Process for dyeing hair keratin fibres comprising the application of at least two reducing agents followed by a (POLY)carbodiimide compound, a particular polymer and a colouring agent

Abstract

The present invention relates to a process for dyeing hair keratin fibres comprising: (i) a step consisting in treating the hair keratin fibres with a composition T comprising: - at least a first reducing agent AR1 in dimer form, and - at least a second reducing agent AR2 different from said reducing agent AR1; and then (ii) a step consisting in applying to the hair keratin fibres at least one dye composition C 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) at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

Description

[0001] DESCRIPTION

[0002] TITLE: Process for dyeing hair keratin fibres comprising the application of at least two reducing agents followed by a (poly)carbodiimide compound, a particular polymer and a colouring agent

[0003] The present invention relates to a process for dyeing hair keratin fibres comprising the application of a treatment with a composition comprising at least two reducing agents, followed by the application to the hair keratin fibres of a dye composition C comprising at least one (poly)carbodiimide compound, at least one particular polymer and at least one colouring agent.

[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 the 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 keratin 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 keratin fibres 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 pigments 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] There is thus still a need for a process for dyeing hair keratin fibres which has the advantage of forming a coating that is persistent with respect to shampoo washing and to the various stresses to which the 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 which has the advantage of forming a coating that is persistent with respect to shampoo washing and to the various stresses to which the 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 thus a process for dyeing hair keratin fibres comprising:

[0012] (i) a step consisting in treating the hair keratin fibres with a composition T comprising:

[0013] - at least a first reducing agent ARI in dimer form, and

[0014] - at least a second reducing agent AR2 different from said reducing agent ARI; and then

[0015] (ii) a step consisting in applying to the hair keratin fibres at least one dye composition C comprising:

[0016] (1) at least one (poly)carbodiimide compound;

[0017] (2) at least one polymer comprising at least one reactive group chosen from carboxylic acids; and

[0018] (3) at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

[0019] By virtue of the process for dyeing hair keratin fibres according to the invention, the colouring obtained on the hair keratin fibres is resistant to shampoo washing and to the various stresses to which the hair keratin fibres may be subjected, such as brushing and / or rubbing.

[0020] The term “at least one" means one or more.

[0021] Unless otherwise indicated, the limits of a range of values are included in that range, notably in the expressions “between” and “ranging from ... to ...”.

[0022] 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.

[0023] For the purposes of the present invention and unless otherwise indicated:

[0024] - 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;

[0025] - a “hydroxyalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an OH group;

[0026] - an “alkylene” radical denotes a linear or branched divalent saturated C2-C4 hydrocarbon-based group such as methylene, ethylene or propylene;

[0027] - a “cycloalkyl” or “alicycloalkyl” radical denotes a saturated monocyclic or polycyclic, preferably monocyclic, bicyclic or tricyclic, 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 norbomyl, 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;

[0028] - a “cycloalkylene" radical denotes a divalent cycloalkyl group with “cycloalkyl” as defined previously, preferably of C3-C12;

[0029] - 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;

[0030] - an “arylene” radical is a divalent aryl radical with “aryl” as defined previously; preferably, arylene represents phenylene;

[0031] - 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 or N, including from 3 to 20 ring members, preferably between 5 and 10 ring members, such as imidazolyl, pyrrolyl and furanyl;

[0032] - a “heterocycloalkylene” radical is a divalent heterocyclic group with “heterocyclic” as defined previously; - an "aryloxy” radical denotes an aryl-oxy radical with “aryl” as defined previously;

[0033] - an “alkoxy” radical denotes an alkyl-oxy radical with “alkyl” as defined previously;

[0034] - an “acyloxy” radical denotes an ester radical R-C(O)-O- with R being an alkyl group as defined previously;

[0035] - a “reactive” group is a group that is capable of forming a covalent bond with another identical or different group, by chemical reaction.

[0036] 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.

[0037] For the purposes of the present invention, the term “the hair keratin fibres” means head hair keratin fibres. This term does not correspond to bodily hairs, the eyebrows or the eyelashes.

[0038] Treatment with reducing agents

[0039] The process according to the invention comprises a step consisting in treating the hair keratin fibres with a composition T comprising at least a first reducing agent ARI in dimer form, and at least a second reducing agent AR2 different from said reducing agent ARI.

[0040] Preferably, the reducing agent(s) ARI are chosen from thioglycolic acid dimers, such as dithiodiglycolic acid, mineral and / or organic salts thereof, such as diammonium dithiodiglycolate, and mixtures thereof.

[0041] More preferentially, the reducing agent ARI is diammonium dithiodiglycolate .

[0042] According to another preferred embodiment, the reducing agent(s) ARI are chosen from thioglycolic acid dimers, such as dithiodiglycolic acid, mineral and / or organic salts thereof, such as diammonium dithiodiglycolate, mercaptopropyltrimethoxysilane dimer and mixtures thereof.

[0043] More preferentially, the reducing agent ARI is diammonium dithiodiglycolate or mercaptopropyltrimethoxysilane dimer.

[0044] Preferably, the reducing agent(s) AR2, different from the reducing agent(s) ARI, are chosen from thiol-based reducing agents, and mixtures thereof. For the purposes of the present invention, the terms “thiol” and “thiol-based” refer to any molecule bearing an -SH group or a group that is capable of generating a thiol by a simple chemical or photochemical reaction (for example hydrolysis). Thus, for the purposes of the present invention, compounds bearing protected thiol functions as defined for example in “Protective Groups in Organic Synthesis”, T.W Greene and P.G.M Wuts, Second edition, Protection of the thiol groups, are assimilated to compounds bearing -SH thiol functions. For the purposes of the present invention, the term “non-thiol reducing agent” refers to a reducing agent which does not include any thiol groups.

[0045] The thiol-based reducing agent(s) AR2 according to the invention may be chosen from organic compounds including one or more -SH groups, and optionally at least one other function chosen from carboxylic acid, amine, amide, ester and alcohol functions and mixtures thereof.

[0046] Preferably, the thiol-based reducing agent(s) AR2 are chosen from the reducing agents of formula (i-1) below, mineral and / or organic salts thereof and mixtures thereof: Ri-SH (i-1), in which formula (i-1):

[0047] ■ Ri represents:

[0048] - a (Ci-C8)alkyl and preferably (Ci-C6)alkyl group, optionally substituted with one or more groups chosen from carboxyl C(O)OH, (di)(Ci-C4)(alkyl)amino, hydroxyl -OH, thiol -SH or -C(O)-NH-CH2-C(O)OH and / or optionally interrupted with one or more heteroatoms or groups chosen from -O-, -S-, -N(R’”)- and C(O) or combinations thereof such as -O-C(O)-, -C(O)-O-, -C(O)-O-R*, -N(R”’)-C(O)-, or -C(O)- N(R’”)-; with R’” representing a hydrogen atom or a (Ci-Ce / alkyl group; R* representing a (Ci-Ce / alkyl group optionally substituted with one or more hydroxyl -OH, thiol -SH or amino -NH2 groups; or

[0049] - a (hetero)aryl group optionally substituted with one or more hydroxyl, thiol or carboxyl groups.

