Process for dyeing hair keratin fibres comprising the application of a dye composition and then the application of a (POLY)carbodiimide compound and a particular polymer

Abstract

The present invention relates to a process for dyeing hair keratin fibres comprising: a) the application to the hair keratin fibres of at least one dye composition C comprising at least one colouring agent chosen from direct dyes, oxidation dye precursors and mixtures thereof, and optionally at least one chemical oxidizing agent; and then b) the application of at least one composition T comprising: (1) at least one (poly)carbodiimide compound; (2) at least one polymer comprising at least one reactive group chosen from carboxylic acids; and (3) optionally at least one silicone.

Description

[0001] DESCRIPTION

[0002] TITLE: Process for dyeing hair keratin fibres comprising the application of a dye composition and then the application of a (poly)carbodiimide compound and a particular polymer

[0003] The present invention concerns a process for dyeing hair keratin fibres comprising the application of at least one dye composition C comprising at least one particular colouring agent, followed by the application of at least one composition T comprising at least one (poly)carbodiimide compound, at least one particular polymer and optionally at least one silicone.

[0004] Technical field

[0005] In the field of dyeing hair keratin fibres, it is already known practice to dye hair keratin fibres via various techniques using direct dyes or pigments for nonpermanent colouring, or dye precursors for permanent colouring.

[0006] There are essentially three types of process for dyeing hair keratin fibres: a) “permanent” dyeing, the function of which is to afford a substantial modification to the natural colour and which uses oxidation dyes which penetrate into the hair fibre and form the dye via an oxidative condensation process; b) non-permanent, semi-permanent or direct dyeing, which does not use the oxidative condensation process and withstands four or five shampoo washes; it consists in dyeing keratin fibres with dye compositions containing direct dyes; c) temporary dyeing, which gives rise to a modification of the natural colour of the head of hair which lasts from one shampoo wash to the next, and which serves to enhance or correct a shade that has already been obtained. It may also be likened to a “makeup” process.

[0007] Another dyeing method consists in using pigments. Specifically, the use of pigment on the surface of keratin fibres generally makes it possible to obtain colourings that are visible on dark hair keratin fibres, since the surface pigment masks the natural colour of the fibre. However, the colourings obtained via this dyeing method have the drawback of having poor resistance to shampoo washing and also to external agents such as sebum, perspiration, brushing and / or rubbing.

[0008] The need thus remains for a process for dyeing hair keratin fibres, dyed with direct dyes and / or oxidation dye precursors, which has the advantage of improving the persistence of the colouring with respect to shampoo washing and the various stresses to which hair keratin fibres may be subjected, such as brushing and / or rubbing.

[0009] Thus, the aim of the present invention is to develop a process for dyeing hair keratin fibres, dyed with direct dye(s) and / or oxidation dye precursors, which has the advantage of improving the persistence of the colouring with respect to shampoo washing and to the various stresses to which hair keratin fibres may be subjected, such as brushing and / or rubbing.

[0010] Disclosure of the invention

[0011] One subject of the present invention is a process for dyeing hair keratin fibres comprising: a) the application to the hair keratin fibres of at least one dye composition C comprising at least one colouring agent chosen from direct dyes, oxidation dye precursors and mixtures thereof, and optionally at least one chemical oxidizing agent; and then b) the application of at least one composition T comprising:

[0012] (1) at least one (poly)carbodiimide compound;

[0013] (2) at least one polymer comprising at least one reactive group chosen from carboxylic acids; and

[0014] (3) optionally at least one silicone.

[0015] By virtue of the process for dyeing hair keratin fibres according to the invention, improved persistence of the colouring with respect to shampoo washing is obtained.

[0016] For the purposes of the present invention, the term “colouring that is persistent with respect to shampoo washing" means that the colouring obtained persists after one shampoo wash, preferably after five shampoo washes.

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

[0018] Unless otherwise indicated, the limits of a range of values are included in that range, notably in the expressions “between” and “ranging from ... to ..." .

[0019] The invention is not limited to the examples illustrated. The characteristics of the various examples may notably be combined within variants which are not illustrated.

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

[0021] - an “alkyl" radical denotes a linear or branched saturated radical containing, for example, from 1 to 20 carbon atoms; - an “aminoalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an NH2 group;

[0022] - a “hydroxyalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an OH group;

[0023] - an “alkylene” radical denotes a linear or branched divalent saturated C2-C4 hydrocarbon-based group such as methylene, ethylene or propylene;

[0024] - a “cycloalkyF or “alicycloalkyl” radical denotes a saturated monocyclic or polycyclic, preferably monocyclic, cyclic hydrocarbon-based group 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 norbornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl; preferably, the cycloalkyl radical is then an isobornyl group;

[0025] - a “cycloalkylene” radical denotes a divalent cycloalkyl group with “cycloalkyF as defined previously, preferably of C3-C12;

[0026] - an “aryl” radical is a monocyclic, bicyclic or tricyclic, fused or non-fused, unsaturated and aromatic hydrocarbon-based cyclic radical, comprising from 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms; preferably, the aryl group comprises 1 ring of 6 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl, preferably tolyl, xylyl, or methylnaphthyl; preferably, the aryl group represents phenyl;

[0027] - an “arylene” radical is a divalent aryl radical with “aryl” as defined previously; preferably, arylene represents phenylene;

[0028] - a “heterocyclic” radical denotes a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based radical, comprising one or more heteroatoms, preferably from 1 to 5 atoms chosen from O, S orN, including from 3 to 20 ring members, preferably between 5 and 10 ring members, such as imidazolyl, pyrrolyl and furanyl;

[0029] - a “heterocycloalkylene” radical is a divalent heterocyclic group with “heterocyclic” as defined previously;

[0030] - an “aryloxy” radical denotes an aryl-oxy radical with “aryl” as defined previously; - an “alkoxy” radical denotes an alkyl-oxy radical with “alkyl” as defined previously;

[0031] - an “acyloxy” radical denotes an ester radical R-C(O)-O- with R being an alkyl group as defined previously;

[0032] - a “reactive” group is a group that is capable of forming a covalent bond with another identical or different group, by chemical reaction.

[0033] Unless otherwise indicated, when compounds are mentioned in the present patent application, this also includes the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof or the salts thereof, alone or as a mixture.

[0034] For the purposes of the present invention, the term “the hair keratin fibres” means head hair. This term does not correspond to bodily hairs, the eyebrows or the eyelashes.

[0035] Dye composition C

[0036] According to the process of the invention, the hair keratin fibres are previously dyed with a dye composition C.

[0037] The dye composition C comprises at least one colouring agent chosen from direct dyes, oxidation dye precursors and mixtures thereof.

[0038] Direct dyes

[0039] The term “direct dye” means natural and / or synthetic dyes, other than oxidation dyes. These are dyes which will spread superficially on the fibre. They may be ionic, for example cationic or anionic, or nonionic.

[0040] Preferably, the direct dye(s) are chosen from 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 the form of mixtures.

[0041] The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances. The term “anionic direct dye” means any direct dye including in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes. As examples of acid dyes, mention may be made of: 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, Acid 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 or Sunset Yellow; Acid Red 111, Acid Red 134, Acid Yellow 38;

[0042] As examples of anionic pyrazolone azo dyes, mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76 or Acid Yellow 17;

[0043] As examples of anthraquinone dyes, mention may be made of: 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; Acid Black 48;

[0044] As examples of nitro dyes, mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XXIF), mention may be made of: Acid Yellow 1, the sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid, 2-piperidino-5- nitrobenzenesulfonic acid, 2-(4’-N, N-(2” -hydroxy ethyl)amino-2’- nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7;

[0045] As examples of triarylmethane dyes, mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50.

[0046] As examples of xanthene dyes, mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9.

[0047] As examples of indole dyes, mention may be made of: Acid Blue 74;

[0048] As examples of quinoline dyes, mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0049] Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions containing these natural dyes and notably henna-based poultices or extracts. The direct dyes are preferably chosen from ionic direct dyes, preferentially from anionic direct dyes, cationic direct dyes and mixtures thereof, more preferentially from cationic dyes and mixtures thereof.

[0050] Advantageously, the direct dye(s) may be present in a total amount ranging from 0.001% to 10% by weight and preferably from 0.005% to 5% by weight relative to the total weight of composition C.

[0051] Advantageously, the ionic direct dye(s), preferably cationic direct dye(s), may be present in a total amount ranging from 0.001% to 10% by weight and preferably from 0.005% to 5% by weight relative to the total weight of composition C.

[0052] Oxidation dye precursors

[0053] The oxidation dye precursors are chosen from oxidation bases and oxidation couplers, and mixtures thereof.

[0054] Preferably, the oxidation bases are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, the corresponding addition salts thereof, the solvates thereof, the salts thereof and mixtures thereof.

[0055] Among the para-phenylenediamines that may be mentioned, for example, are para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3- dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl- para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(P-hydroxyethyl)- para-phenylenediamine, 4-N,N-bis(P-hydroxyethyl)amino-2-methylaniline, 4-N,N- bis(P-hydroxyethyl)amino-2-chloroaniline, 2-P-hydroxyethyl-para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2- isopropyl-para-phenylenediamine, N-(P-hydroxypropyl)-para-phenylenediamine, 2- hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para- phenylenediamine, N-ethyl-N-(P-hydroxyethyl)-para-phenylenediamine, N-(P,y- dihydroxypropyl)-para-phenylenediamine, N-(4’-aminophenyl)-para- phenylenediamine, N-phenyl-para-phenylenediamine, 2-P-hydroxyethyloxy -para- phenylenediamine, 2-P-acetylaminoethyloxy -para-phenylenediamine, N-(P- methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para- phenylenediamine, 2-P-hydroxyethylamino-5-aminotoluene and 3 -hydroxy- 1 -(4’- aminophenyl)pyrrolidine, and the corresponding addition salts with an acid. Among the para-phenylenediamines mentioned above, paraphenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2-P- hydroxyethyl-para-phenylenediamine, 2-P-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3- dimethyl-para-phenylenediamine, N,N-bis(P-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-P-acetylaminoethyloxy-para- phenylenediamine, and the corresponding addition salts with an acid, are particularly preferred.

[0056] Among the bis(phenyl)alkylenediamines that may be mentioned, for example, are N,N’-bis(P-hydroxyethyl)-N,N’-bis(4’-aminophenyl)-l,3-diaminopropanol, N,N’- bis(P-hydroxyethyl)-N,N’-bis(4’-aminophenyl)ethylenediamine, N,N’-bis(4- aminophenyl)tetramethylenediamine, N,N’-bis(P-hydroxyethyl)-N,N’-bis(4- aminophenyl)tetramethylenediamine, N,N’-bis(4- methylaminophenyl)tetramethylenediamine, N,N’-bis(ethyl)-N,N’-bis(4’-amino-3’- methylphenyl)ethylenedi amine and 1 , 8 -bi s(2, 5 -diaminophenoxy)-3 , 6 -di oxaoctane, and the corresponding addition salts.

[0057] Among the para-aminophenols that are mentioned are, for example, paraaminophenol, 4-amino-3 -methylphenol, 4-amino-3 -fluorophenol, 4-amino-3- chlorophenol, 4-amino-3 -hydroxymethylphenol, 4-amino-2-m ethylphenol, 4-amino-

[0058] 2 -hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2- aminomethylphenol, 4-amino-2-(P-hydroxyethylaminomethyl)phenol and 4-amino-2- fluorophenol, and the corresponding addition salts with an acid.

