. An example of an iron oxide is the iron oxide sold by Sun Chemical under the name SunPuro® Red Iron Oxide.

[0291] Direct dye

[0292] Composition C used in the process according to the invention may include one or more direct dye(s).

[0293] By "direct dye" we mean natural and / or synthetic dyes, different from oxidation dyes. These are dyes that will diffuse superficially onto the fiber.

[0294] They can be ionic or non-ionic, preferably cationic or non-ionic.

[0295] 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.

[0296] 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: Het <N0U)-N=C(Rb)-Ar, Q- (Xm)’ Her-C(Ra)=NN(Rb)-Ai, Q (XIV), HeF-N^N-Ar Q- (XV)' (XVI), Ar -N=X-Ai' , Q- v

[0297] formulas (XIII) to (XVI) in which:

[0298] - 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 (CrC8)alkyl group such as methyl;

[0299] - 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;

[0300] - 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 Ar represents a julolidine group;

[0301] - 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)alkoxy or phenyl groups;

[0302] - Ra and Rb, identical or different, representing a hydrogen atom or a (CrC8)alkyl group possibly substituted, preferably by a hydroxyl group;

[0303] 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;

[0304] - Q- represents an organic or mineral anionic counterion such as a halide or an alkyl sulfate.

[0305] In particular, mention may be made of endocyclic cationic azo and hydrazono direct dyes of formula (XIII) to (XVI) as defined above; more particularly, endocyclic cationic direct dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP-714954; preferably the following direct dyes: (XVII),

[0306] Formulas (XVII) and (XVIII) in which:

[0307] - R1 represents an (Ci-C4)alkyl group such as methyl;

[0308] - R2 and R3, whether identical or different, represent a hydrogen atom or a (CrC4)alkyl group such as methyl; and

[0309] - 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,

[0310] - Z represents a CH group or a nitrogen atom, preferably CH,

[0311] - Q- is an anionic counterion as defined above, particularly ha- lohenide such as chloride or an alkylsulfate such as methylsulfate or mesytyl.

[0312] In particular, the colorants of formula (XV) and (XVI) are selected from Basic 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.

[0313] 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 understood to mean 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.

[0314] As examples of acid dyes useful to the invention, the following dyes with formulas (XIX), (XIX'), (XX), (XX'), (XXI), (XXI'), (XXII), (XXII'), (XXIII), (XXIV), (XXV) and (XXVI) may be cited:

[0315] a) Diaryl anionic azo dyes of formula (XIX) or (XIX'):

[0316] formulas (XIX) and (XIX') in which:

[0317] - R7, R8, R9, Rio, R'7, R'8, R'9 and R'1O, whether identical or different, represent an atom of hydrogen or a group chosen from:

[0318] - alkyl;

[0319] - alkoxy, alkylthio;

[0320] - hydroxy, mercapto;

[0321] - nitro, nitroso;

[0322] - 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;

[0323] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0324] - (O)CO—, M+ with M+ as defined above;

[0325] - 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;

[0326] - R'”-S(O)2-X'- with R”' representing an alkyl group, possibly aryl substituted, X' as defined previously;

[0327] - (di)(alkyl)amino;

[0328] - 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;

[0329] - heteroaryl possibly substituted; preferably a benzo- group thiazolyl;

[0330] - cycloalkyl, in particular cyclohexyl;

[0331] - 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;

[0332] - 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;

[0333] - W represents a sigma bond, an oxygen atom, a sulfur atom, or a radical divalent i) -NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb identical or different, representing a hydrogen atom or a aryl group, or Ra and Rb together with the carbon atom that bears them form a spiro cycloalkyl; preferably W represents a sulfur atom or Ra and Rb together form a cyclohexyl;

[0334] it being understood that the 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.