[0050] According to a preferred embodiment of the invention, the thiol-based reducing agent(s) AR2 of formula (i-1) are chosen from those in which Ri represents a (Ci-C8)alkyl and preferably (Ci-C6)alkyl group, substituted with one or more groups chosen from carboxyl C(O)OH, amino, hydroxyl -OH and thiol -SH; and / or optionally interrupted with one or more heteroatoms or groups chosen from -O-, -N(R’ ”)-, C(O) or combinations thereof such as -O-C(O)-, -C(O)-O-, -N(R”’)-C(O)-, or -C(O )- N(R’”)-, with R”’ representing a hydrogen atom or a (Ci-Ce / alkyl group. According to a more preferred embodiment of the invention, the thiol-based reducing agent(s) AR2 of formula (i-1) are chosen from those in which Ri represents a (Ci-Cs)alkyl and preferably (Ci-C6)alkyl group, which is not interrupted and substituted with one or more groups chosen from carboxyl C(O)OH, amino, hydroxyl -OH, and thiol -SH.

[0051] According to another embodiment of the invention, the thiol-based reducing agent(s) AR2 of formula (i-1) are chosen from those in which Ri represents:

[0052] - a phenyl group optionally substituted with one or more groups chosen from carboxyl C(O)OH, amino, hydroxyl -OH, and thiol -SH; or

[0053] - a 5- to 10-membered, preferably 9- or 10-membered bicyclic, heteroaryl group, comprising from 1 to 4 heteroatoms chosen from O, S or N, preferably N, optionally substituted with one or more hydroxyl or thiol groups.

[0054] The thiol-based reducing agent(s) AR2 according to the invention may notably be used in the form of mineral and / or organic salts, in particular alkali metal salts such as sodium and potassium salts, alkaline-earth metal salts, for example magnesium, calcium and strontium salts, which may or may not be hydrated, ammonium salts, hydrochloric acid salts, amine salts and amino alcohol salts, for example ethanolamine salts. Ammonium thioglycolate, cysteine hydrochloride or ethanolamine thioglycolate may thus be used as thiol-based reducing agent.

[0055] Preferably, the thiol-based reducing agent(s) AR2 are chosen from thioglycolic acid, thiolactic acid, cysteine, cysteamine, N-acetylcysteamine, N- proprionylcysteamine, cysteine, homocysteine, glutathione, thioglycerol, thiomalic acid, 3-mercaptopropionic acid, pantetheine, dimercaptosuccinic acid, thiosulfuric acid derivatives, 2-mercaptoethanol, dithiothreitol, thiosalicylic acid, N-acetylcysteine, esters and amides of thioglycolic or thiolactic acids, notably glycerol monothioglycolate, mineral and / or organic salts thereof, and mixtures thereof.

[0056] More preferentially, the thiol-based reducing agent(s) AR2 are chosen from the group consisting of thioglycolic acid, thiolactic acid, cysteine, cysteamine, N- acetylcysteamine, glycerol monothioglycolate, thiosulfuric acid derivatives, mineral and / or organic salts thereof, and mixtures thereof.

[0057] Even more preferentially, the thiol-based reducing agent(s) AR2 may be chosen from thioglycolic acid, mineral and / or organic salts thereof, and mixtures thereof. According to another preferred embodiment, the thiol-based reducing agent(s) AR2 are chosen from the group consisting of thioglycolic acid, thiolactic acid, cysteine, cysteamine, N-acetylcysteamine, glycerol monothioglycolate, thiosulfuric acid derivatives, mineral and / or organic salts thereof, mercaptopropyltrimethoxysilane and mixtures thereof.

[0058] Even more preferentially, the thiol-based reducing agent(s) AR2 may be chosen from thioglycolic acid, mineral and / or organic salts thereof, mercaptopropyltrimethoxysilane and mixtures thereof.

[0059] Composition T may be an aqueous composition. The water may be present in a content ranging from 90% to 99.5% by weight relative to the total weight of composition T.

[0060] When composition T is aqueous, it has a pH that may be acidic or basic.

[0061] According to a preferred embodiment of the invention, the pH of the composition comprising the reducing agent(s) as defined previously is basic, preferably ranging from 7.5 to 11, preferably from 8 to 10.

[0062] According to a preferred embodiment, the reducing agent(s) AR2 are chosen from thiol-based reducing agents chosen from organic compounds including one or more -SH groups and optionally at least one other function chosen from carboxylic acid, amine, amide, ester and alcohol functions, mineral and / or organic salts thereof, and mixtures thereof.

[0063] According to a more preferred embodiment, the reducing agent(s) AR2 are chosen from thiol-based reducing agents, and mineral and / or organic salts thereof, preferably chosen from those of formula (i-1) as defined previously, mineral and / or organic salts thereof, and mixtures thereof.

[0064] According to an even more preferred embodiment, the reducing agent AR2 is thioglycolic acid.

[0065] According to another even more preferred embodiment, the reducing agent AR2 is mercaptopropyltrimethoxysilane.

[0066] Better still, composition T comprises a mixture of thioglycolic acid and diammonium dithiodiglycolate.

[0067] According to another particularly preferred embodiment, composition T comprises a mixture of thioglycolic acid, mercaptopropyltrimethoxysilane and mercaptopropyltrimethoxysilane dimer. Advantageously, the reducing agent(s) ARI as defined previously are present in a total content ranging from 0.01% to 10% by weight, preferentially from 0.1% to 5% by weight, more preferentially from 0.2% to 4% by weight, even more preferentially from 0.2% to 1% by weight relative to the total weight of composition T.

[0068] Advantageously, the reducing agent(s) AR2 are present in a total content ranging from 0.1% to 10% by weight, preferentially from 0.5% to 5% by weight, more preferentially from 0.5% to 3% by weight relative to the total weight of composition T.

[0069] Advantageously, the reducing agent(s) ARI and AR2 as defined previously are present in a total content ranging from 0.1% to 10% by weight, preferentially from 0.5% to 8% by weight, more preferentially from 0.5% to 5% by weight relative to the total weight of composition T.

[0070] Advantageously, the reducing agent(s) AR2 and the reducing agent(s) ARI are present in composition T in a reducing agent AR2 / reducing agent ARI weight ratio greater than or equal to 1, preferably ranging from 1 to 10, more preferentially from 1 to 5, even more preferentially from 1 to 3.

[0071] Polycarbodiimide compound

[0072] Composition C used in the context of the process according to the invention comprises at least one (poly)carbodiimide compound.

[0073] The term “(poly)carbodiimide”, in the meaning of the present invention and in a manner known per se, designates carbodiimides and polycarbodiimides.

[0074] The composition may comprise at least two different (poly)carbodiimide compounds, present as a mixture in the composition.

[0075] 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.

[0076] The term ”carbodiimide group” means a divalent linear triatomic fraction of general formula -(N=C=N)-.

[0077] 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, norbomenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.

[0078] 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, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbomenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.