[0059] Among the ortho-aminophenols that may be mentioned, for example, are 2- aminophenol, 2-amino-5 -methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and the corresponding addition salts.

[0060] Among the heterocyclic bases that may be mentioned, for example, are pyridine, pyrimidine and pyrazole derivatives.

[0061] Among the pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, for example 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3 -aminopyridine and 3,4- diaminopyridine, and the corresponding addition salts.

[0062] Other pyridine oxidation bases that are useful in the present invention are the

[0063] 3-aminopyrazolo[l,5-a]pyridine oxidation bases or the corresponding addition salts described, for example, in patent application FR 2 801 308. Examples that may be mentioned include pyrazolo[l,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[l,5- a]py ri d-3 -ylamine, 2-(morpholin-4-yl)pyrazolo[ 1 ,5 -a]pyrid-3 -ylamine, 3 - aminopyrazolo[l,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[l,5-a]pyrid-3- ylamine, (3 -aminopyrazolof 1 , 5-a]pyrid-7 -yl)m ethanol, 2-(3 -aminopyrazolof 1,5- a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo[l,5-a]pyrid-7-yl)ethanol, (3- aminopyrazolo[l,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[l,5-a]pyridine, 3,4- diaminopyrazolo[l,5-a]pyridine, pyrazolo[l,5-a]pyridine-3,7-diamine, 7-(morpholin- 4-yl)pyrazolo[l,5-a]pyrid-3-ylamine, pyrazolo[l,5-a]pyridine-3,5-diamine, 5- (morpholin-4-yl)pyrazolo[l,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[l,5-a]pyrid-5- yl)(2-hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[l,5-a]pyrid-7-yl)(2- hydroxyethyl)amino] ethanol, 3-aminopyrazolo[l,5-a]pyridin-5-ol, 3- aminopyrazolo[l,5-a]pyridin-4-ol, 3-aminopyrazolo[l,5-a]pyridin-6-ol, 3- aminopyrazolo[l,5-a]pyridin-7-ol, 2-P-hydroxyethoxy-3-aminopyrazolo[l,5- a]pyridine and 2-(4-dimethylpiperazinium-l-yl)-3-aminopyrazolo[l,5-a]pyridine; and the corresponding addition salts.

[0064] More particularly, the oxidation bases that are useful in the present invention are chosen from 3-aminopyrazolo[l,5-a]pyridines preferably substituted on carbon atom 2 with: a) a (di)(Ci-C6)(alkyl)amino group, said alkyl group possibly being substituted with at least one hydroxyl, amino or imidazolium group; b) an optionally cationic 5- to 7-membered heterocycloalkyl group comprising from 1 to 3 heteroatoms, optionally substituted with one or more (Ci- Ce)alkyl groups such as a di(Ci-C4)alkylpiperazinium group; or c) a (Ci-Ce)alkoxy group optionally substituted with one or more hydroxyl groups, such as a P-hydroxyalkoxy group, and the corresponding addition salts.

[0065] Among the pyrimidine derivatives that may be mentioned are the compounds described, for example, in patents DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96 / 15765, such as 2,4,5,6-tetraaminopyrimidine, 4- hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4- dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and the addition salts thereof and the tautomeric forms thereof, when a tautomeric equilibrium exists.

[0066] Among the pyrazole derivatives that may be mentioned are the compounds described in patents DE 3843892 and DE 4133957 and patent applications WO 94 / 08969, WO 94 / 08970, FR-A-2 733 749 and DE 195 43 988, for instance 4,5- diamino- 1 -methylpyrazole, 4, 5-diamino- 1 -(P-hydroxyethyl)pyrazole, 3 ,4- diaminopyrazole, 4,5 -diamino- 1 -(4’ -chlorobenzyl)pyrazole, 4,5 -diamino- 1,3- dimethylpyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, 4,5-diamino-l-methyl-3- phenylpyrazole, 4-amino-l,3-dimethyl-5-hydrazinopyrazole, l-benzyl-4,5-diamino-3- methylpyrazole, 4, 5-diamino-3-tert-butyl-l -methylpyrazole, 4,5-diamino- l - / c / 7- butyl-3-methylpyrazole, 4,5-diamino- l-(P-hydroxyethyl)-3-methylpyrazole, 4,5- diamino- 1 -ethyl-3 -methylpyrazole, 4,5-diamino- 1 -ethyl-3 -(4’ - methoxyphenyl)pyrazole, 4,5-diamino- l-ethyl-3-hydroxymethylpyrazole, 4,5- diamino-3 -hydroxymethyl- 1 -methylpyrazole, 4,5-diamino-3 -hydroxymethyl- 1 - isopropylpyrazole, 4,5-diamino-3-methyl-l-isopropylpyrazole, 4-amino-5-(2’- aminoethyl)amino-l,3-dimethylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5- triaminopyrazole, 3,5-diamino-l-methyl-4-methylaminopyrazole and 3,5-diamino-4- (P-hydroxyethyl)amino-l -methylpyrazole, and the corresponding addition salts. Use may also be made of 4,5-diamino-l-(P-methoxyethyl)pyrazole.

[0067] A 4,5-diaminopyrazole will preferably be used and even more preferentially 4,5-diamino-l-(P-hydroxyethyl)pyrazole and / or a corresponding salt, for example 4,5- diamino- 1 -(P-hydroxyethyl)pyrazole sulfate.

[0068] The pyrazole derivatives that may also be mentioned comprise diamino-N,N- dihydropyrazolopyrazolones and in particular those described in patent application FR- A-2 886 136, such as the following compounds and the corresponding addition salts: 2,3-diamino-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-l-one, 2-amino-3- ethylamino-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-l-one, 2-amino-3- isopropylamino-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-l-one, 2-amino-3-

[0069] (pyrrolidin-l-yl)-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-l-one, 4,5-diamino- 1,2- dimethyl- 1 ,2-dihydropyrazol-3 -one, 4,5-diamino- 1 ,2-di ethyl- 1 ,2-dihydropyrazol-3 - one, 4, 5-diamino-l,2-bis(2 -hydroxy ethyl)- l,2-dihydropyrazol-3-one, 2-amino-3-(2- hydroxyethyl)amino-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-l-one, 2-amino-3- dimethylamino-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-l-one, 2,3-diamino- 5,6,7,8-tetrahydro-lH,6H-pyridazino[l,2-a]pyrazol-l-one, 4-amino-l,2-diethyl-5- (pyrrolidin- 1 -yl)- 1 ,2-dihydropyrazol-3 -one, 4-amino-5-(3 -dimethylaminopyrrolidin- 1 -yl)-l ,2-di ethyl- l,2-dihydropyrazol-3 -one and 2,3-diamino-6-hydroxy-6,7-dihydro- lH,5H-pyrazolo[l,2-a]pyrazol-l-one.

[0070] Among the oxidation bases, para-toluenediamine, para-aminophenol, 4,5- diamino- l-(P-hydroxyethyl)pyrazole sulfate and mixtures thereof will preferably be used.

[0071] Preferably, the oxidation couplers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents and heterocyclic coupling agents, the corresponding addition salts thereof, solvates thereof, salts thereof and mixtures thereof.

[0072] Mention may be made, for example, of 1,3-dihydroxybenzene, 1,3- dihydroxy-2-m ethylbenzene, 4-chl oro-1, 3 -dihydroxybenzene, 2,4-diamino-l-(P- hydroxy ethyloxy )benzene, 2-amino-4-(P-hydroxy ethylamino)- 1 -methoxybenzene, 1,3 -diaminobenzene, l,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido- 1 -dimethylaminobenzene, sesamol, l-P-hydroxyethylamino-3,4- methylenedioxybenzene, a-naphthol, 2-methyl-l-naphthol, 6-hydroxyindole, 4- hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3 -hydroxypyridine, 6- hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(P- hydroxyethyl)amino-3,4-methylenedi oxybenzene, 2,6-bis(P- hydroxyethylamino)toluene, 4-amino-2-hydroxytoluene, 2-methyl-5- hydroxy ethylaminophenol, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H- 3-methylpyrazol-5-one, l-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[l,5- b][l,2,4]triazole, 2,6-dimethyl[3,2-c][l,2,4]triazole and 6-methylpyrazolo[l,5- a]benzimidazole, 2-methyl-5-aminophenol, 5-N-(P-hydroxyethyl)amino-2- methylphenol, 3 -aminophenol, 3-amino-2-chloro-6-methylphenol, 5-amino-6-chloro- o-cresol, 2-([3-amino-4-methoxyphenyl]amino)ethanol, and the corresponding addition salts with an acid.

[0073] Among the oxidation couplers, 4-amino-2-hydroxytoluene, 2-methyl-5- hydroxyethylaminophenol, 6-hydroxyindole, 5-amino-6-chloro-o-cresol and mixtures thereof will preferably be used.

[0074] In general, the addition salts of oxidation bases or of oxidation couplers which can be used in the context of the invention are chosen in particular from the addition salts with an acid, such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

[0075] Advantageously, when the oxidation dye precursor(s) are present in composition C, the total content of oxidation dye precursor(s) is from 0.01%to 20% by weight, preferentially from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight, even more preferentially from 0.5% to 10% by weight, better still from 0.7% to 6% by weight relative to the total weight of composition C.

[0076] Advantageously, when the oxidation base(s) are present in composition C, the total content of oxidation base(s) is from 0.01% to 20% by weight, preferentially from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight, even more preferentially from 0.3% to 10% by weight, better still from 0.5% to 5% by weight relative to the total weight of composition C.

[0077] Advantageously, when the oxidation coupler(s) are present in composition C, the total content of oxidation coupler(s) is from 0.01% to 20% by weight, preferentially from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight, even more preferentially from 0.5% to 10% by weight, better still from 0.7% to 3% by weight relative to the total weight of composition C.

[0078] Advantageously, the colouring agent(s) chosen from direct dyes, oxidation dye precursors, and mixtures thereof, are present in composition C in a content ranging from 0.001% to 20% by weight, preferentially from 0.005% to 15% by weight, relative to the total weight of composition C.

[0079] Chemical oxidizing agents

[0080] Composition C may also comprise at least one chemical oxidizing agent.

[0081] For the purposes of the present invention, the term “ chemical oxidizing agent” means an oxidizing agent other than atmospheric oxygen.

[0082] The chemical oxidizing agent(s) (or bleaching agents) that may be used in the present invention may be chosen from hydrogen peroxide, urea hydrogen peroxide, alkali metal bromates, persalts, such as perborates and persulfates, in particular sodium persulfate, potassium persulfate and ammonium persulfate, peracids and oxidase enzymes (with their optional cofactors), among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, and mixtures thereof; more preferentially, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, persalts, and mixtures thereof, even more preferentially hydrogen peroxide.

[0083] According to a preferred embodiment, composition C comprises at least one chemical oxidizing agent, preferably hydrogen peroxide.

[0084] According to another embodiment, composition C does not contain any chemical oxidizing agent.

[0085] Advantageously, when composition C comprises at least one chemical oxidizing agent, the total content of chemical oxidizing agent(s) ranges from 0.1% to 40% by weight, preferentially from 1% to 30% by weight, more preferentially from 5% to 20% by weight, even more preferentially from 6% to 20% by weight relative to the total weight of composition C. Organic solvents

[0086] Composition C used in the context of the process according to the invention may comprise one or more organic solvents.

[0087] Examples of organic solvents that may be mentioned include C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, for instance 2- butoxy ethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols, notably aromatic monoalcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0088] The organic solvents may be present in a total content of between 1% and 80% by weight, preferably between 5% and 70% by weight and more preferentially between 10% and 40% by weight relative to the total weight of composition C.