[0335] 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;

[0336] et à titre d’exemple de colorants de formule (XIX’) on peut citer : Acid Red 111, Acid Red 134, Acid yellow 38 ;

[0337] b) les colorants azo anioniques pyrrazolone de formule (XX) et (XX’) :

[0338] formulas (XX) and (XX') in which:

[0339] - Ru, R12 and Rn, whether identical or different, represent a hydrogen atom, halogen, an alkyl group or -(O)2S(O-), M+ with M+ as defined previously;

[0340] - Ru represents a hydrogen atom, an alkyl group or a group - C(O)O-, M+ with M+ as defined previously;

[0341] - Rn represents a hydrogen atom;

[0342] - Ri6 represents an oxo group in which case R'i6 is absent, or else R[5 with R[6 together form a double bond;

[0343] - Rn and Ri8, whether identical or different, represent a hydrogen atom, or a group chosen from:

[0344] - (O)2S(O-)-, M+ with M+ as defined above;

[0345] - Ar-OS(O)2- with Ar representing an aryl group possibly substituted; preferably a phenyl possibly substituted by one or more alkyl groups;

[0346] - R19 and R20 together form either a double bond or a benzo D' group, possibly substituted;

[0347] - R' 16, R' 19 and R'2O, whether identical or different, represent a hydrogen atom or a alkyl group, or hydroxy;

[0348] - R2i represents a hydrogen atom, an alkyl group, or alkoxy;

[0349] - Ra and Rb, whether identical or different, are as defined above, preferably Ra represents a hydrogen atom and Rb represents an aryl group;

[0350] - Y represents either a hydroxy group or an oxo group;

[0351] - * » - - represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group;

[0352] 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;

[0353] 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;

[0354] c) the anthraquinone dyes of formula (XXI) and (XXI'):

[0355] formulas (XXI) and (XXI') in which:

[0356] - R22, R23, R24, R25, R26 and R27, whether identical or different, represent an atom of hydrogen, halogen, or a group chosen from:

[0357] - alkyl;

[0358] - hydroxy, mercapto;

[0359] - alkoxy, alkylthio;

[0360] - 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;

[0361] - aryl(alkyl)amino optionally substituted by one or more selected groups among alkyl and (O)2S(O-)-, M+ with M+ as defined previously;

[0362] - (di)(alkyl)amino;

[0363] - (di)(hydroxyalkyl)amino

[0364] - (O)2S(O-)-, M+ with M+ as defined above;

[0365] - 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:

[0366] - alkyl;

[0367] - polyhydroxyalkyl such as hydroxyethyl;

[0368] - 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;

[0369] - cycloakyl, in particular cyclohexyl;

[0370] - 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;

[0371] 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;

[0372] 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;

[0373] d) Nitrated dyes of formula (XXII), (XXII'):

[0374] formulas (XXII) and (XXII') in which:

[0375] - R3o, R3i and R32, whether identical or different, represent a hydrogen atom, halogen, or a group selected from:

[0376] - alkyl;

[0377] - alkoxy possibly substituted by one or more hydroxy groups, alkylthio possibly substituted by one or more hydroxy groups;

[0378] - hydroxy, mercapto;

[0379] - nitro, nitroso;

[0380] - polyhalogenoalkyl;

[0381] - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° ; X, X' and X” as defined previously;

[0382] - (O)2S(O-)-, M+ with M+ as defined above;

[0383] - (O)CO—, M+ with M+ as defined above;

[0384] - (di)(alkyl)amino;

[0385] - (di)(hydroxyalkyl)amino;

[0386] - heterocycloalkyl such as piperidino, piperazino or morpholino; particularly R 30, R31 and R32 represent a hydrogen atom;

[0387] - Rc and Rd, whether identical or different, represent a hydrogen atom or a alkyl group;

[0388] - W is as defined above; W particularly represents a grouping -NH-;

[0389] - ALK represents a linear or branched divalent alkylene group, in Ci-C6; particularly ALK represents a grouping -CH2-CH2-;

[0390] - n is equal to 1 or 2;

[0391] - p represents an integer between 1 and 5 inclusive;

[0392] - q represents an integer between 1 and 4 inclusive;

[0393] - u is equal to 0 or 1;

[0394] - when n equals 1, J represents a nitro or nitroso group; particularly nitro;

[0395] - 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-;

[0396] - M' represents a hydrogen atom or a cationic counter-ion;

[0397] - .... ... present or absent represents a benzo group possibly replaced by one or more R30 groups as defined above,

[0398] 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.

[0399] 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;

[0400] e) triarylmethane dyes of formula (XXIII): (XXIII),

[0401] formula (XXIII) in which:

[0402] - 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;

[0403] - R37, R38, R39, R4o, R4i, R42, R43 and R^, identical or different, represent an atom of hydrogen or a group chosen from:

[0404] - alkyl;

[0405] - alkoxy, alkylthio;

[0406] - (di)(alkyl)amino;

[0407] - hydroxy, mercapto;

[0408] - nitro, nitroso;

[0409] - 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;

[0410] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0411] - (O)CO—, M+ with M+ as defined above;

[0412] - 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;

[0413] particularly R37 to R40 represent a hydrogen atom, and R41 to R44, identical or different, represent a hydroxyl group or (O)2S(O-)-, M+; and when R43 with R40 together form a benzo group, it is preferentially substituted by a grouping (O)2S(O-)- ;

[0414] 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.