[0079] According to a particular embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) below:

[0080] (I), in which:

[0081] - Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0082] - 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, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbomenylsilyl, 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, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbomenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups;

[0083] - n denotes an integer ranging from 1 to 1000; and

[0084] - A is a monomer chosen from the compounds below:

[0085] According to another embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I’) below:

[0086] (D in which: - Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0087] - Y 1 and Y2 independently represent a divalent organic radical chosen from a saturated Ci to C36 aliphatic group or a Ci> 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; - Zi and Z2 independently represent a reactive end group or an inert end group;

[0088] - as inert end group, Zi and Z2 may represent, independently, a saturated, linear or branched or cyclic Ci to C50 aliphatic group, or a C<> 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;

[0089] - as reactive end group, Zi and Z2 may be chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbomenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups;

[0090] - 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;

[0091] - 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;

[0092] - r denotes an integer equal to 0 or 1 ;

[0093] - m denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0094] - m’ denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0095] - n denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1, with m + (m’*n ) > 2.

[0096] Preferably, Zi and Z2 independently represent a reactive end group; more preferentially, Zi and Z2 independently represent a group chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbomenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.

[0097] 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.

[0098] Preferably, the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) below:

[0099] (II), in which:

[0100] - Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0101] - Ri and R2 independently represent a hydrocarbon-based radical optionally interrupted with one or more heteroatoms;

[0102] - 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;

[0103] - Li independently represents a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a C6-C14 arylene group, and mixtures thereof;

[0104] - E independently represents a group chosen from:

[0105] -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; - Rs independently represents a covalent bond or a saturated divalent hydrocarbonbased radical, optionally interrupted with one or more heteroatoms;

[0106] - Re independently represents a hydrogen atom or a hydrocarbon-based radical, optionally interrupted with one or more heteroatoms.

[0107] 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.

[0108] The hydrocarbon-based radical may comprise one or more cyclic groups.

[0109] 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.

[0110] The term 'Vie / o / n / .sJ” 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.

[0111] Preferably, Xi and X2 independently represent an oxygen atom.

[0112] Preferably, 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.

[0113] According to a preferred embodiment, Ri and R2 are independently chosen from groups (i) to (iv) below:

[0114] (i) the compound of formula (III) below:

[0115] R7-O-C(O)-C(R8)(H)- (III), in which R7 represents a C1-C3 alkyl group, and R8represents a hydrogen atom or a C1-C3 alkyl group; preferably, R7 is a methyl and R8is a hydrogen atom or a methyl.

[0116] (ii) the compound of formula (IV) below:

[0117] 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.

[0118] (iii) the compound of formula (V) below:

[0119] (Rii)2N-CH2-C(H)(Ri2)- (V), in which Rn represents a C1-C4 alkyl group and R12 represents a hydrogen atom or a C1-C4 alkyl group; preferably, Rn is a methyl, ethyl or butyl and R12 is a hydrogen atom or a methyl.

[0120] (iv) the compound of formula (VI) below:

[0121] 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.

[0122] Preferably, Ri and R2 independently 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.

[0123] According to an alternative embodiment, Ri and R2 are different and one of the radicals Ri or R2 represents a compound of formula (IV) as described above and the other radical Ri or R2 represents a compound of formula (VI) as described above.

[0124] 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.

[0125] 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.

[0126] According to another alternative embodiment, Ri and R2 are 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.

[0127] Preferably, n denotes an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0128] Preferably, z denotes an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0129] Preferably, w is equal to 1.

[0130] Preferably, w is equal to 1, n+z denotes an integer ranging from 4 to 10.

[0131] 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 C6-C14 arylene group such as phenylene, and mixtures thereof. 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)- 1 ,3-dioctylcyclobutane, 4,4’ - dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-napththylene diisocyanate, 4,4’ -diphenylmethane diisocyanate, 4,4’- diphenyldimethylmethane diisocyanate and phenylene diisocyanate, and mixtures thereof.

[0132] 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:

[0133] Preferably, Li is 4,4-dicyclohexylenemethane corresponding to formula (VIII) below:

[0134] (VIII). According to another embodiment, when LI is a C6-C14 arylene group, Li is not the m-tetramethylxylylene radical represented by formula (IX) below: 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;

[0135] - R5 independently represents a covalent bond or a saturated divalent hydrocarbonbased radical, optionally interrupted with one or more heteroatoms; and

[0136] - Re independently represents a hydrogen atom or a hydrocarbon-based radical, optionally interrupted with one or more heteroatoms.

[0137] Preferably, R3 and R4 are independently chosen from a Ce-Ci4 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.

[0138] 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.

[0139] Preferably, when R5 is not a covalent bond, R5 is chosen from a C6-C14 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.

[0140] Preferably, Re is chosen from a Ce-Ci4 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.

[0141] 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.

[0142] 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.

[0143] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from a-methylstyryl isocyanates of formula (X) below:

[0144]

[0145] (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.

[0146] In this embodiment, the term “alkyl group” is as defined previously.

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

[0148] In this embodiment, n may denote an integer ranging from 2 to 50, preferably from 3 to 30 and more preferentially from 5 to 10.

[0149] According to another particular embodiment, the (poly)carbodiimide compound is a compound of formula (XI) below:

[0150] (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.

[0151] The “alkyl group”, the “cycloalkyl group” and the “aryl group” are as defined previously.

[0152] According to a preferred embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) or of formula (II) in which:

[0153] - Xi and X2 independently represent an oxygen atom;

[0154] - 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, Ru represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q denotes an integer ranging from 4 to 30;

[0155] - 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 ;

[0156] - 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 C6-C14 arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical;

[0157] - 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 C6-C14 arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical;

[0158] - E, when it is present, independently represents a group chosen from:

[0159] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a C6-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;

[0160] - when R5 is not a covalent bond, R5, when it is present, is chosen from a C6-C14 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

[0161] - Re, when it is present, is chosen from a Ce-Ci4 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.

[0162] Preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0163] - Xi and X2 independently represent an oxygen atom;

[0164] - 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;

[0165] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1 ;

[0166] - Li is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a C6-C14 arylene group, and mixtures thereof;

[0167] - E independently represents a group chosen from:

[0168] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a C6-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;

[0169] - when R5 is not a covalent bond, R5 is chosen from a C6-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; and

[0170] - 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.

[0171] More preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0172] - Xi and X2 independently represent an oxygen atom;

[0173] - Ri and R2 are, independently, monoalkyl ethers of (poly) alkylene glycol, in which a hydroxyl group has been removed;

[0174] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1 ;

[0175] - Li is a C3-C15 cycloalkylene radical;

[0176] - E independently represents a group chosen from:

[0177] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a C6-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;

[0178] - when R5 is not a covalent bond, R5 is chosen from a C6-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; and

[0179] - Re is chosen from a Ce-Ci4 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.

[0180] Even more preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0181] - Xi and X2 independently represent an oxygen atom;

[0182] - Ri and R2 independently represent the compound of formula (VI) below:

[0183] 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;

[0184] - 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;

[0185] - Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylenemethane; and

[0186] - E represents a group -O-R3-O- in which R3 is chosen from a C6-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.

[0187] Even more preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0188] - Xi and X2 independently represent an oxygen atom;

[0189] - 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;

[0190] - 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 ;

[0191] - Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylenemethane, preferably 4,4- dicyclohexylenemethane; and

[0192] - 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.