[0089] Composition C used in the context of 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 and more preferentially from 20% to 75% by weight relative to the total weight of composition C.

[0090] Additives

[0091] Composition C used in the context of the process according to the invention may contain any adjuvant or additive usually used.

[0092] Among the additives that may be contained in the composition, mention may be made of reducing agents, softeners, antifoams, moisturizers, clays, mineral fillers, UV-screening agents, peptizers, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers, preserving agents, oils, waxes other than silicones in wax form, and mixtures thereof.

[0093] According to a particular embodiment, composition C is free of (poly)carbodiimide compounds as described hereinbelow.

[0094] Composition T

[0095] Polycarbodiimide compound

[0096] Composition T used in the context of the process according to the invention comprises at least one (poly)carbodiimide compound.

[0097] The term “(poly)carbodiimide”, in the meaning of the present invention and in a manner known per se, designates carbodiimides and polycarbodiimides. The composition may comprise at least two different (poly)carbodiimide compounds, present as a mixture in the composition.

[0098] The term “ (poly) carbodiimide compound" means a compound comprising one or more carbodiimide groups, preferably at least two carbodiimide groups, more preferentially at least three carbodiimide groups; in particular, the number of carbodiimide groups does not exceed 200, preferably 150, more preferentially 100.

[0099] The term “ carbodiimide group"" means a divalent linear triatomic fraction of general formula -(N=C=N)-.

[0100] The (poly)carbodiimide compound(s) according to the invention may optionally comprise in their structure one or more reactive groups different from carbodiimide groups, chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.

[0101] The reactive group(s) other than the carbodiimide groups may be side or end groups. Preferably, the (poly)carbodiimide compound(s) comprise one or more end groups different from carbodiimide groups, preferably one or more end groups chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carb oxy alkyl silyl, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.

[0102] According to a particular embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) below:

[0103] (I), in which:

[0104] - Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; - Ri and R2 independently represent a group chosen from a hydrocarbon-based radical, preferably alkyl, optionally interrupted with one or more heteroatoms, a group chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups, and a hydrocarbon-based radical, preferably alkyl, optionally interrupted with one or more heteroatoms and with one or more groups chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups; - n denotes an integer ranging from 1 to 1000; and

[0105] - A is a monomer chosen from the compounds below:

[0106] According to another embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I’) below: in which:

[0107] - Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0108] - Yi and Y2 independently represent a divalent organic radical chosen from a saturated Ci to C36 aliphatic group or a Ce to C24 aromatic or alkylaromatic group, the aliphatic or aromatic group optionally comprising one or more non-pendent heteroatoms, such as a nitrogen atom, an oxygen atom, a sulfur atom, or combinations thereof;

[0109] - Zi and Z2 independently represent a reactive end group or an inert end group;

[0110] - as inert end group, Zi and Z2 may represent, independently, a saturated, linear or branched or cyclic Ci to C50 aliphatic group, or a Ce to Cis aromatic group, said aliphatic and aromatic groups optionally comprising from 1 to 10 heteroatoms chosen from nitrogen, oxygen, sulfur and combinations thereof, and the aliphatic or aromatic group may be partially or totally fluorinated; in this variant, Zi and Z2 comprise a bonding group CG connecting Zi to Yi and Z2 to Y2, the group CG possibly 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;

[0111] - as reactive end group, Zi and Z2 may be chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryl alkyl silyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups;

[0112] - Q represents an organopolymer or an organooligomer comprising repeating units of saturated, linear or branched or cyclic aliphatic groups, or of aromatic groups or alkylaromatic groups, coupled via carbonate, ester, ether, amide, urethane or urea repeating bonds or combinations thereof;

[0113] - A represents a divalent aliphatic, aromatic, alkylaromatic or linear, saturated, branched or cyclic radical containing from 2 to 30 carbon atoms, which may optionally comprise one or more non-pendent heteroatoms such as a nitrogen atom, an oxygen atom, a sulfur atom, or combinations thereof, in the aliphatic chain or the aromatic chain;

[0114] - r denotes an integer equal to 0 or 1;

[0115] - m denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0116] - m’ denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0117] - n denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1, with m + (m’*n ) > 2.

[0118] Preferably, Zi and Z2 independently represent a reactive end group; more preferentially, Zi and Z2 independently represent a group chosen from alkoxy silyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.

[0119] Such (poly)carbodiimide compounds are sold, for example, by the company Stahl B.V, under the name Permutex XR, or under the name RelcaLinklO., under the name Picassian XL and Nisshinbo compounds sold 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.

[0120] Preferably, the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) below:

[0121] (II), in which: - Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0122] - Ri and R2 independently represent a hydrocarbon-based radical optionally interrupted with one or more heteroatoms;

[0123] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w denotes an integer ranging from 1 to 3;

[0124] - Li independently represents a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof;

[0125] - E independently represents a group chosen from:

[0126] - -0-R3-0-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-, in which R3 and R4 independently represent a divalent hydrocarbon-based radical optionally interrupted with one or more heteroatoms;

[0127] - Rs independently represents a covalent bond or a saturated divalent hydrocarbonbased radical, optionally interrupted with one or more heteroatoms;

[0128] - Re independently represents a hydrogen atom or a hydrocarbon-based radical, optionally interrupted with one or more heteroatoms.

[0129] The term “ hydrocarbon-based radical" means a saturated or unsaturated, linear or branched radical containing from 1 to 300 carbon atoms, preferably from 1 to 250 carbon atoms, more preferentially from 1 to 200 carbon atoms. Preferably, the hydrocarbon-based radical is a saturated linear radical.

[0130] The hydrocarbon-based radical may comprise one or more cyclic groups.

[0131] The hydrocarbon-based radical may be interrupted with one or more heteroatoms, in particular chosen from O, S or N and / or substituted with one or more cations, anions or zwitterions or cationic groups such as ammonium, anionic groups such as carboxylate, or zwitterionic groups, and / or comprising a metal ion which may be incorporated in the form of a salt.

[0132] The term "heleroalom(s)" means an oxygen O, sulfur S or nitrogen N atom, and also halogen atoms such as Cl, F, Br and I. If the heteroatom is included in the chain of the hydrocarbon-based radical, the heteroatom is preferably chosen from oxygen O, sulfur S or nitrogen N atoms.

[0133] Preferably, Xi and X2 independently represent an oxygen atom.

[0134] Preferably, Ri and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxy carboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, and mixtures thereof. According to a preferred embodiment, Ri and R2 are independently chosen from groups (i) to (iv) below:

[0135] (i) the compound of formula (III) below:

[0136] R7-O-C(O)-C(R8)(H)- (III), in which R7 represents a C1-C3 alkyl group, and Rs represents a hydrogen atom or a C1-C3 alkyl group; preferably, R7 is a methyl and Rs is a hydrogen atom or a methyl.

[0137] (ii) the compound of formula (IV) below:

[0138] R9-[0-CH2-C(H)(RIO)]P- (IV), in which R9 represents a C1-C4 alkyl group, Rio represents a hydrogen atom or a C1-C4 alkyl group and p denotes an integer ranging from 1 to 3; preferably, R9 is a methyl, ethyl or butyl, Rio is a hydrogen atom or a methyl and p is equal to 1.

[0139] (iii) the compound of formula (V) below:

[0140] (Rii)2N-CH2-C(H)(Ri2) (V), in which Rn represents a C1-C4 alkyl group and RI2represents a hydrogen atom or a C1-C4 alkyl group; preferably, Rn is a methyl, ethyl or butyl and RI2is a hydrogen atom or a methyl.

[0141] (iv) the compound of formula (VI) below:

[0142] Ri3-[O-CH2-C(H)(Ri4)]q- (VI), in which R13 represents a C1-C4 alkyl group or a phenyl, R14 represents a hydrogen atom or a C1-C4 alkyl group and q denotes an integer ranging from 4 to 30; preferably, R13 is a methyl, ethyl or butyl and R14 is a hydrogen atom or a methyl.

[0143] Preferably, Ri and R2independently represent a compound of formula (VI) in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.

[0144] According to an alternative embodiment, Ri and R2are different and one of the radicals Ri or R2represents a compound of formula (IV) as described above and the other radical Ri or R2represents a compound of formula (VI) as described above.

[0145] Preferably, in formula (IV), R9 is a methyl, ethyl or butyl and Rio is a hydrogen atom or a methyl and p is equal to 1.

[0146] Preferably, in formula (VI), R13 is a methyl, ethyl or butyl and R14 is a hydrogen atom or a methyl and q denotes an integer ranging from 4 to 30.

[0147] According to another alternative embodiment, Ri and R2are identical and represent a compound of formula (VI) in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.

[0148] Preferably, n denotes an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0149] Preferably, z denotes an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0150] Preferably, w is equal to 1.

[0151] Preferably, w is equal to 1, n+z denotes an integer ranging from 4 to 10.

[0152] Preferably, Li is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical such as methylene, ethylene and propylene, a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene and cyclohexylene, a C3-C12 heterocycloalkylene group such as imidazolene, pyrrolene and furanylene, or a Ce-Cu arylene group such as phenylene, and mixtures thereof.

[0153] For example, Li may be chosen from a radical derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4- trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-l,3-dioctylcyclobutane, 4,4’- dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-napththylene diisocyanate, 4,4’-diphenylmethane diisocyanate, 4, d’diphenyldimethylmethane diisocyanate and phenylene diisocyanate, and mixtures thereof.

[0154] Preferably, Li is chosen from a C3-C15 cycloalkylene radical or a Ce-Cu arylene group, and mixtures thereof, such as the compounds of formula (VII) below:

[0155]

[0156] Preferably, Li is 4,4-dicyclohexylenemethane corresponding to formula (VIII) below:

[0157] (VIII). According to another embodiment, when LI is a Ce-Cu arylene group, Li is not the m-tetramethylxylylene radical represented by formula (IX) below:

[0158] (IX).

[0159] As indicated previously, E independently represents a group chosen from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 independently represent a divalent hydrocarbon-based radical optionally interrupted with one or more heteroatoms;

[0160] - Rs independently represents a covalent bond or a saturated divalent hydrocarbonbased radical, optionally interrupted with one or more heteroatoms; and

[0161] - Re independently represents a hydrogen atom or a hydrocarbon-based radical, optionally interrupted with one or more heteroatoms. Preferably, R3 and R4 are independently chosen from a Ce-Cu arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Cis alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatom(s), and mixtures thereof.

[0162] More preferentially, R3 and R4 are independently chosen from a linear or branched Ci-Cis alkylene radical such as methylene, butylene, propylene or ethylene, optionally interrupted with one or more heteroatoms.

[0163] Preferably, when R5 is not a covalent bond, R5 is chosen from a Ce-Cu arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Cis alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatom(s), and mixtures thereof.

[0164] Preferably, Re is chosen from a Ce-Cu arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Cis alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatom(s), and mixtures thereof.

[0165] Preferably, E represents a group -O-R3-O- in which R3 is chosen from a Ce- C14 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

[0166] More preferentially, E represents a group -O-R3-O- in which R3 represents a linear or branched Ci-Cis alkylene radical such as methylene, butylene, propylene or ethylene, optionally interrupted with one or more heteroatoms.