[0415] 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.

[0416] f) xanthene-derived dyes of formula (XXIV):

[0417] formula (XXIV) in which:

[0418] - R45, R46, R47 and R48, whether identical or different, represent a hydrogen atom or an atom of halogen;

[0419] - R49. R50, R51 and R52, whether identical or different, represent a hydrogen atom, halogen, or a group selected from:

[0420] - alkyl;

[0421] - alkoxy, alkylthio;

[0422] - hydroxy, mercapto;

[0423] - nitro, nitroso;

[0424] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0425] - (O)CO—, M+ with M+ as defined above;

[0426] particularly R49, R50, R51 and R52 represent a hydrogen or halogen atom

[0427] - 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;

[0428] - 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;

[0429] - 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;

[0430] - Q and Q', identical or different, represent an oxygen or sulfur atom; in particular Q and Q' represent an oxygen atom;

[0431] - M+ is as defined previously.

[0432] 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;

[0433] g) dyes derived from indole of formula (XXV): (XXV),

[0434] formula (XXV) in which:

[0435] - R53, R54, R55, R56, R57, R58, R59 and R60, whether identical or different, represent an atom of hydrogen or a group chosen from:

[0436] - alkyl;

[0437] - alkoxy, alkylthio;

[0438] - hydroxy, mercapto;

[0439] - nitro, nitroso;

[0440] - 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;

[0441] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0442] - (O)CO—, M+ with M+ as defined above;

[0443] - 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;

[0444] - Ri and Rh, whether identical or different, represent a hydrogen atom or a alkyl group;

[0445] it being understood that formula (XXIII) comprises at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical -C(O)O-, M+; preferably sodium sulfonate.

[0446] As an example of colorants of formula (XXV) we can cite: Acid Blue 74;

[0447] h) quinoline-derived dyes of formula (XXVI):

[0448] formula (XXVI) in which:

[0449] - R6i represents a hydrogen atom, a halogen atom or an alkyl group;

[0450] - 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;

[0451] 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;

[0452] it being understood that formula (XXVI) comprises at least one sulfonate radical (O)2 S(O-)-, M+ preferably sodium sulfonate.

[0453] Examples of colorants of formula (XXVI) include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0454] 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.

[0455] Preferably, the direct dyes are chosen from among the anionic direct dyes.

[0456] The colouring agent(s) 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 colouring agent(s) are chosen from pigments.

[0457] The pigment(s) may be present in a total quantity ranging 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.

[0458] The direct colorant(s) may be present in a total quantity ranging from 0.001 at 10% by weight, preferably from 0.005 to 5% by weight relative to the total weight of composition C. Compound having at least one carboxylic acid function

[0459] The composition C used in the process according to the invention may further comprise at least one compound having at least one carboxylic function.

[0460] 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

[0461] 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.

[0462] 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.

[0463] 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.

[0464] The dispersion(s) may be simple dispersions in the aqueous medium of the cosmetic composition. Latexes are a particular example of a dispersion.

[0465] The aqueous dispersion(s) of polymer particles can be chosen from aqueous dispersions of polyurethane particles.

[0466] More particularly, the polyurethane(s) present in the aqueous dispersions used in the present invention are derived from the reaction of

[0467] - a prepolymer of the following formula (A):

[0468] (A),

[0469] in which

[0470] - Ri represents a divalent radical of a dihydroxylated compound;

[0471] - R2 represents a radical of an aliphatic or cycloaliphatic polyisocyanate;

[0472] - R3 represents a radical of a low molecular weight diol, possibly substituted by one or more ionic groups;

[0473] - n represents an integer from 1 to 5, and

[0474] - m is greater than 1;

[0475] - at least one chain extender according to the following formula (B):

[0476] H2N-R4-NH2 (B),

[0477] wherein R4 represents an alkylene radical or alkylene oxide that is not substituted by one or more ionic or potentially ionic groups; and

[0478] - at least one string extender according to the following formula (C):

[0479] H2N-R5-NH2 (C),

[0480] in which R5 represents an alkylene radical substituted by one or more ionic or potentially ionic groups.