[0193] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of formula (XII) below:

[0194]

[0195] (XII), 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.

[0196] 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 C.

[0197] Polymer comprising at least one reactive group chosen from carboxylic acids

[0198] Composition C 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.

[0199] 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. Thus, preferably, composition C comprises at least one acrylic polymer in the form of aqueous dispersions of acrylic polymer particles.

[0200] 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.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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).

[0205] 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.

[0206] 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.

[0207] Among the hydroxyalkyl (meth)acrylates that may be mentioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2- hydroxypropyl methacrylate.

[0208] Among the aryl (meth)acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.

[0209] The (meth)acrylic acid esters that are particularly preferred are alkyl, preferably Ci to C30, more preferentially Ci to C20, better still Ci to C10, and even more particularly Ci to C4 alkyl, (meth)acrylates. 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.

[0210] As (meth)acrylic acid amides, examples that may be mentioned include (meth)acrylamides and also N-alkyl(meth)acrylamides, in particular N-(Ci 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 .

[0211] 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.

[0212] 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, preferably Ci to C20, more preferentially Ci to C10 and even more preferentially Ci to C4 alkyl (meth)acrylate.

[0213] 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.

[0214] 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 Eubrizol, or the compound Acrylate Copolymer sold under the trade name Daitosol 3000VP3 by the company Daito Kasei Kogyo, or the compound Acrylate Copolymer sold under the trade name Daitosol 3000 SEPN-PE1 by the company Daito Kasei Kogyo.

[0215] 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.

[0216] As additional monomer, mention will be made, for example, of styrene monomers, in particular styrene and a-methylstyrene, and preferably styrene.

[0217] 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.

[0218] 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.

[0219] 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.

[0220] Preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles. More preferentially, composition C 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 particularly Ci to C4, alkyl (meth)acrylate.

[0221] 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.

[0222] 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 C.

[0223] 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 C.

[0224] 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 C. Colouring agent

[0225] Composition C used in the context of the process according to the invention comprises at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

[0226] Preferably, composition C used in the context of the process according to the invention comprises at least one pigment.

[0227] The term “pigment” refers to any pigment that gives colour to keratin materials. Their solubility in water at 25°C and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

[0228] The pigments that may be used are notably chosen from the organic and / or mineral pigments known in the art, notably those described in Kirk-Othmer’s Encyclopedia of Chemical Technology and in Ullmann’s Encyclopedia of Industrial Chemistry.

[0229] They may be natural, of natural origin, or non-natural.

[0230] These pigments may be in pigment powder or paste form. They may be coated or uncoated.

[0231] The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, special-effect pigments such as nacres or glitter flakes, and mixtures thereof.

[0232] The pigment may be a mineral pigment. The term “mineral pigment” refers to any pigment that satisfies the definition in Ullmann’s Encyclopedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

[0233] The pigment may be an organic pigment. The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’s Encyclopedia in the chapter on organic pigments.

[0234] The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

[0235] In particular, the white or coloured organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.

[0236] Examples that may also be mentioned include pigment pastes of organic pigments, such as the products sold by the company Hoechst under the names:

[0237] - Cosmenyl Yellow 10G: Yellow 3 pigment (CI 11710);

[0238] - Cosmenyl Yellow G: Yellow 1 pigment (CI 11680);

[0239] - Cosmenyl Orange GR: Orange 43 pigment (CI 71105);

[0240] - Cosmenyl Red R: Red 4 pigment (CI 12085);

[0241] - Cosmenyl Carmine FB: Red 5 pigment (CI 12490);

[0242] - Cosmenyl Violet RL: Violet 23 pigment (CI 51319);

[0243] - Cosmenyl Blue A2R: Blue 15.1 pigment (CI 74160);

[0244] - Cosmenyl Green GG: Green 7 pigment (CI 74260);

[0245] - Cosmenyl Black R: Black 7 pigment (CI 77266).

[0246] The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may notably be composed of particles including an inorganic core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core.

[0247] The organic pigment may also be a lake. The term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.

[0248] The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

[0249] Among the dyes, mention may be made of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42090).

[0250] An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (CI 15 850:1).

[0251] The pigment may also be a special-effect pigment. The term “special-effect pigments” means pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non- uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from coloured pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.

[0252] Several types of special-effect pigments exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.

[0253] Examples of special-effect pigments that may be mentioned include nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and notably with ferric blue or with chromium oxide, mica covered with titanium and with an organic pigment as defined previously, and also nacreous pigments based on bismuth oxychloride. Nacreous pigments that may be mentioned include the nacres Cellini sold by BASF (mica-TiOi-lake), Prestige sold by Eckart (mica-TiOi), Prestige Bronze sold by Eckart (mica-FeiOa) and Colorona sold by Merck (mica-TiOi-FeiOa).

[0254] Mention may also be made of the gold-coloured nacres sold notably by the company BASF under the name Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); the bronze nacres sold notably by the company Merck under the name Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super Bronze (Cloisonne); the orange nacres sold notably by the company BASF under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion Orange (Colorona) and Matte Orange (17449) (Microna); the brown nacres sold notably by the company BASF under the name Nu-antique Copper 340XB (Cloisonne) and Brown CE4509 (Chromalite); the nacres with a copper tint sold notably by the company BASF under the name Copper 340A (Timica); the nacres with a red tint sold notably by the company Merck under the name Sienna Fine (17386) (Colorona); the nacres with a yellow tint sold notably by the company BASF under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold notably by the company BASF under the name Sunstone GO 12 (Gemtone); the pink nacres sold notably by the company BASF under the name Tan Opale G005 (Gemtone); the black nacres with a gold tint sold notably by the company BASF under the name Nu-antique Bronze 240 AB (Timica), the blue nacres sold notably by the company Merck under the name Matte Blue (17433) (Microna), the white nacres with a silvery tint sold notably by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold notably by the company Merck under the name Indian Summer (Xirona), and mixtures thereof.

[0255] Still as examples of nacres, mention may also be made of particles including a borosilicate substrate coated with titanium oxide.

[0256] Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.

[0257] Finally, examples of nacres that may also be mentioned include polyethylene terephthalate glitter flakes, notably those sold by the company Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver glitter flakes). It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.

[0258] The special-effect pigments may also be chosen from reflective particles, i.e. notably from particles whose size, structure, notably the thickness of the layer(s) of which they are made and their physical and chemical nature, and surface state, allow them to reflect incident light. This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. more luminous points that contrast with their environment, making them appear to sparkle.

[0259] The reflective particles may be selected so as not to significantly alter the colouring effect generated by the colouring agents with which they are combined, and more particularly so as to optimize this effect in terms of colour rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and / or coppery colour or tint.

[0260] These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form. The reflective particles, whatever their form, may or may not have a multilayer structure and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, notably of a reflective material.

[0261] When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, notably titanium or iron oxides obtained synthetically.

[0262] When the reflective particles have a multilayer structure, they may include, for example, a natural or synthetic substrate, notably a synthetic substrate at least partially coated with at least one layer of a reflective material, notably of at least one metal or metallic material. The substrate may be made of one or more organic and / or mineral materials.