[0167] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from a-methyl styryl isocyanates of formula (X) below:

[0168] (X), in which R independently represents an alkyl group containing from 1 to 24 carbon atoms, a cycloalkyl group containing from 3 to 24 carbon atoms or an aryl group containing from 6 to 24 carbon atoms, and n denotes an integer ranging from 2 to 100.

[0169] In this embodiment, the term “alkyl group” is as defined previously.

[0170] In this embodiment, the term “cycloalkyl group” is as defined previously.

[0171] In this embodiment, n may denote an integer ranging from 2 to 50, preferably from 3 to 30 and even more preferentially from 5 to 10.

[0172] According to another particular embodiment, the (poly)carbodiimide compound is a compound of formula (XI) below:

[0173] (XI), in which R independently represents an alkyl group containing from 1 to 24 carbon atoms, a cycloalkyl group containing from 3 to 24 carbon atoms or an aryl group containing from 6 to 24 carbon atoms.

[0174] The “alkyl group”, the “cycloalkyl group” and the “aryl group” are as defined previously.

[0175] According to a preferred embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) or of formula (II) in which:

[0176] - Xi and X2 independently represent an oxygen atom;

[0177] - Ri and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, more preferentially the compound of formula (VI) as described previously in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q denotes an integer ranging from 4 to 30;

[0178] - n and z, when they are present, denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0179] - Li, when it is present, is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical;

[0180] - A, when it is present, is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical; - E, when it is present, independently represents a group chosen from:

[0181] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;

[0182] - when R5 is not a covalent bond, R5, when it is present, is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatom(s), and mixtures thereof; and

[0183] - Re, when it is present, is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatom(s), and mixtures thereof.

[0184] Preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

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

[0186] - Ri and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, and mixtures thereof;

[0187] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0188] - Li is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof;

[0189] - E independently represents a group chosen from:

[0190] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;

[0191] - when R5 is not a covalent bond, R5 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof; and

[0192] - Re is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

[0193] More preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0194] - Xi and X2 independently represent an oxygen atom; - Ri and R2 are, independently, monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed;

[0195] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0196] - Li is a C3-C15 cycloalkylene radical;

[0197] - E independently represents a group chosen from:

[0198] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;

[0199] - when R5 is not a covalent bond, R5 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof; and

[0200] - Re is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

[0201] Even more preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0202] - Xi and X2 independently represent an oxygen atom;

[0203] - Ri and R2 independently represent the compound of formula (VI) below:

[0204] Ri3-[O-CH2-C(H)(Ri4)]q- (VI), in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;

[0205] - 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;

[0206] - Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4, 4-di cyclohexylenemethane; and

[0207] - E represents a group -O-R3-O- in which R3 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

[0208] Even more preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0209] - Xi and X2 independently represent an oxygen atom;

[0210] - Ri and R2 independently represent the compound of formula (VI) below: Ri3-[O-CH2-C(H)(Ri4)]q- (VI) in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q denotes an integer ranging from 4 to 30;

[0211] - 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;

[0212] - Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylenemethane, preferably 4,4- dicyclohexylenemethane; and

[0213] - E represents a group -O-R3-O- in which R3 represents a linear or branched Ci-Cis alkylene radical such as methylene, propylene, butylene or ethylene, optionally interrupted with one or more heteroatoms.

[0214] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of formula (XII) below: in which LI is 4,4-dicyclohexylenemethane, n and z denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10, E represents a group -O-R3-O- in which R3 represents a linear or branched Ci-Cis alkylene radical such as methylene, propylene, butylene or ethylene, optionally interrupted with one or more heteroatoms, and r and s denote an integer ranging from 4 to 30. Advantageously, the (poly)carbodiimide compound(s) as defined previously are present in a total content ranging from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferentially from 0.2% to 10% by weight, even more preferentially from 0.5% to 8% by weight, and better still from 1% to 6% by weight relative to the total weight of composition T.

[0215] Polymer comprising at least one reactive group chosen from carboxylic acids.

[0216] Composition T used in the context of the process according to the invention comprises at least one polymer comprising at least one reactive group chosen from carboxylic acids, preferably at least one acrylic polymer.

[0217] Preferably, the acrylic polymer(s) are in the form of aqueous dispersions of acrylic polymer particles, more preferentially in the form of aqueous dispersions of film-forming acrylic polymer particles.

[0218] Thus, preferably, composition T comprises at least one acrylic polymer in the form of aqueous dispersions of acrylic polymer particles.

[0219] The dispersion(s) may be simple dispersions in the aqueous medium of the cosmetic composition. As a particular case of dispersions, mention may be made of latices.

[0220] For the purposes of the invention, the term "polymer" means a compound corresponding to the repetition of one or more units (these units being derived from compounds known as monomers). This or these unit(s) are repeated at least twice and preferably at least three times.

[0221] The term ‘film-forming polymer" refers to a polymer that is capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, notably on the hair keratin fibres, and preferably a cohesive film.

[0222] For the purposes of the present invention, the term “acrylic polymer" means a polymer synthesized from at least one monomer chosen from (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide.

[0223] The unit(s) derived from the (meth)acrylic acid monomers of the polymer may optionally be in the form of salt(s), notably of alkali metal, alkaline-earth metal or ammonium salt(s), or organic base salt(s).

[0224] The (meth)acrylic acid esters (also known as (meth)acrylates) are advantageously chosen from alkyl (meth)acrylates, in particular Ci to C30, preferably Ci to C20 and better still Ci to C10 alkyl (meth)acrylates, aryl (meth)acrylates, in particular Ce to C10 aryl (meth)acrylates, and hydroxyalkyl (meth)acrylates, in particular C2 to Ce hydroxyalkyl (meth)acrylates.

[0225] Among the alkyl (meth)acrylates that may be mentioned are methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, lauryl (meth)acrylate and cyclohexyl (meth)acrylate.

[0226] Among the hydroxyalkyl (meth)acrylates that may be mentioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2- hydroxypropyl methacrylate.

[0227] Among the aryl (meth)acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.

[0228] The (meth)acrylic acid esters that are particularly preferred are alkyl alkyl (meth)acrylates, preferably Ci to C30, more preferentially Ci to C20, better still Ci to C10, and even more particularly Ci to C4 alkyl (meth)acrylates.

[0229] According to the present invention, the alkyl group of the esters may be fluorinated, or even perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are replaced with fluorine atoms.

[0230] As (meth)acrylic acid amides, examples that may be mentioned include (meth)acrylamides and also N-alkyl(meth)acrylamides, in particular N-(C2 to C12 alkyl)(meth)acrylamides. Among the N-alkyl(meth)acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and N- undecylacrylamide.

[0231] The acrylic polymer according to the invention may be a homopolymer or a copolymer, advantageously a copolymer, better still a copolymer of (meth)acrylic acid and of (meth)acrylic acid esters.

[0232] Preferably, the acrylic polymer(s) according to the invention comprise one or more units derived from the following monomers: a) (meth)acrylic acid; and b) Ci to C30, more preferentially Ci to C20, better still Ci to C10, and even more particularly Ci to C4 alkyl (meth)acrylate.

[0233] Preferably, the aqueous dispersion of acrylic polymer particles does not comprise any surfactant. The term “surfactant” refers to any agent that is capable of modifying the surface tension between two surfaces.

[0234] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and of methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and of ethyl acrylate such as the compound sold under the trade name Luvimer MAE by the company BASF, or the compound Polyacrylate- 2 Crosspolymer sold under the trade name Fixate Superhold Polymer by the company Lubrizol, or the compound Acrylate Copolymer sold under the trade name Daitosol 3000VP3 by the company Daito Kasei Kogyo, or the compound Acrylate Polymer sold under the trade name Daitosol 3000 SLPN-PE1 by the company Daito Kasei Kogyo.

[0235] 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.

[0236] As additional monomer, mention will be made, for example, of styrene monomers, in particular styrene and a-m ethyl styrene, and preferably styrene.

[0237] In particular, the acrylic polymer may be a styrene / (meth)acrylate copolymer and notably a polymer chosen from copolymers resulting from the polymerization of at least one styrene monomer and at least one Ci to C20, preferably Ci to C10, alkyl (meth)acrylate monomer.

[0238] The Ci to C10 alkyl (meth)acrylate monomer may be chosen from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate.

[0239] As acrylic polymer, mention may be made of the styrene / (meth)acrylate copolymers sold under the name Joncryl 77 by the company BASF, under the name Yodosol GH41F by the company Akzo Nobel and under the name Syntran 5760 CG by the company Interpolymer.

[0240] Preferably, composition T comprises at least one aqueous dispersion of acrylic polymer particles. More preferentially, composition T comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more units derived from the following monomers: a) (meth)acrylic acid; and b) Ci to C30, preferably Ci to C20, more preferentially Ci to C10 and even more preferentially Ci to C4 alkyl (meth)acrylate.

[0241] Preferably, the aqueous dispersion of acrylic polymer particles has an acrylic polymer (or active material, or solids) content, on the basis of the weight of the dispersion, of from 20% to 60% by weight, more preferentially from 22% to 55% by weight and better still from 25% to 50% by weight.

[0242] Advantageously, the total content of polymer(s) comprising at least one reactive group chosen from carboxylic acids ranges from 0.1% to 35% by weight, more preferentially from 0.5% to 30% by weight, better still from 1% to 20% by weight, and even more preferentially from 3% to 15% by weight relative to the total weight of composition T.

[0243] Advantageously, the total content of acrylic polymer(s) ranges from 0.1% to 35% by weight, more preferentially from 0.5% to 30% by weight, better still from 1% to 20% by weight and even more preferentially from 3% to 15% by weight relative to the total weight of composition T.

[0244] According to a particular embodiment, the total content of the aqueous dispersion(s) of acrylic polymer particle(s) preferably ranges from 0.1% to 35% by weight, more preferentially from 0.5% to 30% by weight, better still from 1% to 20% by weight, and even more preferentially from 3% to 15% by weight relative to the total weight of composition T.

[0245] Silicone

[0246] Composition T according to the invention optionally comprises at least one silicone.

[0247] Preferably, said silicone is different from the polymer comprising at least one reactive group chosen from carboxylic acids as defined previously.

[0248] Preferably, composition T according to the invention comprises at least one silicone chosen from non-amino silicones, amino silicones and mixtures thereof.

[0249] The silicones that may be used may be soluble or insoluble in the composition according to the invention; they may be in the form of oil, wax, resin or gum; silicone oils and gums are preferred.

[0250] Silicones are notably described in detail in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press.

[0251] The volatile silicones may be chosen from those with a boiling point of between 60 and 260°C (at atmospheric pressure) and more particularly from: i) cyclic polydialkylsiloxanes including from 3 to 7 and preferably 4 to 5 silicon atoms, such as

[0252] - octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

[0253] Mention may be made of the products sold under the name Volatile Silicone 7207 by Union Carbide or Silbione 70045 V 2 by Rhodia, Volatile Silicone 7158 by Union Carbide or Silbione 70045 V 5 by Rhodia;

[0254] - cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type having the chemical structure:

[0255] Mention may be made of Volatile Silicone FZ 3109 sold by the company Union Carbide;

[0256] - mixtures of cyclic silicones with silicon-based organic compounds, such as the mixture of octamethylcyclotetrasiloxane and of tetratrimethylsilylpentaerythritol (50 / 50) and the mixture of octamethylcyclotetrasiloxane and of oxy-1,1’- bis(2,2,2’,2’,3,3’-hexatrimethylsilyloxy)neopentane; ii) linear polydialkylsiloxanes containing 2 to 9 silicon atoms, which generally have a viscosity of less than or equal to 5>< 10'6m2 / s at 25°C, such as decamethyltetrasiloxane.