[0481] Among the dihydroxylated compounds usable according to the present invention, particular examples include compounds having two hydroxyl groups and a number molecular weight of about 700 to about 16,000, and preferably of about 750 to about 5,000. By way of example of dihydroxylated compounds having a high molecular weight, examples 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.

[0482] 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.

[0483] 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.

[0484] 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 toluene diisocyanate (TDI) isomers such as 2,4-toluene diisocyanate and 2,6-diisocyanate. toluene and mixtures thereof, hydrogenated toluene diisocyanate, 4,4'-diisocyanate diphenyl methane and mixtures with its isomers 2,4-diphenylmethane diisocyanate and possibly 2,2'-diphenylmethane diisocyanate, naphthalene-1,5 diisocyanate, and mixtures thereof.

[0485] 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.

[0486] 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.

[0487] 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.

[0488] 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.

[0489] If lower molecular weight diols containing ionic or potentially ionic groups are used, they are preferably used in such an amount that less than 0.30 meq of COOH per gram of polyurethane in the polyurethane dispersion are present.

[0490] The prepolymer is elongated using two families of chain extenders. The first family of chain extenders corresponds to the compounds of general formula (B).

[0491] The chain extenders of formula (B) are preferably selected from among the alkylene diamines, such as hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine; the 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 (Dytec A from DuPont), hexanediamine, isophoronediamine, 4,4-methylenedi-(cyclohexylamine), the ether-amines of the DPA series available from Tomah Products, Milton, Wis., such as dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropylene glycol, dipropylamine poly(propylene glycol), dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propane diol, dipropylamine 2-methyl-l,3-propane diol, dipropylamine 1,4-butane diol, dipropylamine 1,3-butane diol, dipropylamine 1,6-hexane diol and dipropylamine cyclohexane-l,4-dimethanol; and their mixtures.

[0492] 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.

[0493] 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 salt-converting groups of ternary or quaternary ammonium groups may take place before or during mixing with water.

[0494] 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.

[0495] 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.

[0496] 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.

[0497] Preferably, the aqueous polyurethane dispersion has a polyurethane (or active ingredient, 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.

[0498] Also preferred, 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.

[0499] 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).

[0500] 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).

[0501] 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 polyurethane (such as the NEOREZ® series, DSM, such as NEOREZ® R989, NEOREZ® and R-2202).

[0502] According to a preferred embodiment, the aqueous dispersion of polyurethane particles can be selected from aqueous dispersions of particles of compounds having the INCI name polyurethane-35 or compounds having the INCI name poly-urethane-34.

[0503] 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.

[0504] 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.

[0505] 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.

[0506] 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.

[0507] The motif(s) derived 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.

[0508] 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.

[0509] 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.

[0510] Among the hydroxyalkyl (meth)acrylates, hydroxyethyl acrylate may be mentioned, 2-Hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-Hydroxypropyl methacrylate.

[0511] Among the aryl (meth)acrylates, benzyl acrylate and acrylate may be mentioned phenyl.

[0512] Particularly preferred esters of (meth)acrylic acid are the 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.

[0513] 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.

[0514] Examples of (meth)acrylic acid amides include (meth)acrylamides, as well as N-alkyl (meth)acrylamides, in particular alkyl in C2 to Ci2. Among the N-alkyl (meth)acrylamides, we can mention N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide and N-undecylacrylamide.

[0515] 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.

[0516] Preferably, the acrylic polymer(s) according to the invention comprise one or more motifs derived from the following monomers:

[0517] a) (meth)acrylic acid; and

[0518] 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.

[0519] Preferably, the aqueous dispersion of acrylic polymer particles does not Does not contain a surfactant.

[0520] The term “surfactant” means any agent capable of modifying the surface tension between two surfaces.

[0521] Among the acrylic polymers according to the invention, mention may be made of 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.

[0522] 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.

[0523] As an additional monomer, examples include styrenic monomers, in particular styrene and alpha-methylstyrene, and preferably styrene.

[0524] 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.

[0525] 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.

[0526] 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.

[0527] Preferably, composition C comprises at least an aqueous dispersion of acrylic polymer particles.