[0263] More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, notably aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.

[0264] The reflective material may include a layer of metal or of a metallic material.

[0265] Reflective particles are notably described in JP-A-09188830, JP- A- 10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0266] Again as an example of reflective particles including a mineral substrate coated with a layer of metal, mention may also be made of particles including a silver- coated borosilicate substrate.

[0267] Particles with a silver-coated glass substrate, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by the company Toyal. Particles with a glass substrate coated with a nickel / chromium / molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.

[0268] Use may also be made of particles comprising a metal substrate, such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

[0269] Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiOi sold under the name Visionaire by the company Eckart.

[0270] Mention may also be made of interference pigments which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f / x from Spectratek). Special-effect pigments also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.

[0271] The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects.

[0272] The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 pm, preferably between 20 nm and 80 pm and more preferentially between 30 nm and 50 pm.

[0273] The pigments may be dispersed in the composition by means of a dispersant.

[0274] The dispersant serves to protect the dispersed particles against agglomeration or flocculation thereof. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxy stearic acid in particular and of Cs to C20 fatty acid and of polyols such as glycerol or diglycerol are used, such as poly( 12-hydroxy stearic acid) stearate with a molecular weight of approximately 750 g / mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or else polyhydroxystearic acid such as the product sold under the reference Arlacel Pl 00 by the company Uniqema, and mixtures thereof.

[0275] As other dispersants that can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane / oxypropylene mixtures such as those sold by the company Dow Coming under the references DC2-5185 and DC2-5225 C.

[0276] The pigments used in the composition may be surface-treated with an organic agent.

[0277] Thus, the pigments surface-treated beforehand that are useful in the context of the invention are pigments which have been completely or partially subjected to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those described notably in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxy stearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, notably poly dimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.

[0278] The surface-treated pigments that are useful in the composition may also have been treated with a mixture of these compounds and / or may have undergone several surface treatments.

[0279] The surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.

[0280] Preferably, the surface-treated pigments are coated with an organic layer.

[0281] The organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.

[0282] The surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in patent US 4 578 266.

[0283] An organic agent covalently bonded to the pigments will preferably be used.

[0284] The agent for the surface treatment may represent from 0.1% to 50% by weight relative to the total weight of the surface-treated pigment, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of the surface-treated pigment.

[0285] Preferably, the surface treatments of the pigments are chosen from the following treatments: - a PEG- silicone treatment, for instance the AQ surface treatment sold by

[0286] LCW;

[0287] - a methicone treatment, for instance the SI surface treatment sold by LCW;

[0288] - a dimethicone treatment, for instance the Covasil 3.05 surface treatment sold by LCW;

[0289] - a dimethicone / trimethyl siloxysilicate treatment, for instance the Covasil 4.05 surface treatment sold by LCW;

[0290] - a magnesium myristate treatment, for instance the MM surface treatment sold by LCW;

[0291] - an aluminium dimyristate treatment, for instance the MI surface treatment sold by Miyoshi;

[0292] - a perfluoropolymethyl isopropyl ether treatment, for instance the LHC surface treatment sold by LCW;

[0293] - an isostearyl sebacate treatment, for instance the HS surface treatment sold by Miyoshi;

[0294] - a perfluoroalkyl phosphate treatment, for instance the PE surface treatment sold by Daito;

[0295] - an acrylate / dimethicone copolymer and perfluoroalkyl phosphate treatment, for instance the ESA surface treatment sold by Daito;

[0296] - a polymethylhydrogenosiloxane / perfluoroalkyl phosphate treatment, for instance the ES01 surface treatment sold by Daito;

[0297] - an acrylate / dimethicone copolymer treatment, for instance the ASC surface treatment sold by Daito;

[0298] - an isopropyl titanium triisostearate treatment, for instance the ITT surface treatment sold by Daito;

[0299] - an acrylate copolymer treatment, for instance the APD surface treatment sold by Daito;

[0300] - a perfluoroalkyl phosphate / isopropyl titanium triisostearate treatment, for instance the PL + ITT surface treatment sold by Daito.

[0301] According to a particular embodiment of the invention, the dispersant is present with organic or mineral pigments in submicron-sized particulate form.

[0302] The term “submicron-sized” or “submicronic” refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometre (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm. According to one embodiment, the dispersant and the pigment(s) are present in a (dispersant:pigment) amount, according to a weight ratio, of between 1: 4 and 4: 1, particularly between 1.5: 3.5 and 3.5: 1 or better still between 1.75: 3 and 3: 1.

[0303] The dispersant(s) may therefore have a silicone backbone, such as silicone polyether and dispersants of amino silicone type. Among the suitable dispersants that may be mentioned are:

[0304] - amino silicones, i.e. silicones comprising one or more amino groups, such as those sold under the following names and references: BYK LPX 21879, by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, sold by Genesee Polymers,

[0305] - silicone acrylates such as Tego® RC 902, Tego® RC 922, Tego® RC 1041, and Tego® RC 1043, sold by Evonik,

[0306] - polydimethylsiloxane (PDMS) silicones bearing carboxylic groups such as X-22162 and X-22370 by Shin-Etsu, epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695 by Genesee Polymers, or Tego® RC 1401, Tego® RC 1403, Tego® RC 1412 by Evonik.

[0307] According to a particular embodiment, the dispersant(s) are of amino silicone type and are cationic.

[0308] Preferably, the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments.

[0309] In one variant of the invention, the pigment(s) are organic pigments, preferentially organic pigments surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment(s) are mineral pigments.

[0310] Preferably, the pigment(s) are chosen from iron oxides, notably red, brown or black iron oxides. As an example of an iron oxide, mention may be made of the iron oxide sold by the company Sun Chemical under the name SunPuro® Red Iron Oxide.

[0311] Direct dye

[0312] Composition C used in the context of the process according to the invention may comprise one or more direct dyes.

[0313] 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. Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.

[0314] 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.

[0315] 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.

[0316] 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.

[0317] 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.

[0318] As examples of nitro dyes, mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XXII’), 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”-hydroxyethyl)amino-2’ - nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7. 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.

[0319] 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.

[0320] As examples of indole dyes, mention may be made of: Acid Blue 74.

[0321] As examples of quinoline dyes, mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0322] 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.

[0323] The colouring agent(s) may be present in a total amount ranging from 0.001% to 20% by weight and preferably from 0.005% to 15% by weight relative to the total weight of composition C; preferably, the colouring agents are chosen from pigments.

[0324] The pigment(s) may be present in a total amount ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight and better still from 0.5% to 10% by weight, relative to the total weight of composition C.

[0325] 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.

[0326] Associative polymers

[0327] Composition C 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.

[0328] As recalled above, “associative polymers” are polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

[0329] 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.

[0330] 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.

[0331] 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.

[0332] The associative polymers may be of nonionic, anionic, cationic or amphoteric nature. Preferably, the associative polymer(s) are chosen from anionic associative polymers.

[0333] 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.

[0334] Preferentially, these compounds also comprise, as monomer, an ester of an a,P-monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.

[0335] 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.

[0336] 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.

[0337] 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 C.