[0257] Other silicones belonging to this category are described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pages 27-32 - Todd & Byers Volatile silicone fluids for cosmetics,' mention may be made of the product sold under the name SH 200 by the company Toray Silicone.

[0258] Among the non-volatile silicones, mention may be made, alone or as a mixture, of polydialkylsiloxanes and notably polydimethylsiloxanes (PDMS), polydiarylsiloxanes, poly alkylaryl siloxanes, silicone gums and resins, and also organopolysiloxanes (or organomodified polysiloxanes, or alternatively organomodified silicones) which are polysiloxanes including in their structure one or more organofunctional groups, generally attached via a hydrocarbon-based group, and preferably chosen from aryl groups, amine groups, alkoxy groups and polyoxyethylene or polyoxypropylene groups.

[0259] The organomodified silicones may be polydiarylsiloxanes, notably polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously. The polyalkylarylsiloxanes are particularly chosen from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes.

[0260] Among the organomodified silicones, mention may be made of organopolysiloxanes including:

[0261] - polyoxyethylene and / or polyoxypropylene groups optionally including G>- C24 alkyl groups, such as dimethicone copolyols, and notably those sold by the company Dow Coming under the name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 711 from the company Union Carbide; or alternatively (Ci2)alkylmethicone copolyols, and notably those sold by the company Dow Corning under the name Q2- 5200;

[0262] - substituted or unsubstituted amine groups, in particular C1-C4 aminoalkyl groups; mention may be made of the products sold under the name GP4 Silicone Fluid and GP7100 by the company Genesee, or under the names Q2-8220 and DC929 or DC939 by the company Dow Corning;

[0263] - thiol groups, such as the products sold under the names GP 72 A and GP 71 from Genesee;

[0264] - alkoxylated groups, such as the product sold under the name Silicone Copolymer F- 755 by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by the company Goldschmidt;

[0265] - hydroxylated groups, for instance polyorganosiloxanes bearing a hydroxyalkyl function;

[0266] - acyloxyalkyl groups, such as the polyorganosiloxanes described in patent US-A-4 957 732;

[0267] - anionic groups of the carboxylic acid type, as described, for example, in EP 186 507, or of the alkylcarboxylic type, such as the product X-22-3701E from the company Shin-Etsu; or alternatively of the 2 -hydroxy alkyl sulfonate or 2- hydroxyalkylthiosulfate type, such as the products sold by the company Goldschmidt under the names Abil® S201 and Abil® S255.

[0268] - hydroxy acyl amino groups, such as the polyorganosiloxanes described in patent application EP 342 834; mention may be made, for example, of the product Q2-8413 from the company Dow Corning.

[0269] The silicones may also be chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes bearing trimethyl silyl end groups. Among these polydialkylsiloxanes, mention may be made of the following commercial products:

[0270] - the Silbione® oils of the 47 and 70 047 series or the Mirasil® oils sold by Rhodia, for instance the oil 70 047 V 500 000;

[0271] - the oils of the Mirasil® series sold by the company Rhodia;

[0272] - the oils of the 200 series from the company Dow Coming, such as DC200, with a viscosity of 60 000 mm2 / s; - the Viscasil® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.

[0273] Mention may also be made of polydimethylsiloxanes bearing dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.

[0274] In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil Wax® 9800 and 9801 by the company Goldschmidt, which are poly(Ci-C2o)dialkylsiloxanes.

[0275] Products that may be used more particularly in accordance with the invention are mixtures such as:

[0276] - mixtures formed from a polydimethylsiloxane with a hydroxy-terminated chain, or dimethiconol (CTFA), and from a cyclic polydimethylsiloxane, also known as cyclomethicone (CTFA), such as the product Q2-1401 sold by the company Dow Corning.

[0277] The polyalkylarylsiloxanes are chosen particularly from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes with a viscosity ranging from 1 * 10'5to 5* 10'2m2 / s at 25°C.

[0278] Among these polyalkylarylsiloxanes, mention may be made of the products sold under the following names:

[0279] - the Silbione® oils of the 70 641 series from Rhodia;

[0280] - the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;

[0281] - the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;

[0282] - the silicones of the PK series from Bayer, such as the product PK20;

[0283] - the silicones of the PN and PH series from Bayer, such as the products PN1000 and PHlOOO;

[0284] - certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

[0285] The silicones that may be used may be amino silicones. The term “amino silicone” denotes any silicone including at least one primary, secondary or tertiary amine or a quaternary ammonium group.

[0286] The weight-average molecular masses of these amino silicones may be measured by gel permeation chromatography (GPC) at room temperature (25°C), as polystyrene equivalent. The columns used are p styragel columns. The eluent is THF and the flow rate is 1 ml / min. 200 pl of a 0.5% by weight solution of silicone in THF are injected. Detection is performed by refractometry and UV-metry.

[0287] Preferably, the amino silicone(s) that may be employed within the context of the invention are chosen from: a) the poly siloxanes corresponding to formula (A): in which x’ and y’ are integers such that the weight-average molecular weight (Mw) is between 5000 and 500 000 approximately; b) the amino silicones corresponding to formula (B):

[0288] R’ aG3-a-Si(O SiG2)n-(OSiGbR’ 2-b)m-O-SiG3-a-R’ a (B) in which:

[0289] - G, which may be identical or different, denotes a hydrogen atom or a group from among phenyl, OH, Ci-Cs alkyl, for example methyl, or Ci-Cs alkoxy, for example methoxy;

[0290] - a, which may be identical or different, denotes 0 or an integer from 1 to 3, in particular 0,

[0291] - b denotes 0 or 1, in particular 1,

[0292] - m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10;

[0293] - R', which may be identical or different, denotes a monovalent radical of formula -CqH2qL in which q is a number ranging from 2 to 8 and L is an optionally quatemized amino group chosen from the following groups:

[0294] - N(R”)2; -N+(R”)3A’; -NR”-Q-N(R”)2and -NR”-Q-N+(R”)3A’, in which R”, which may be identical or different, denotes hydrogen, phenyl, benzyl, or a saturated monovalent hydrocarbon-based radical, for example a C1-C20 alkyl radical; Q denotes a linear or branched group of formula CrH2r, r being an integer ranging from 2 to 6, preferably from 2 to 4; and A' represents a cosmetically acceptable anion, notably a halide such as fluoride, chloride, bromide or iodide. Preferably, the amino silicones are chosen from the amino silicones of formula (B). Preferably, the amino silicones of formula (B) are chosen from the amino silicones corresponding to formulae (C), (D), (E), (F) and / or (G) below.

[0295] Thus, the amino silicones corresponding to formula (B) can be chosen from, alone or as a mixture: b-1) the “trimethyl silyl amodimethicone” silicones corresponding to formula (C): in which m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10. b-2) the silicones of formula (D) below: in which:

[0296] - m and n are numbers such that the sum (n + m) ranges from 1 to 1000, in particular from 50 to 250 and more particularly from 100 to 200; n possibly denoting a number from 0 to 999, notably from 49 to 249 and more particularly from 125 to 175, and m possibly denoting a number from 1 to 1000, notably from 1 to 10 and more particularly from 1 to 5;

[0297] - Ri, R2 and R3, which may be identical or different, represent a hydroxy or C1-C4 alkoxy radical, at least one of the radicals Ri to R3 denoting an alkoxy radical.

[0298] Preferably, the alkoxy radical is a methoxy radical. The hydroxy / alkoxy mole ratio preferably ranges from 0.2: 1 to 0.4: 1 and preferably from 0.25: 1 to 0.35: 1 and more particularly is equal to 0.3: 1.

[0299] The weight-average molecular mass (Mw) of these silicones preferably ranges from 2000 to 1 000 000 and more particularly from 3500 to 200 000. b-3) the silicones of formula (E) below: in which:

[0300] - p and q are numbers such that the sum (p + q) ranges from 1 to 1000, in particular from 50 to 350 and more particularly from 150 to 250; p possibly denoting a number from 0 to 999, notably from 49 to 349 and more particularly from 159 to 239, and q possibly denoting a number from 1 to 1000, notably from 1 to 10 and more particularly from 1 to 5;

[0301] - Ri and R2, which are different, represent a hydroxy or C1-C4 alkoxy radical, at least one of the radicals Ri or R2 denoting an alkoxy radical.

[0302] Preferably, the alkoxy radical is a methoxy radical.

[0303] The hydroxy / alkoxy mole ratio generally ranges from 1 :0.8 to 1 : 1.1 and preferably from 1 :0.9 to 1 :1 and more particularly is equal to 1 :0.95.

[0304] The weight-average molecular mass (Mw) of the silicone preferably ranges from 2000 to 200 000, even more particularly from 5000 to 100 000 and more particularly from 10 000 to 50 000.

[0305] The commercial products comprising silicones of structure (D) or (E) may include in their composition one or more other amino silicones whose structure is other than formula (D) or (E).

[0306] A product containing amino silicones of structure (D) is sold by the company Wacker under the name Belsil® ADM 652.

[0307] A product containing amino silicones of structure (E) is sold by Wacker under the name Fluid WR 1300®.

[0308] When these amino silicones are used, a particularly advantageous embodiment consists in using them in the form of an oil-in-water emulsion. The oil- in-water emulsion may comprise one or more surfactants. The surfactants may be of any nature but are preferably cationic and / or nonionic. The number-average size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nm. Preferably, notably as amino silicones of formula (E), use is made of microemulsions with a mean particle size ranging from 5 nm to 60 nm (limits included) and more particularly from 10 nm to 50 nm (limits included). Thus, use may be made according to the invention of the amino silicone microemulsions of formula (E) sold under the names Finish CT 96 E® or SLM 28020® by the company Wacker; b-4) the silicones of formula (F) below: in which:

[0309] - m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10;

[0310] - A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably linear.

[0311] The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 2000 to 1 000 000 and even more particularly from 3500 to 200 000.

[0312] A silicone corresponding to this formula is, for example, Xiameter MEM 8299 Emulsion from Dow Coming; b-5) the silicones of formula (G) below: in which: - m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10;

[0313] - A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably branched.

[0314] The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 500 to 1 000 000 and even more particularly from 1000 to 200 000.

[0315] A silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning; c) the amino silicones corresponding to formula (H): in which:

[0316] - Rs represents a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a Ci-Cis alkyl or C2-C18 alkenyl radical, for example methyl;

[0317] - Re represents a divalent hydrocarbon-based radical, notably a Ci-Cis alkylene radical or a divalent Ci-Cis, for example Ci-Cs, alkyleneoxy radical linked to the Si via an SiC bond;

[0318] - Q’ is an anion such as a halide ion, notably chloride, or an organic acid salt, notably acetate;

[0319] - r represents a mean statistical value ranging from 2 to 20 and in particular from 2 to 8;

[0320] - s represents a mean statistical value ranging from 20 to 200 and in particular from 20 to 50;

[0321] Such amino silicones are notably described in patent US 4 185 087. d) the quaternary ammonium silicones of formula (I): in which: - R.7, which may be identical or different, represent a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a Ci-Cis alkyl radical, a C2-C18 alkenyl radical or a ring comprising 5 or 6 carbon atoms, for example methyl;

[0322] - Re represents a divalent hydrocarbon-based radical, notably a Ci-Cis alkylene radical or a divalent Ci-Cis, for example Ci-Cs, alkyleneoxy radical linked to the Si via an SiC bond;

[0323] - Rs, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a Ci-Cis alkyl radical, a C2-C18 alkenyl radical or a radical -Re-NHCOR?;

[0324] - X' is an anion such as a halide ion, notably chloride, or an organic acid salt, notably acetate;

[0325] - r represents a mean statistical value ranging from 2 to 200 and in particular from 5 to 100.