[0528] More preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more motifs derived from the following monomers:

[0529] a) (meth)acrylic acid; and

[0530] 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.

[0531] 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

[0532] According to a particular embodiment, the silicone compound(s) comprising at minus one carboxylic group are chosen from silicone acrylic copolymers.

[0533] Thus, according to a particular embodiment, the compound or compounds having at least one carboxylic function are chosen from among silicone acrylic copolymers.

[0534] Preferably, said silicone acrylic copolymer(s) comprise:

[0535] - at least one acrylic, methacrylic, or crotonic motif; and

[0536] - at least one polydimethylsiloxane (PDMS) motif.

[0537] 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.

[0538] 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.

[0539] 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.

[0540] Preferably, the polymerizable radical group comprises at least one vinyl group.

[0541] 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.

[0542] 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.

[0543] 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.

[0544] Preferably, said silicone acrylic copolymer(s) comprise:

[0545] - at least one acrylic or methacrylic or crotonic motif, and at least one motif acrylic ester or methacrylic ester or vinyl ester; and

[0546] - at least one polydimethylsiloxane (PDMS) motif.

[0547] 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.

[0548] By crotonic motif is meant a motif derived from a crotonic acid monomer or one of its salts.

[0549] By alkyl crotonate motif is meant a motif derived from a crotonic acid ester monomer, having a saturated linear or branched alkyl radical containing from 1 to 20 carbon atoms.

[0550] 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.

[0551] A vinyl acetate motif is defined as a motif derived from a vinyl acetate monomer.

[0552] 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.

[0553] 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

[0554] - at least one polydimethylsiloxane (PDMS) motif comprising at least one group polymerizable radical comprising at least one vinyl group.

[0555] 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 2 to 20 carbon atoms, preferably 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.

[0556] Even more preferably, the composition comprises one or more silicone acrylic copolymers comprising:

[0557] - 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

[0558] - at least one polydimethylsiloxane (PDMS) motif comprising at least one group polymerizable radical comprising at least one vinyl group.

[0559] Among the silicone acrylic copolymers that can be used in the context of the invention, mention can be made of the compound sold by 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.

[0560] 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.

[0561] 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.

[0562] 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.

[0563] 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. Organic solvents

[0564] Composition C used in the process according to the invention may comprise one or more organic solvents.

[0565] Examples of organic solvents include lower CrC4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, mono- propylene glycol methyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols, including aromatic monoalcohols such as benzyl alcohol, phenoxyethanol, and mixtures thereof.

[0566] 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.

[0567] 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

[0568] Composition C used in the process according to the invention may contain any adjuvant or additive usually used.

[0569] Among the additives that may be contained in composition C, we may 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.

[0570] 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, vesicle dispersion in particular of ionic or non-ionic lipids, bi-phase or multi-phase lotion.

[0571] 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

[0572] Composition T as defined above can be applied to dry or damp hair, as well as to all types of hair, light or dark, natural or colored, permed, bleached or straightened.

[0573] Preferably, a washing, rinsing, spinning and / or drying step is implemented after the application of composition T as defined above.

[0574] More preferably, a drying step is implemented after application of the composition T as defined previously.

[0575] The application of composition T can be carried out at room temperature (between 15 to 25°C).

[0576] After application of composition T, it is possible to wait between 1 minute and 12 hours, in particular between 1 minute and 10 hours, more particularly between 1 minute and 7 hours, more preferably between 1 minute and 6 hours, before the application of composition C to the hair or for example a washing, rinsing, wringing or drying step.

[0577] Preferably, the application time is between 1 minute and 5 hours, preferably between 5 minutes and 1 hour, after application of composition T and before application of composition C to the hair.

[0578] 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.

[0579] Preferably, a washing, rinsing, wringing and / or drying step is carried out after the application of composition C to the hair.

[0580] More preferably, a drying step is implemented after the application of composition C to the hair.

[0581] The application of composition C 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.

[0582] The application of composition C to the hair is generally carried out at room temperature (between 15 and 25 °C).

[0583] After application of composition C to the hair, one can 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, wringing and / or drying step.

[0584] After application of composition C, the hair may be left to dry or dried, for example at a temperature of 30 °C or higher.

[0585] The process according to the invention can thus include a step of applying heat to the hair using a heating tool.

[0586] 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...

[0587] Preferably, the heat application step of the process of the invention is carried out using a hair dryer.

[0588] 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.