[0338] Solvents

[0339] 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 5% to 80% by weight and more preferentially from 10% to 70% by weight relative to the total weight of composition C.

[0340] In addition, composition C may comprise one or more organic solvents. 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- butoxyethanol, 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.

[0341] The organic solvents may be present in a total amount of between 0.01% and 90% by weight, preferably between 1% and 80% by weight and more preferentially inclusively between 10% and 70% by weight relative to the total weight of composition C.

[0342] Additives

[0343] Composition C used in the context of the process according to the invention may contain any adjuvant or additive usually used.

[0344] Among the additives that may be contained in the composition, mention may be made of softeners, antifoams, moisturizers, UV-screening agents, peptizers, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers described previously, preserving agents, silicones, oils, waxes other than silicones in wax form, and mixtures thereof.

[0345] Composition C 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 / W / O), 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.

[0346] 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.

[0347] Composition D

[0348] The process for dyeing hair keratin fibres according to the invention may also comprise the application to the hair keratin fibres of a composition D comprising at least one silicone compound comprising at least one acidifying agent.

[0349] Preferably, the acidifying agent is chosen from citric acid, lactic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid and mixtures thereof. Advantageously, composition D has a pH ranging from 1 to 6, preferably from 1.5 to 5, more preferentially from 2 to 4.

[0350] According to a preferred embodiment, composition C and the optional composition D are applied simultaneously to the hair keratin fibres.

[0351] According to another preferred embodiment, composition D is applied to the hair keratin fibres after applying composition C to the hair keratin fibres.

[0352] According to yet another preferred embodiment, composition D is applied to the hair keratin fibres before applying composition C to the hair keratin fibres.

[0353] According to a particularly preferred embodiment, composition D is applied to the hair keratin fibres after applying composition C to the hair keratin fibres.

[0354] Protocol

[0355] Treatment with a composition T comprising at least two reducing agents as defined previously may be performed on dry or damp hair keratin fibres, and also on all types of light or dark, natural or coloured, permanent waved, bleached or relaxed hair keratin fibres.

[0356] According to a particular embodiment of the invention, the hair keratin fibres is rinsed with water or washed after treatment with at least two reducing agents as defined previously.

[0357] Preferably, a washing or rinsing, draining or drying step is performed after treatment with at least two reducing agents as defined previously.

[0358] More preferentially, a drying step is performed after treatment with at least two reducing agents as defined previously.

[0359] The treatment with at least two reducing agents as defined previously may be performed between 15 and 100°C.

[0360] After treatment with at least two reducing agents as defined previously, a waiting time of 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 30 minutes, may be observed before applying composition C to the hair keratin fibres.

[0361] Preferably, the leave-on time is between 1 minute and 20 minutes before applying composition C to the hair keratin fibres.

[0362] Composition C and the optional composition D described above may be used on wet or dry hair keratin fibres, and also on any type of fair or dark, natural or dyed, permanent- waved, bleached or relaxed hair keratin fibres. According to a preferred embodiment, composition C and the optional composition D are applied simultaneously to the hair keratin fibres.

[0363] According to another preferred embodiment, composition D is applied to the hair keratin fibres after applying composition C to the hair keratin fibres.

[0364] According to another preferred embodiment, composition D is applied to the hair keratin fibres before applying composition C to the hair keratin fibres.

[0365] According to a particular embodiment of the invention, the hair keratin fibres is rinsed before applying composition C and the optional composition D.

[0366] Preferably, a rinsing, draining and / or drying step is performed after applying composition C to the hair keratin fibres and before applying the optional composition D to the hair keratin fibres.

[0367] More preferentially, a drying step is performed after applying composition C to the hair keratin fibres and before applying the optional composition D to the hair keratin fibres.

[0368] 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.

[0369] The application of composition C and of the optional composition D to the hair keratin fibres is generally performed at room temperature (between 15 and 25 °C).

[0370] After applying composition C to 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 30 minutes, before, for example, applying composition D to the hair keratin fibres or, for example, a drying step.

[0371] Preferably, there is no leave-on time after applying composition C to the hair keratin fibres and before applying the optional composition D to the hair keratin fibres.

[0372] After applying composition C and the optional composition D, 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.

[0373] The process according to the invention may thus comprise a step of applying heat to the keratin fibres using a heating tool.

[0374] 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.

[0375] Preferably, the heat application step of the process of the invention is performed using a hairdryer. When the process of the invention involves a step of applying heat to the hair keratin fibres, the step of applying heat to the hair keratin fibres takes place after applying composition C and the optional composition D to the hair keratin fibres.

[0376] 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.

[0377] Preferably, the locks are combed using a comb during the application of heat to the hair keratin fibres.

[0378] 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.

[0379] When the step of applying heat to the hair keratin fibres is performed using a straightening iron, the temperature is preferably between 110°C and 220°C, preferably between 140°C and 200°C.

[0380] In a particular variant, the process of the invention involves a step (cl) of applying heat using a hood, a hairdryer or a Climazon hood, preferably a hairdryer, and a step (c2) of applying heat using a straightening or curling iron, preferably a straightening iron.

[0381] Step (cl) may be performed before step (c2).

[0382] During step (cl), also referred to as the drying step, the hair keratin fibres may be dried, for example at a temperature above or equal to 30°C. According to a particular embodiment, this temperature is above 40°C. According to a particular embodiment, this temperature is above 45°C and below 110°C.

[0383] Preferably, if the hair keratin fibres is dried, it is 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 coating.

[0384] During the drying, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through.

[0385] During step (c2), the passage of the straightening or curling iron, preferably the straightening iron, may be performed at a temperature ranging from 11 C C to 220°C, preferably between 140°C and 200°C.

[0386] After the heating step, a shaping step may be performed, for example with a straightening iron; the temperature for the shaping step is between 110 and 220°C, preferably between 140 and 200°C.

[0387] The process for dyeing hair keratin fibres according to the invention comprises: (i) a step consisting in treating the hair keratin fibres with a composition T comprising:

[0388] - at least a first reducing agent ARI in dimer form as defined previously, and

[0389] - at least a second reducing agent AR2 different from said reducing agent ARI, as defined previously; and then

[0390] (ii) a step consisting in applying to the hair keratin fibres at least one dye composition C comprising:

[0391] (1) at least one (poly)carbodiimide compound as defined previously;

[0392] (2) at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously; and

[0393] (3) at least one colouring agent chosen from pigments, direct dyes and mixtures thereof as defined previously.