[0326] These silicones are described, for example, in patent EP-A 0 530 974; in which:

[0327] - Ri, R2, R3 and R4, which may be identical or different, denote a C1-C4 alkyl radical or a phenyl group,

[0328] - R5 denotes a C1-C4 alkyl radical or a hydroxyl group,

[0329] - n is an integer ranging from 1 to 5,

[0330] - m is an integer ranging from 1 to 5, and

[0331] - x is chosen such that the amine number ranges from 0.01 to 1 meq / g; f) multiblock polyoxyalkylene amino silicones, of the type (AB)n, A being a polysiloxane block and B being a polyoxyalkylene block including at least one amine group.

[0332] Said silicones are preferably formed from repeating units having the following general formulae: [-(SiMe2O)xSiMe2-R-N(R")-R'-O(C2H4O)a(C3H6O)b-R'-N(H)-R-] or else [-(SiMe2O)xSiMe2-R-N(R")-R'-O(C2H4O)a(C3H6O)b-] in which: - a is an integer greater than or equal to 1, preferably ranging from 5 to 200 and more particularly ranging from 10 to 100;

[0333] - b is an integer between 0 and 200, preferably ranging from 4 to 100 and more particularly between 5 and 30;

[0334] - x is an integer ranging from 1 to 10 000 and more particularly from 10 to 5000;

[0335] - R” is a hydrogen atom or a methyl;

[0336] - R, which may be identical or different, represent a linear or branched divalent C2-C12 hydrocarbon-based radical, optionally including one or more heteroatoms such as oxygen; preferably, R denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a CH2CH2CH2OCH2CH(OH)CH2- radical; preferentially, R denotes a CH2CH2CH2OCH2CH(OH)CH2- radical;

[0337] - R’, which may be identical or different, represent a linear or branched divalent C2- C12 hydrocarbon-based radical, optionally including one or more heteroatoms such as oxygen; preferably, R’ denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a -CH2CH2CH2OCH2CH(OH)CH2- radical; preferentially, R’ denotes -CH(CH3)-CH2-.

[0338] The siloxane blocks preferably represent between 50 mol% and 95 mol% of the total weight of the silicone, more particularly from 70 mol% to 85 mol%.

[0339] The amine content is preferably between 0.02 and 0.5 meq / g of copolymer in a 30% by weight solution in dipropylene glycol, more particularly between 0.05 and 0.2 meq / g.

[0340] The weight-average molecular mass (Mw) of the silicone is preferably between 5000 and 1 000 000 and more particularly between 10 000 and 200 000.

[0341] Mention may notably be made of the silicones sold under the name Sil soft A- 843 or Sil soft A+ by Momentive; g) and mixtures thereof.

[0342] The silicone(s) are preferably chosen from amino silicones, better still the amino silicones of formulae (A), (D), (E), (F) and (G) above, and mixtures thereof.

[0343] Advantageously, the total amount of silicone(s) ranges from 0.1% to 15% by weight, preferentially from 0.5% to 10% by weight, more preferentially from 1% to 6% by weight relative to the total weight of composition T.

[0344] Advantageously, the total amount of amino silicones ranges from 0.1% to 15% by weight, preferentially from 0.5% to 10% by weight, more preferentially from 0.8% to 3% by weight relative to the total weight of composition T. Advantageously, the total amount of non-amino silicones ranges from 0.1% to 15% by weight, preferentially from 0.5% to 10% by weight, more preferentially from 1% to 6% by weight relative to the total weight of composition T.

[0345] Associative polymers

[0346] Composition T used in the context of the process according to the invention may also comprise at least one associative polymer different from the polymer comprising at least one reactive group chosen from carboxylic acids as defined previously.

[0347] As recalled above, “associative polymers” are polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

[0348] Their chemical structure more particularly comprises at least one hydrophilic zone, such as a hydrophilic group, and at least one hydrophobic zone, such as a hydrophobic group.

[0349] The term “hydrophobic group'" means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.

[0350] The term “hydrophilic group" means a radical comprising a number of carbon atoms less than or equal to 9, preferably less than or equal to 6.

[0351] The associative polymers may be of nonionic, anionic, cationic or amphoteric nature. Preferably, the associative polymer(s) are chosen from anionic associative polymers.

[0352] Among the associative polymers of anionic type, mention may be made of copolymers including, among their monomers, an a,P-monoethylenically unsaturated carboxylic acid and an ester of an a,P-monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.

[0353] Preferentially, these compounds also comprise, as monomer, an ester of an a,P-monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.

[0354] An example of a compound of this type that may be mentioned is Aculyn 22® sold by the company Rohm & Haas, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer; and also Aculyn 88, also sold by the company Rohm & Haas.

[0355] Preferably, the associative polymer(s) other than the polymers comprising at least one reactive group chosen from the carboxylic acids described previously are chosen from copolymers including, among their monomers, a carboxylic acid containing a,P-monoethylenic unsaturation and an ester of a carboxylic acid containing a,P-monoethylenic unsaturation and of an oxyalkylenated fatty alcohol.

[0356] Advantageously, the total content of the associative polymer(s) other than the polymer(s) comprising at least one reactive group chosen from the carboxylic acids as defined previously ranges from 0.05% to 15% by weight, preferably from 0.05% to 10% by weight, more preferentially from 0.1% to 5% by weight, and even more preferentially from 0.1% to 1% by weight relative to the total weight of composition T.

[0357] Organic solvents

[0358] Composition T used in the context of the process according to the invention may comprise one or more organic solvents.

[0359] Examples of organic solvents that may be mentioned include C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, for instance 2- butoxy ethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols, notably aromatic monoalcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0360] The organic solvents may be present in a total content of between 1% and 80% by weight, preferably between 5% and 70% by weight and more preferentially inclusively between 10% and 65% by weight relative to the total weight of composition T.

[0361] Composition T used in the context of 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 and more preferentially from 20% to 75% by weight relative to the total weight of composition T.

[0362] Additives

[0363] Composition T used in the context of the process according to the invention may contain any adjuvant or additive usually used.

[0364] Among the additives that may be contained in the composition, mention may be made of reducing agents, softeners, antifoams, moisturizers, clays, mineral fillers, peptizers, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers described previously, preserving agents, oils, waxes other than silicones, and mixtures thereof.

[0365] Preferably, composition T is free of colouring agent(s) chosen from pigments, oxidation dye precursors, direct dyes and mixtures thereof.

[0366] For the purposes of the present invention, the term “composition free of colouring agent(s)” means that said composition comprises less than 0.5% by weight of colouring agent(s) relative to the total weight of the composition, preferably less than 0.1% by weight, and more preferentially does not comprise any colouring agent (0% by weight).

[0367] Particularly preferably, composition T does not comprise any colouring agent(s) chosen from pigments, oxidation dye precursors, direct dyes, and mixtures thereof.

[0368] Composition T used in the context of the process according to the invention may notably be in the form of a suspension, a dispersion, a gel, an emulsion, notably an oil-in-water (O / W) or water-in-oil (W / O) emulsion, or a multiple emulsion (W / O / W or polyol / O / W or O / W7O), in the form of a cream, a mousse, a stick, a dispersion of vesicles, notably of ionic or nonionic lipids, or a two-phase or multi-phase lotion.

[0369] A person skilled in the art may select the appropriate presentation form, and also the method for preparing it, on the basis of his general knowledge, taking into account firstly the nature of the constituents used, notably their solubility in the support, and secondly the intended application of the composition.

[0370] The above additives may generally be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of composition T.

[0371] Process

[0372] Before being treated with composition T, the hair keratin fibres are first dyed with dye composition C during step a).

[0373] The dyeing of the hair keratin fibres by applying composition C may be performed on dry or damp hair keratin fibres, and also on all types of light or dark, natural or dyed, permanent waved, bleached or relaxed hair keratin fibres.

[0374] The dyeing of hair keratin fibres by applying dye composition C is performed before applying composition T to the hair keratin fibres.

[0375] Preferably, a rinsing, draining and / or drying step is performed after the application of composition C to the hair keratin fibres. More preferentially, a drying step is performed after applying composition C to the hair keratin fibres. Advantageously, a rinsing step is performed between step a) and step b).

[0376] The application of composition C to the hair keratin fibres may be performed via any conventional means, in particular using a comb, a fine brush, a coarse brush, a sponge or with the fingers.

[0377] The application of composition C to the hair keratin fibres is generally performed at room temperature (between 15 and 25°C).

[0378] After applying composition C on the hair keratin fibres, it is possible to wait for between 1 minute and 6 hours, in particular between 1 minute and 2 hours, more particularly between 1 minute and 1 hour, more preferentially between 1 minute and 45 minutes, before, for example, a drying step.

[0379] After applying composition C, the hair keratin fibres may be left to dry or may be dried, for example at a temperature of greater than or equal to 30°C.

[0380] The dyeing process may thus comprise a step of applying heat to the hair keratin fibres using a heating tool after the application of composition C.

[0381] The heat application step may be performed using a hood, a hairdryer, a straightening or curling iron, a Climazon, etc. Preferably, the heat application step is performed using a hairdryer after the application of composition C.

[0382] When the dyeing process involves a step of applying heat to the hair keratin fibres, the step of applying heat to the hair keratin fibres takes place after the application of composition C.

[0383] During the step of applying heat to the hair keratin fibres, after the application of composition C, a mechanical action can be exerted on the locks, such as combing, brushing or passing the fingers through.

[0384] When the step of applying heat to the hair keratin fibres, after the application of composition C, is performed using a hood or a hairdryer, the temperature is preferably between 30 and 110°C, preferentially between 50 and 90°C.

[0385] Preferably, if the hair keratin fibres are dried, they are dried, in addition to a supply of heat, with a flow of air. This flow of air during drying makes it possible to improve the strand separation of the treated hair keratin fibres.

[0386] In the process according to the invention, composition T is applied during step b) to the hair keratin fibres after the application of composition C.

[0387] It is possible to wait for between 30 seconds and 6 hours, in particular between 30 seconds and 2 hours, more particularly between 30 seconds and 1 hour, more preferentially between 30 seconds and 30 minutes, after applying composition T to the hair keratin fibres. Preferably, the leave-on time is between 30 seconds and 20 minutes after applying composition T to the hair keratin fibres.

[0388] Composition T is preferably a leave-on composition. Following the application of composition T, a step of draining and / or drying the hair keratin fibres is performed. More preferentially, a drying step is performed after the application of composition T to the hair keratin fibres.

[0389] The application to the hair keratin fibres may be performed via any conventional means, in particular using a comb, a fine brush, a coarse brush, a sponge or with the fingers.

[0390] The application of composition T to the hair keratin fibres is generally performed at room temperature (between 15°C and 25°C).

[0391] After applying composition T, the hair keratin fibres may be left to dry or may be dried, for example at a temperature of greater than or equal to 30°C.

[0392] The process according to the invention may thus comprise a step of applying heat to the keratin fibres using a heating tool.

[0393] The heat application step of the process of the invention may be performed using a hood, a hairdryer, a straightening iron, a curling iron, a Climazon hood, etc. Preferably, the heat application step of the process of the invention is performed using a hairdryer.

[0394] During the step of applying heat to the hair keratin fibres, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through.