[0589] During the heat application stage on the hair, a mechanical action on the strands can be exerted such as combing, brushing, passing with fingers.

[0590] 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.

[0591] 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.

[0592] 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.

[0593] Step (cl) can be carried out before step (c2).

[0594] 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.

[0595] 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.

[0596] During drying, mechanical action on the strands can be exerted such as combing, brushing, passing with fingers.

[0597] 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.

[0598] After the heating step, a shaping step can be implemented with, for example, a straightening iron; the temperature for the shaping step can be between 110 and 220°C, preferably between 140 and 200°C.

[0599] Preferably, the invention is a hair coloring process comprising the following steps:

[0600] i) the application to the hair of a composition T comprising at least one agent AA selected from amino acids and their derivatives;

[0601] ii) optionally a leave-on time of said composition T on the hair of 1 minute to 6 hours, preferably from 1 minute to 5 hours;

[0602] iii) optionally a step of washing, rinsing, wringing and / or drying said hair, preferably drying; then (iv) the application to the hair of at least one composition C comprising:

[0603] - at least one (poly)carbodiimide compound as described above; and

[0604] - at least one coloring agent selected from pigments, direct colorants, and their mixtures as described previously; then (v) optionally, a processing time of said composition C on the hair of 1 to 30 minutes, preferably 1 to 20 minutes; then vi) optionally a step of washing, rinsing, wringing and / or drying said hair.

[0605] Preferably, composition C further comprises at least one compound having at least one carboxylic function as described above.

[0606] Advantageously, the step of applying composition C to the hair is repeated several times.

[0607] According to a preferred embodiment, step b) consists 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:

[0608] - composition A comprising at least one (poly)carbodiimide compound such that as defined previously,

[0609] composition A and / or composition B comprising at least one colouring agent selected from pigments, direct colorants, and mixtures thereof as defined above.

[0610] Composition A and / or composition B may optionally include at least one compound having at least one carboxylic function as described above.

[0611] Advantageously, composition B comprises at least one compound having at least one carboxylic function as described above.

[0612] Preferably, composition B comprises at least one colouring agent selected from pigments, direct colorants, and mixtures thereof as described above.

[0613] Preferably, composition A does not include at least one colouring agent selected from pigments, direct colorants, and mixtures thereof as described above.

[0614] 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.

[0615] 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.

[0616] 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, and even more preferably from 1 to 12% by weight relative to the total weight of Composition A.

[0617] The total quantity of the compound or compounds having at least one carboxylic function is 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.

[0618] 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.

[0619] 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.

[0620] The present invention will now be described more specifically by means of examples, which are in no way limiting to the scope of the invention. However, the examples allow for the support of specific features, variants, and preferred embodiments of the invention. EXAMPLES

[0621] The (poly)carbodiimide(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.

[0622] More particularly, the process for preparing the (poly)carbodiimides of the invention uses, in a first step, a diisocyanate reagent (1): O=C=N-LrN=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 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 previously. Benzoyl halogen such as benzoyl chloride can be added to deactivate the catalyst.

[0623] 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 0.5 eq. of HEH reagent with Rb Xi and E as defined above, to give the "symmetrical" compound according to the invention (4): [R1-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.

[0624] 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.

[0625] According to a 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.

[0626] 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'),

[0627] 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),

[0628] Formula (7) in which Rb Xb Lb R2, X2, n, z and E are as defined previously.

[0629] 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),

[0630] 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.

[0631] This last compound (8) can then react with 1 eq of compound (4'): Ri-Xi-C(O)-NH-Lr(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 give rise to the (poly)carbodiimide 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 as defined above.

[0632] (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.

[0633] Example 1: Process for the synthesis of the (poly)carbodiimide compound

[0634] 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.

[0635] 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.

[0636] 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.

[0637] 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

[0638] The compositions T1 and T2 as described in Tables 1 and 2 below were prepared: quantities are expressed in g of active material / 100g, unless otherwise stated.

[0639] [Tables 1] Compositions Tl T2 L-Glycine 5 - Poly-e-lysine - 1.25 Agent pH Qs pH 2.6 Qs pH 2.6 Water Qsp 100 Qsp 100

[0640] Compositions A and B as described in Tables 2 and 3 below were also prepared: quantities are expressed in g of raw material as is / 100g, unless otherwise stated.