[0394] Preferably, the invention is a process for dyeing hair keratin fibres comprising:

[0395] (i) a step consisting in treating the hair keratin fibres with a composition T comprising:

[0396] - at least a first reducing agent ARI in dimer form as defined previously, and

[0397] - at least a second reducing agent AR2 different from said reducing agent ARI, as defined previously; and then

[0398] (ii) optionally a leave-on time of said composition T on the hair keratin fibres of from

[0399] 1 minute to 30 minutes, preferably from 1 to 20 minutes; and then

[0400] (iii) a step consisting in applying to the hair keratin fibres at least one dye composition C comprising:

[0401] (1) at least one (poly)carbodiimide compound as defined previously;

[0402] (2) at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously; and

[0403] (3) at least one colouring agent chosen from pigments, direct dyes and mixtures thereof as defined previously;

[0404] (iv) optionally a leave-on time of said composition C on the hair keratin fibres of from

[0405] 1 minute to 30 minutes, preferably from 1 to 20 minutes; and then

[0406] (v) optionally a step of washing, rinsing, draining and / or drying said hair keratin fibres; and then

[0407] (vi) optionally the application to the hair keratin fibres of at least one composition D comprising at least one acidifying agent as described previously, and then

[0408] (vii) optionally a leave-on time of said composition D on the hair keratin fibres of from

[0409] 1 minute to 30 minutes, preferably from 1 to 20 minutes; and then (viii) optionally a step of washing, rinsing, draining and / or drying the hair keratin fibres.

[0410] Preferably, composition C also comprises at least one associative polymer different from the polymer comprising at least one reactive group chosen from the carboxylic acids as described previously.

[0411] Advantageously, the dyeing process comprises step (vi) of applying to the hair keratin fibres a composition D comprising at least one acidifying agent as described previously.

[0412] According to a preferred embodiment, the dyeing process according to the invention comprises a step which consists in extemporaneously mixing, at the time of use, at least two compositions A and B to obtain a composition C and in applying composition C to the hair keratin fibres during step (ii), with:

[0413] - composition A comprising (1) at least one (poly)carbodiimide compound as defined previously;

[0414] - composition B comprising (2) at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously and (3) at least one colouring agent as defined previously.

[0415] According to another preferred embodiment, the dyeing process according to the invention comprises a step which consists in extemporaneously mixing, at the time of use, at least two compositions A and B to obtain a composition C and in applying composition C to the hair keratin fibres during step (ii), with:

[0416] - composition A comprising (1) at least one (poly)carbodiimide compound as defined previously;

[0417] - composition B comprising (2) at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously and optionally at least one associative polymer different from the polymer (2), composition A and / or composition B comprising (3) at least one colouring agent as defined previously.

[0418] According to another preferred embodiment, the dyeing process according to the invention is a process for dyeing hair keratin fibres comprising:

[0419] (i) a step consisting in treating the hair keratin fibres with a composition T comprising:

[0420] - at least a first reducing agent ARI in dimer form as defined previously, and

[0421] - at least a second reducing agent AR2 different from said reducing agent ARI, as defined previously; and then (ii) a step consisting in applying to the hair keratin fibres at least one dye composition C obtained by extemporaneously mixing at the time of use at least two compositions A and B, with:

[0422] - composition A comprising (1) at least one (poly)carbodiimide compound as defined previously;

[0423] - composition B comprising (2) at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously and (3) at least one colouring agent as defined previously. composition A and / or composition B optionally comprising at least one associative polymer different from the polymer comprising at least one reactive group chosen from the carboxylic acids as described previously.

[0424] According to another preferred embodiment, the dyeing process according to the invention is a process for dyeing hair keratin fibres comprising:

[0425] (i) a step consisting in treating the hair keratin fibres with a composition T comprising:

[0426] - at least a first reducing agent ARI in dimer form as defined previously, and

[0427] - at least a second reducing agent AR2 different from said reducing agent ARI, as defined previously; and then

[0428] (ii) a step consisting in applying to the hair keratin fibres at least one dye composition C obtained by extemporaneously mixing at the time of use at least two compositions A and B, with:

[0429] - composition A comprising (1) at least one (poly)carbodiimide compound as defined previously;

[0430] - composition B comprising (2) at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously, composition A and / or composition B comprising (3) at least one colouring agent as defined previously.

[0431] Advantageously, the dyeing process also involves applying to the hair keratin fibres at least one composition D comprising at least one acidifying agent as described previously.

[0432] Preferably, composition A does not comprise at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

[0433] 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. 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.

[0434] 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.

[0435] 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.

[0436] According to a particular embodiment, composition B comprises at least one associative polymer as defined previously. The total amount 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.

[0437] Multi-compartment device (kit)

[0438] The present invention also relates to a device for dyeing the hair keratin fibres, comprising several compartments containing:

[0439] * in a first compartment, a composition T comprising:

[0440] - at least a first reducing agent ARI in dimer form, and at least a second reducing agent AR2 different from said reducing agent ARI, as defined previously; and

[0441] * in a second compartment, a composition C comprising:

[0442] - at least one (poly)carbodiimide compound as defined previously;

[0443] - at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously;

[0444] - at least one colouring agent as defined previously;

[0445] * optionally, in a third compartment, a composition D comprising at least one acidifying agent as defined previously.

[0446] More preferentially, the device for dyeing the hair keratin fibres, comprising several compartments, contains: * in a first compartment, a composition T:

[0447] - at least a first reducing agent ARI in dimer form, and at least a second reducing agent AR2 different from said reducing agent ARI, as defined previously;

[0448] * in a second compartment, a composition A comprising at least one (poly)carbodiimide compound as defined previously;

[0449] * in a third compartment, a composition B comprising at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously, composition A and / or composition B comprising at least one colouring agent as defined previously;

[0450] * optionally, in a fourth compartment, a composition D comprising at least one acidifying agent as defined previously.

[0451] 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.

[0452] EXAMPLES

[0453] 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.

[0454] More particularly, the process for preparing the (poly)carbodiimides of the invention involves, in a first step, a diisocyanate reagent (1):

[0455] 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-dioxane 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): 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.

[0456] 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:

[0457] [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.

[0458] 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):

[0459] 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.

[0460] 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.

[0461] During a third step, compound (5) reacts with 1 eq. of compound (6) 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):

[0462] 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.

[0463] 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.

[0464] This last compound (8) can then react with 1 eq. of compound (4’):

[0465] 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 Ri-Xi-H with 1 equivalent of compound (3)), to give the (poly)carbodiimide (9) of the invention:

[0466] 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.

[0467] 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.

[0468] Example 1: Process for synthesizing the (poly)carbodiimide compound

[0469] 50 g of 4,4’ -dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3- methyl-1 -phenyl- IH-phosphole 1-oxide were placed with stirring in a 500 mL threenecked round-bottomed flask equipped with a thermometer, a stirrer and a reflux tube.

[0470] The reaction medium was 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.

[0471] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4- butanediol is 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 the reaction medium is then cooled to room temperature.

[0472] 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.

[0473] Example 2

[0474] Compositions A and B 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). [Table 1]

[0475] (1) synthesized according to the synthetic process described in Example 1 (containing 40% active material in water), [Table 2]

[0476] (2) sold by the company Daito Kasei Kogyo under the trade name Daitosol 3000SLPN- PE1 (aqueous dispersion containing 30% active material)

[0477] (3) 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)

[0478] (4) 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 A was then mixed with composition B in a 50 / 50 mass ratio to obtain a composition C.

[0479] Pretreatment with a reducing agent:

[0480] Certain locks were pretreated with a composition T as described in Table 3 below, comprising a combination of two reducing agents as described below: the amounts are expressed as g of raw material as obtained / 100 g, unless otherwise mentioned.