[0395] When the step of applying heat to the hair keratin fibres is performed using a hood or a hair dryer, the temperature is preferably between 30°C and 110°C, preferentially between 50°C and 90°C.

[0396] Preferably, if the hair keratin fibres are dried, they are dried, in addition to a supply of heat, with a flow of air. This flow of air during drying makes it possible to improve the strand separation of the treated hair keratin fibres.

[0397] Preferably, the invention is a process for dyeing hair keratin fibres comprising: i) the application to the hair keratin fibres of at least one dye composition C as described previously; and then ii) optionally a step of washing, rinsing or draining said hair keratin fibres, and then iii) the application to said hair keratin fibres of at least one composition T as described previously; and then ii) optionally a step of washing, rinsing or draining said hair keratin fibres. According to one embodiment, step a) consists in mixing extemporaneously at the time of use at least one composition C as described previously, with at least one chemical oxidizing agent, preferably hydrogen peroxide, to obtain a mixture, followed by applying said mixture to the hair keratin fibres.

[0398] According to another embodiment, step a) consists in applying to the hair keratin fibres at least one composition C which contains one or more direct dyes, and optionally an oxidizing agent.

[0399] Preferably, composition T also comprises at least one associative polymer as described above, different from the polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously.

[0400] Advantageously, step b) consists in mixing extemporaneously at the time of use at least two compositions A and B to obtain a hair keratin fibre treatment composition T and applying composition T to the hair keratin fibres with:

[0401] - composition A comprising at least one (poly)carbodiimide compound as defined previously;

[0402] - composition B comprising at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously and optionally at least one silicone, and preferably, composition A and / or composition B being free of colouring agent(s) chosen from pigments, direct dyes, oxidation dye precursors and mixtures thereof.

[0403] According to a preferred embodiment, the process according to the invention is a process for dyeing hair keratin fibres comprising: i) the application to the hair keratin fibres of at least one dye composition C as described previously; and then ii) a step of washing, rinsing or draining said hair keratin fibres; and then iii) a step consisting in extemporaneously mixing, at the time of use, at least two compositions A and B to obtain a composition T and in applying composition T to the hair keratin fibres, with:

[0404] - composition A comprising at least one (poly)carbodiimide compound as defined previously;

[0405] - composition B comprising at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously and optionally at least one silicone, and composition A and / or composition B being free of colouring agent(s) chosen from pigments, direct dyes, oxidation dye precursors and mixtures thereof; iv) optionally a step of washing, rinsing, draining and / or drying said hair keratin fibres.

[0406] Preferably, the polymer comprising at least one reactive group chosen from carboxylic acids is chosen from acrylic polymers.

[0407] According to this embodiment, compositions A and B are mixed preferably less than 15 minutes before application to the hair keratin fibres, more preferentially less than 10 minutes before application, better still less than 5 minutes before application.

[0408] The weight ratio between composition A and composition B preferably ranges from 0.1 to 10, preferentially from 0.2 to 5 and better still 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.

[0409] The total amount of the (poly)carbodiimide compound(s) preferably ranges from 0.01% to 40% by weight, more preferentially from 0.1% to 30% by weight, better still from 0.5% to 20% by weight and even more preferentially from 1% to 15% by weight relative to the total weight of composition A.

[0410] The total amount of polymer(s) comprising at least one reactive group chosen from carboxylic acids preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 50% by weight, better still from 1% to 40% by weight, and even more preferentially from 2% to 30% by weight relative to the total weight of composition B.

[0411] According to a particular embodiment, composition B comprises at least one associative polymer as defined previously. The total content of the associative polymer(s) preferably ranges from 0.05% to 15% by weight, preferably from 0.05% to 10% by weight, more preferentially from 0.1% to 5% by weight and even more preferentially from 0.1% to 1% by weight relative to the total weight of composition B.

[0412] The present invention will now be described more specifically by means of examples, which do not in any way limit the scope of the invention. However, the examples make it possible to support specific features, variants and preferred embodiments of the invention.

[0413] EXAMPLES

[0414] The (poly)carbodiimide(s) of the invention are accessible via synthetic methods known to those skilled in the art starting from commercial products or reagents that can be synthesized according to chemical reactions that are also known to those skilled in the art. Mention may be made, for example, of the book Sciences of Synthesis - Houben - Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D-70469 Stuttgart, or the American patent US 4 284 730 or the Canadian patent application CA 2 509 861.

[0415] More particularly, the process for preparing the (poly)carbodiimides of the invention involves, in a first step, a diisocyanate reagent (1):

[0416] O=C=N-Li-N=C=O (1), in which formula (1) Li is as defined previously, which reacts in the presence of a carboimidation catalyst (2) such as those described in US 4 284 730, notably phosphorus-based catalysts particularly chosen from phospholene oxides and phospholene sulfoxides, diaza- and oxaza-phospholanes, preferably under an inert atmosphere (nitrogen or argon), and in particular in a polar solvent which is preferably aprotic such as THF, glyme, diglyme, 1,4-di oxane or DMF, at a temperature between room temperature and the reflux temperature of the solvent, preferably at about 140°C; to give the carbodiimide diisocyanate compound (3):

[0417] O=C=N-Li-(N=C=N-Li)n-N=C=O (3), in which formula (3) Li and n are as defined previously. Benzoyl halogen such as benzoyl chloride may be added to deactivate the catalyst.

[0418] To obtain “symmetrical” (poly)carbodiimides, during the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq.) of nucleophilic reagent Ri-Xi-H and then 0.5 eq. of reagent H-E-H with Ri, Xi and E as defined previously, to give the “symmetrical” compound (4) according to the invention:

[0419] [Ri-Xi-C(O)-NH-Li-(N=C=N-Li)n-NH-C(O)]2-E (4), in which formula (4) Ri, Xi, Li, n and E are as defined previously. According to one variant to obtain compound (4) from (3), it is possible first to add 0.5 eq. of reagent H- E-H and then 1 eq. of reagent Ri-Xi-H.

[0420] To obtain “dissymmetrical” (poly)carbodiimides, during the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq.) of nucleophilic reagent Ri-Xi-H and then 1 eq. of reagent H-E-H with Ri, Xi and E as defined previously, to give compound (5):

[0421] Ri-Xi-C(O)-NH-Li-(N=C=N-Li)n-NH-C(O)-E-H (5), in which formula (5) Ri, Xi, Li, n and E are as defined previously. According to one variant to obtain compound (5) from (3), it is possible first to add 1 eq. of reagent Ri-Xi-H and then 0.5 eq. of reagent H-E-H.

[0422] During a third step, compound (5) reacts with 1 eq. of compound (6)

[0423] R2-X2-C(O)-NH-LI-(N=C=N-LI)Z-N=C=O (6), said compound (6) is prepared beforehand from compound (3’): O=C=N-Li-(N=C=N-Li)z-N=C=O (3’), in which formula (3’) Li and z are as defined previously, which reacts with 1 eq. of nucleophilic reagent R2-X2-H with Li, R2, X2 and z as defined previously, to give the dissymmetrical compound (7):

[0424] Ri-Xi-C(O)-NH-Li-(N=C=N-Li)n-NH-C(O)-E-C(O)-NH-Li-(N=C=N-Li)z-NH- C(O)-X2-R2(7), in which formula (7) Ri, Xi, Li, R2, X2, n, z and E are as defined previously.

[0425] It is also possible to react 1 molar equivalent of compound O=C=N-Li- (N=C=N-Li)z-N=C=O (3’) with 1 / w molar equivalent of H-E-H, followed by 1 eq. of nucleophilic reagent R2-X2-H to give compound (8): H-[E-C(O)-NH-LI-(N=C=N-LI)Z]W-NH-C(O)-X2-R2(8), in which formula (8) Li, R2, X2, z and E are as defined previously, and w is an integer between 1 and 3; more preferentially, w = 1.

[0426] This last compound (8) can then react with 1 eq. of compound (4’): Ri-Xi-C(O)-NH-Li-(N=C=N-Li)n-N=C=O (4’), (said compound (4’) being able to be synthesized by reaction of 0.5 eq. of nucleophilic reagent R1-X1-H with 1 equivalent of compound (3)), to give the (poly)carbodiimide (9) of the invention: Ri-Xi-C(O)-NH-Li-(N=C=N-Li)n-NH-C(O)-[E-C(O)-NH-Li-(N=C=N-Li)z]w-NH C(O)-X2-R2(9), in which formula (9) Li, Ri, Xi, R2, X2, n, z, w and E are as defined previously.

[0427] The (poly)carbodiimide compounds, and similarly all the reaction intermediates and reagents, may be purified via 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.

[0428] Example 1: Process for synthesizing the (poly)carbodiimide compound

[0429] 50 g of 4,4’ -di cyclohexylmethane diisocyanate and 0.5 g of 4, 5 -dihydro-3 - methyl- 1 -phenyl- IH-phosphole 1 -oxide are placed with stirring in a 500 mL threenecked round-bottomed flask equipped with a thermometer, a stirrer and a reflux tube. The reaction medium is heated at 140°C under nitrogen for 4 hours, the reaction being monitored by infrared spectroscopy by means of the absorption of the isocyanate functions between 2200 and 2300 cm'1, and then cooled to 120°C.

[0430] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4- butanediol are introduced with stirring into the reaction medium. The temperature of 120°C is maintained until the isocyanate functions have totally disappeared, monitored by infrared spectroscopy at 2200-2300 cm'1, and is then cooled to room temperature.

[0431] After cooling to room temperature, the reaction medium is poured dropwise with vigorous stirring into a 500 mL glass beaker containing 85 g of distilled water, to give the desired product in the form of a translucent yellow liquid.

[0432] Example 2

[0433] The Preference dyeing product, shade 6.66 from L'Oreal Paris©, is used in the following examples. Composition CPI corresponds to the colouring gel of this dyeing product and contains oxidation bases and oxidation couplers. Composition CP2 corresponds to the developing milk containing hydrogen peroxide.

[0434] Composition CNP corresponds to the L'Oreal Professionnel direct dyeing product, Nuancelle Blue, which contains violet and blue direct dyes.

[0435] Composition CPI was then mixed with composition CP2 in a 1 / 1.5 mass ratio to obtain composition CP.

[0436] In addition, compositions T1 and T2 as described in Tables 1 and 2 below were prepared: the amounts are expressed as g of raw material as obtained / 100 g, unless otherwise mentioned. Thus, the amounts may be expressed in g of active material (AM) / 100 g.

[0437] [Table 1] (1) synthesized according to the synthetic process described in Example 1 (containing 40% active material in water),

[0438] (2) sold by the company SEPPIC under the trade name Sepinov EMTIO (containing 90% active material).

[0439] [Table 2]

[0440] (3) sold by the company Daito Kasei Kogyo under the trade name Daitosol 3000SLPN- PE1 (aqueous dispersion containing 30% active material)

[0441] (4) sold by the company Dow Corning under the name Dow Corning HMW 2220 Nonionic Emulsion (divinyl dimethicone / dimethicone block copolymer as an aqueous emulsion) (containing 60% active material)

[0442] (5) sold by the company Rohm & Haas under the trade name Aculyn 22® (oxyalkylenated methacrylic acid / ethyl acrylate / stearyl methacrylate terpolymer containing 30% active material) Composition T1 was then mixed with composition T2 in a 50 / 50 mass ratio to obtain composition T.

[0443] Compositions CP, CNP and T are summarized in Table 3 below: [Table 3]

[0444] Evaluation of the persistence with respect to shampoo washing

[0445] Protocol

[0446] Four application processes were used.