[0641] [Tables2] Composition A Polycarbodiimide (1) 17.5 Ethanol 20 Water Qsp 100

[0642] (1) synthesized according to the synthesis process described in Example 1 (at 40% of material active in water).

[0643] [Tables3] Composition B Acrylates copolymer (2) 29.2 Red iron oxide 12 Divinyldimethicone / Dimethicone copolymer (3) (and) Ci2-n Pareth-3 (and) Ci2-n Pareth-23 10.2 Ethanol 3.75 Preservative(s) qs Water qsp 100

[0644] (2) sold by the company DAITO KASEI KOGYO under the trade name DAITOSOL 3000SLPN-PE1 (aqueous dispersion with 30% active ingredient).

[0645] (3) sold by Dow Corning under the trade name DOW CORNING HMW 2220 NON-IONIC EMULSION (Divinyldimethicone / dimethicone block copolymer in aqueous emulsion) (with 60% active material)).

[0646] Composition A was then mixed with composition B at a mass ratio of 50 / 50 to obtain composition C according to the invention. Protocol

[0647] Three different processes were implemented.

[0648] According to the first and second processes, compositions T1, for the first process, or T2, for the second process, were first applied to strands of different hair types. Each of these compositions was applied to strands of hair at a rate of 1 g of composition per gram of strand. The treatment was left to act for 1 hour on a plate at a temperature of 39°C. Then, the strands were rinsed and then dried with a hairdryer.

[0649] Composition C was then applied to the strands previously treated with composition T1 or composition T2, at a rate of 0.8 g of composition per gram of strand. The hair strands were then detangled and dried with a hairdryer.

[0650] The process using compositions T1 or T2, and then composition C, are therefore processes according to the invention. Hereafter, they are referred to as processes PI and P2, respectively.

[0651] According to the third method, neither composition T1 nor composition T2 was applied. Only composition C was applied to strands of different types, at a rate of 0.8 g of composition per gram of strand. The hair strands were then detangled and dried with a hairdryer.

[0652] This process is therefore a comparative process, referred to hereafter as process P3.

[0653] The processes applied are summarized in Table 4 below:

[0654] [Tables4] PI (invention) P2 (invention) P3 (comparative) Processes Application of compositions T1 + C T2 + CC

[0655] The different strands of hair treated by the PI to P3 processes were then subjected to a test of several repeated shampoos in order to evaluate the tenacity (the persistence) of the color obtained with the shampoos, according to the shampoo protocol described below. Shampooing protocol:

[0656] The colored hair strands are combed, moistened under water at 35°C before being passed between the fingers 5 times for 5 seconds. The hair strands are then squeezed between two fingers.

[0657] A standard shampoo (Garnier Ultra Doux) is applied evenly to the colored strands at a rate of 0.4g of standard shampoo per gram of strands, gently massaging the strands of hair along their length (6 passes) for 15 seconds, from root to tip.

[0658] The strands of hair are then placed in a watch glass and left to rest for 1 minute.

[0659] Next, the hair strands are rinsed with water by passing the strand between the fingers (15 passes). The hair strands are then squeezed dry between two fingers before the next shampoo.

[0660] Once the tests of several shampoos have been carried out, the strands of hair are combed and dried with a hairdryer. Results

[0661] The persistence of the color of the highlights was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, specular component included).

[0662] In this L*a*b* system, L* represents the intensity of the color, a* indicates the green / red color axis and b* the blue / yellow color axis.

[0663] The permanence of the color is assessed by the color difference AE between the colored strands before shampooing, and then after 5 shampoos according to the protocol described above. The lower the AE value, the more the color remains after shampooing.

[0664] The value of AE is calculated according to the following equation: A ™ "i'ASC 'Sy-, 't' 'S?.; )

[0665] In this equation, L*, a*, b* represent the values ​​measured after hair coloring and after shampooing, and Lo*, a0*, b0* represent the values ​​measured after hair coloring but before shampooing.

[0666] As indicated above, the different processes were carried out on different types of hair. In particular, they were carried out on strands of dry natural hair that were 90% white, referred to hereafter as BN90, and on strands of dry white hair that were 90% permed, referred to hereafter as BP90.

[0667] Thus, in the tables below, for example, the PI process implemented on BN90 hair strands is called P1BN90, or the P3 process implemented on BP90 hair strands is called P3BP90, etc.

[0668] The results are summarized in the tables below.