[0447] According to process 1, the dye composition CP was applied with a dyeing brush to locks of moderately sensitized hair keratin fibres (AS20), at a rate of 5 g of composition per gram of lock. The previously dyed locks were left for 15 minutes on one side and then 15 minutes on the other, on a hotplate at 31°C. The locks were then rinsed with water before being dried with a hairdryer. Next, composition T was applied to the locks previously dyed with composition CP, at a rate of 0.8 g of composition per gram of locks. The locks treated with composition T were left to dry naturally for 1 minute, and were then dried for 1 minute with a hairdryer while being brushed.

[0448] According to process 2, the dye composition CP was applied with a dyeing brush to locks of moderately sensitized hair keratin fibres (AS20), at a rate of 5 g of composition per gram of lock. The previously dyed locks were left for 15 minutes on one side and then 15 minutes on the other, on a hotplate at 31°C. The locks were then rinsed with water before being dried with a hairdryer.

[0449] Process 1 is a process according to the invention and process 2 is a comparative process. In the text hereinbelow, they are referred to as Pl and P2.

[0450] According to process 3, the dye composition CNP was applied using a dyeing brush to locks of moderately sensitized hair keratin fibres (AS20), at a rate of 5 g of composition per gram of lock. The previously dyed locks were left for 15 minutes on one side and then 15 minutes on the other, on a hotplate at 31°C. The locks were then rinsed with water before being dried with a hairdryer. Next, composition T was applied to the locks previously dyed with composition CNP, at a rate of 0.8 g of composition per gram of locks. The locks treated with composition T were left to dry naturally for 1 minute, and were then dried for 1 minute while being brushed.

[0451] According to process 4, the dye composition CNP was applied using a dyeing brush to locks of moderately sensitized hair keratin fibres (AS20), at a rate of 5 g of composition per gram of lock. The previously dyed locks were left for 15 minutes on one side and then 15 minutes on the other, on a hotplate at 31°C. The locks were then rinsed with water before being dried with a hairdryer.

[0452] Process 3 is a process according to the invention and process 4 is a comparative process. In the text hereinbelow, they are referred to as P3 and P4.

[0453] The processes applied are summarized in Table 4 below:

[0454] [Table 4]

[0455] The various locks of hair treated via processes Pl to P4 were then subjected to a test consisting of several repeated shampoo washes in order to evaluate the resistance (persistence) of the colouring obtained with respect to shampoo washing, according to the shampoo washing protocol described below.

[0456] Shampoo washing protocol:

[0457] The locks of dyed hair keratin fibres are combed, moistened with water at 35°C and then passed between the fingers five times for 5 seconds. The locks of hair keratin fibres are then squeezed dry between two fingers.

[0458] A standard shampoo (Garnier Ultra Doux) is applied uniformly to the dyed locks, in a proportion of 0.4 g of standard shampoo per gram of locks, the locks of hair keratin fibres being massaged gently along the length (6 passes) for 15 seconds, from the root to the end.

[0459] The locks of hair keratin fibres are then placed on a watch glass and left to stand for 1 minute.

[0460] Next, the locks of hair keratin fibres are rinsed with water while passing the locks between the fingers (15 passes). The locks of hair keratin fibres are then squeezed dry between two fingers before the next shampoo wash.

[0461] Once the tests of several shampoo washes have been performed, the locks of hair keratin fibres are combed and dried with a hairdryer.

[0462] Results

[0463] The persistence of the colour of the locks was evaluated in the CIE L*a*b* system, using a Konica Minolta CM3600A spectrophotometer (illuminant D65, angle 10°, specular component included).

[0464] In this L*a*b* system, L* represents the intensity of the colour, a* indicates the green / red colour axis and b* the blue / yellow colour axis.

[0465] The persistence of the colouring is evaluated by the colour difference AE between the measurements taken on the dyed locks before shampoo washing, then after having undergone five shampoo washes according to the protocol described above. The lower the AE value, the more persistent the colour with respect to shampoo washing.

[0466] The AE value is calculated according to the following equation:

[0467] In this equation, L*, a* and b* represent the values measured after dyeing the hair and after performing shampoo washes, and Lo*, ao* and bo* represent the values measured after dyeing the hair but before shampoo washing.

[0468] The results are summarized in Table 5 below.

[0469] [Table 5]

[0470] The locks of hair keratin fibres treated by means of process Pl according to the invention and washed with five shampoo washes show improved persistence with respect to shampoo washing relative to the locks of hair keratin fibres treated by means of comparative process P2.

[0471] Similarly, the locks of hair keratin fibres treated by means of process P3 according to the invention and washed with five shampoo washes show improved persistence with respect to shampoo washing relative to the locks of hair keratin fibres treated by means of comparative process P4.

[0472] Thus, the application of composition T to hair keratin fibres which have been previously dyed improves the persistence of said colouring.

Claims

CLAIMS1. Process for dyeing hair keratin fibres comprising: a) the application to the hair keratin fibres of at least one dye composition C comprising at least one colouring agent chosen from direct dyes, oxidation dye precursors and mixtures thereof, and optionally at least one chemical oxidizing agent; and then b) the application of at least one composition T comprising:(1) at least one (poly)carbodiimide compound;(2) at least one polymer comprising at least one reactive group chosen from carboxylic acids; and(3) optionally at least one silicone.

2. Process according to Claim 1, characterized in that the oxidation dye precursor(s) are chosen from oxidation bases, oxidation couplers and mixtures thereof.

3. Process according to Claim 2, characterized in that the oxidation bases are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, paraaminophenols, ortho-aminophenols, heterocyclic bases, the corresponding addition salts thereof, the solvates thereof, the salts thereof and mixtures thereof.

4. Process according to Claim 2 or 3, characterized in that the oxidation couplers are chosen from meta-phenylenediamines, meta-aminophenols, metadiphenols, naphthalene-based coupling agents and heterocyclic coupling agents, the corresponding addition salts thereof, solvates thereof, salts thereof and mixtures thereof.

5. Process according to any one of the preceding claims, characterized in that the direct dye(s) are chosen from 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, natural direct dyes, and mixtures thereof.

6. Process according to any one of the preceding claims, characterized in that the colouring agent(s) chosen from direct dyes, oxidation dye precursors, and mixtures thereof, are present in composition C in a content ranging from 0.001% to 20% byweight, preferentially from 0.005% to 15% by weight relative to the total weight of composition C.

7. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (I) below:(I), in which:- Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;- Ri and R2 independently represent a group chosen from a hydrocarbon-based radical, preferably alkyl, optionally interrupted with one or more heteroatoms, a group chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups, and a hydrocarbon-based radical, preferably alkyl, optionally interrupted with one or more heteroatoms and with one or more groups chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups;- n denotes an integer ranging from 1 to 1000; and- A is a monomer chosen from the compounds below:

8. Process according to any one of Claims 1 to 6, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) below:(II), in which:- Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;- Ri and R2 independently represent a hydrocarbon-based radical optionally interrupted with one or more heteroatoms;- n and z denote an integer ranging from 1 to 20, with n+z > 2 and w denotes an integer ranging from 1 to 3;- Li independently represents a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof;- E independently represents a group chosen from:-0-R3-0-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-, in which R3 and R4 independently represent a divalent hydrocarbon-based radical optionally interrupted with one or more heteroatoms;- Rs independently represents a covalent bond or a saturated divalent hydrocarbonbased radical, optionally interrupted with one or more heteroatoms;- Re independently represents a hydrogen atom or a hydrocarbon-based radical, optionally interrupted with one or more heteroatoms.

9. Process according to Claim 8, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) in which:- Xi and X2 independently represent an oxygen atom;- Ri and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl 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;- LI is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof;- E independently represents a group chosen from:- -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;- when R5 is not a covalent bond, R5 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof; and- Re is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

10. Process according to Claim 8 or 9, characterized in that the (poly)carbodiimide compound(s) are chosen 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 hydroxyl 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-C15 cycloalkylene radical;- E independently represents a group chosen from:-O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;- when R5 is not a covalent bond, R5 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof; and- Re is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

11. Process according to any one of Claims 8 to 10, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) in which:- Xi and X2 independently represent an oxygen atom;- Ri and R2 independently represent the compound of formula (VI) below: Ri3-[O-CH2-C(H)(Ri4)]q- (VI), in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging 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-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4, 4-di cyclohexylenemethane; and- E represents a group -O-R3-O- in which R3 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

12. Process according to any one of Claims 8 to 11, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) in which:- Xi and X2 independently represent an oxygen atom;- Ri and R2 independently represent the compound of formula (VI) below:Ri3-[O-CH2-C(H)(Ri4)]q- (VI), in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging 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-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylenemethane, preferably 4,4- dicyclohexylenemethane; and- E represents a group -O-R3-O- in which R3 represents a linear or branched Ci-Cis alkylene radical such as methylene, propylene, butylene or ethylene, optionally interrupted with one or more heteroatoms.

13. Process according to any one of Claims 8 to 12, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (XII) below:in which Li is 4,4-dicyclohexylenemethane, n and z denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10, E represents a group -O-R3-O- in which R3 represents a linear or branched Ci-Cis alkylene radical such as methylene, propylene, butylene or ethylene, optionally interrupted with one or more heteroatom(s), and r and s denote an integer ranging from 4 to 30.

14. 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 preferentially from 0.2% to 10% by weight, even more preferentially from 0.5% to 8% by weight, and better still from 1% to 6% by weight relative to the total weight of composition T.

15. Process according to any one of the preceding claims, characterized in that the polymer comprising at least one reactive group chosen from carboxylic acids is an acrylic polymer.

16. Process according to the preceding claim, characterized in that the acrylic polymer(s) comprise one or more units derived from the following monomers: a) (meth)acrylic acid; andb) Ci to C30, preferably Ci to C20, more preferentially Ci to C10 and even more preferentially Ci to C4 alkyl (meth)acrylate.

17. Process according to any one of the preceding claims, characterized in that the polymer(s) comprising at least one reactive group chosen from carboxylic acids, preferably acrylic polymers, are present in a total amount ranging from 0.1% to 35% by weight, more preferentially from 0.5% to 30% by weight, better still from 1% to 20% by weight, and even more preferentially from 3% to 15% by weight relative to the total weight of composition T.

18. Process according to any one of the preceding claims, characterized in that the silicone(s) are chosen from non-amino silicones, amino silicones and mixtures thereof.

19. Process according to any one of the preceding claims, characterized in that composition T is free of colouring agent(s) chosen from pigments, oxidation dye precursors, direct dyes and mixtures thereof.

20. Process according to any one of the preceding claims, characterized in that step a) consists in mixing extemporaneously at the time of use at least one composition C as defined in any one of Claims 1 to 6, with at least one chemical oxidizing agent, preferably hydrogen peroxide, to obtain a mixture, followed by applying said mixture to the hair keratin fibres.

21. Process according to any one of the preceding claims, characterized in that step b) consists in extemporaneously mixing, at the time of use, at least two compositions A and B to obtain a composition T and then in applying composition T to the hair keratin fibres, with:- composition A comprising at least one (poly)carbodiimide compound as defined in any one of Claims 1 and 7 to 13;- composition B comprising at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined in any one of Claims 1 and 15 to 16, preferably, composition A and / or B being free of colouring agent(s) chosen from pigments, direct dyes, oxidation dye precursors and mixtures thereof.

22. Process according to any one of the preceding claims, characterized in that a rinsing step is performed between step a) and step b).

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