[0669] [Tables5] Processes Number of shampoos L* a* b* AE P3BN90 (comparative) 0 36.2 25.8 19.9 - 5 42.6 16.1 14.1 13.0 P1BN90 (invention) 0 37.5 23.4 18.0 - 5 39.7 18.7 15.1 5.9

[0670] [Tableauxô] P3BP90 Processes (comparative) Number of shampoos L* a* b* AE 0 34.1 25.6 19.7 - 5 55.1 7.3 12.9 28.7 P2BP90 (invention) 0 31.0 27.9 21.6 - 5 35.4 25.0 19.0 5.9

[0671] Hair strands treated with the processes according to the invention and washed with five shampoos exhibit lower AE values ​​than those of hair strands treated with the comparative process, for different types of hair, whether on BN90 or BP90 hair strands.

[0672] Thus, the coloured coating obtained with the processes according to the invention exhibits improved resistance to shampoos.

Claims

Demands

1. A hair coloring process comprising: a) applying to the hair at least one composition T comprising at least one agent AA selected from amino acids and their derivatives; then b) applying to the hair at least one composition C comprising: - at least one (poly)carbodiimide compound; and - at least one coloring agent selected from pigments, direct dyes, and mixtures thereof.

2. A method according to claim 1, characterized in that the agent AA is selected from natural amino acids, synthetic amino acids, in their L, D, or racemic form, and comprising at least one acid function selected from carboxylic, sulfonic, phosphonic or phosphoric acid functions, peptides, polypeptides, and mixtures thereof.

3. A process according to claim 1 or 2, characterized in that the AA agent is selected from aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, camitine, cysteine, glutamine, glycine, histidine, lysine, polylysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine, valine, and mixtures thereof, preferably from lysine, polylysine, glycine, and mixtures thereof.

4. A process according to any one of the preceding claims, characterized in that agent AA is present in a total content of 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 0.75 to 15% by weight, even more preferably 1 to 10% by weight, better 1 to 5% relative to the total weight of composition T.

5. A process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) is / are selected from the compounds of the following formula (I): O q ® À r % Ri—Xr "N—A——A4—N' H l AH 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 group selected from a hydrocarbon radical, preferably alkyl, possibly interrupted by one or more heteroatoms, a group selected from the following groups: alkoxysilyl, 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, possibly interrupted by one or more heteroatoms and by one or more groups chosen from among the alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl groups,hydroxyalkylsilyl, aldehyde alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylmylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and azacyclopropane; - n denotes an integer ranging from 1 to 1000; and - A is a monomer chosen from the compounds below:

6. A process according to any one of claims 1 to 4, 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 their mixtures; - 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); - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more he- teroatom(s).

7. A process according to claim 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 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; - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1; - L1 is chosen from a divalent aliphatic hydrocarbon radical in Ci-Ci8, 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 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 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.

8. A process according to claim 6 or 7, 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 ranging from 1 to 20, with n+z > 2 and w is equal to 1; - Li is a C3-Ci5 cycloalkylene radical; - E independently represents a grouping chosen from: -0-R3-0-; -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 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.

9. A method according to any one of claims 6 to 8, 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 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 Ci-C4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30; - n and z denote an integer ranging from 1 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.

10. A method according to any one of claims 6 to 9, 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 of 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 a CrC4 alkyl group, more preferably a methyl group, 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 from 1 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 Ci-Ci8 branched alkylene radical such as methylene, propylene, butylene, ethylene, possibly interrupted by one or more heteroatom(s).

11. A method according to any one of claims 6 to 10, characterized in that the (poly)carbodiimide compound(s) is / are selected from the compounds of the following formula (XII): 7 / M 0 V'"" y-0 V ... jNH . àC V ly s. 0 Xy,X ' ' WH 1 ¥ 0 (XII), in which Li is 4,4-dicyclohexylene methane, n and z denote a an integer from 1 to 20, with n+z from 4 to 10, 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), and r and s denote an integer from 4 to 30.

12. 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.

13. A process according to any one of the preceding claims, characterized in that the total quantity of colouring agent(s) selected from pigments, direct colourings, and mixtures thereof ranges from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight relative to the total weight of composition C.

14. A method according to any one of the preceding claims, characterized in that step b) 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 and 5 to 11, composition A and / or composition B comprising at least one coloring agent selected from pigments, direct dyes, and mixtures thereof as defined in claim 1.