[0481] [Table 3]

[0482] (5) sold by the company Bruno Bock under the trade name Thiocare H100 (containing 99% active material)

[0483] (6) sold by the company Bruno Bock under the trade name Thiocare H801 (containing 48% active material)

[0484] Protocol

[0485] Two processes were performed on 1 g locks of TH8 (tone height 8) natural hair keratin fibres.

[0486] According to process 1, the locks of hair keratin fibres were treated by applying composition T comprising a combination of two reducing agents, as described previously, at a rate of 2 g of composition per gram of lock. The application of composition T was followed by a leave-on time of 5 minutes at room temperature. The locks were then rinsed with water, after which they were dried with a hairdryer.

[0487] Composition C was then applied to the locks previously treated with composition T, at a rate of 0.8 g per gram of lock, using a mascara brush. The locks were then dried using a hairdryer, while at the same time combing them until they were totally dry. According to process 2, composition C was applied to the locks of hair keratin fibres at a rate of 0.8 g of composition per gram of lock, using a mascara brush, and the locks were then dried with a hairdryer, while at the same time being combed until they were completely dry.

[0488] Process 1, referred to hereinbelow as process Pl, is a process according to the invention.

[0489] Process 2, referred to hereinbelow as process P2, is a comparative process.

[0490] The processes applied are summarized in Table 4 below:

[0491] [Table 4]

[0492] The locks of hair keratin fibres treated via processes Pl and P2 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.

[0493] Shampoo washing protocol

[0494] 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.

[0495] A standard shampoo (Gamier 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.

[0496] The locks of hair keratin fibres are then placed on a watch glass and left to stand for 1 minute.

[0497] 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. Once the tests of five shampoo washes have been performed, the locks of hair keratin fibres are combed and dried with a hairdryer.

[0498] Results

[0499] The persistence of the colour of the locks was evaluated in the CIE L*a*b* system, using a Minolta CM3610A spectrophotometer (illuminant D65, angle 10°, specular component included).

[0500] 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.

[0501] 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 the shampoo washing protocol described above. The lower the AE value, the more persistent the colour with respect to shampoo washing.

[0502] The AE value is calculated according to the following equation:

[0503] In this equation, L*, a* and b* represent the values measured after dyeing the hair keratin fibres and after performing five shampoo washes, and Lo*, ao* and bo* represent the values measured after dyeing the hair keratin fibres but before shampoo washing.

[0504] The results are collated in Table 5 below.

[0505] [Table 5] 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 relative to the locks of hair keratin fibres treated by means of comparative process 2.

[0506] Example 3

[0507] Compositions A and B as described above were used in example 3.

[0508] Composition A was then mixed with composition B in a 50 / 50 mass ratio to obtain a composition C.

[0509] Pretreatment with a reducing agent

[0510] The locks were pretreated with a composition T1 or with a composition T2 as described in Table 6 below, 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).

[0511] [Table 6]

[0512] (7) sold by the company Sigma Aldrich (CAS: 4420-74-0)

[0513] Protocol

[0514] Two processes were performed on 1 g locks of TH8 (tone height 8) natural hair keratin fibres.

[0515] The locks of hair keratin fibres were treated by applying composition T1 or composition T2, at a rate of 2 g of composition per gram of lock. The application of composition Tl, or T2, was followed by a leave-on time of 5 minutes at room temperature. The locks were then rinsed with water, after which they were dried with a hairdryer. Composition C was then applied to the locks previously treated with composition T1 (process P3), or T2 (process P4), at a rate of 0.8 g per gram of lock, using a mascara brush. The locks were then dried using a hairdryer, while at the same time combing them until they were totally dry.

[0516] The locks of hair keratin fibres treated via processes P3 and 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. The protocol for shampoo washing is described above in example 2.

[0517] Results

[0518] The persistence of the colour of the locks was evaluated in the CIE L*a*b* system, using a Minolta CM3610A spectrophotometer (illuminant D65, angle 10°, specular component included), in the same way as described above in example 2.

[0519] The AE value is calculated according to the same equation as specified above.

[0520] The results are collated in Table 7 below.

[0521] [Table 7]

[0522] 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 relative to the locks of hair keratin fibres treated by means of comparative process P4.

Claims

1. CLAIMS1. Process for dyeing hair keratin fibers comprising:(i) a step consisting in treating the hair keratin fibers with a composition T comprising:- at least a first reducing agent ARI in dimer form, and- at least a second reducing agent AR2 different from said reducing agent ARI; and then(ii) a step consisting in applying to the hair keratin fibers at least one dye composition C 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) at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

2. Process according to Claim 1, characterized in that the reducing agent(s) ARI are chosen from thioglycolic acid dimers, such as dithiodiglycolic acid, mineral and / or organic salts thereof, such as diammonium dithiodiglycolate, and mixtures thereof; preferably, the reducing agent ARI is diammonium dithiodiglycolate.

3. Process according to Claim 1 or 2, characterized in that the reducing agent(s) AR2 are chosen from thiol-based reducing agents, mineral and / or organic salts thereof, and mixtures thereof, preferably from the reducing agents of formula (i-1) below, mineral and / or organic salts thereof, and mixtures thereof: Ri-SH (i-1) in which formula (i-1):■ Ri represents:- a (Ci-Cs)alkyl and preferably (Ci-C6)alkyl group, optionally substituted with one or more groups chosen from carboxyl C(O)OH, (di)(Ci-C4)(alkyl)amino, hydroxyl -OH, thiol -SH or -C(O)-NH-CH2-C(O)OH and / or optionally interrupted with one or more heteroatoms or groups chosen from -O-, -S-, -N(R”’)-, C(O) or combinations thereof such as -O-C(O)-, -C(O)-O-, -N(R”’)-C(O)-, or-C(O)-N(R”’)-; with R’” representing a hydrogen atom or a (Ci-Ce / alkyl group; or- a (hetero)aryl group optionally substituted with one or more hydroxyl, thiol or carboxyl groups.

4. Process according to any one of the preceding claims, characterized in that the reducing agent(s) AR2 are chosen from thioglycolic acid, thiolactic acid, cysteine, cysteamine, N-acetylcysteamine, glycerol monothioglycolate, thiosulfuric acid derivatives, mineral and / or organic salts thereof, and mixtures thereof, preferably from thioglycolic acid, mineral and / or organic salts thereof, and mixtures thereof.

5. Process according to any one of the preceding claims, characterized in that the reducing agent(s) ARI and AR2 are present in a total content ranging from 0.1% to 10% by weight, preferably from 0.5% to 8%, more preferentially from 0.5% to 5% by weight relative to the total weight of composition T.

6. 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: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, hydroxyalkylsilyl, 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, hydroxyalkylsilyl, 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:

7. Process according to any one of Claims 1 to 5, 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 C6-C14 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 independently represent a divalent hydrocarbon-based radical optionally interrupted with one or more heteroatoms;- R5 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.

8. Process according to Claim 7, 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 C6-C14 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 C6-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;- when Rs is not a covalent bond, R5 is chosen from a C6-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; 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.

9. Process according to Claim 7 or 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, 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 C6-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;- when R5 is not a covalent bond, R5 is chosen from a C6-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; and- Re is chosen from a Ce-Ci4 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 any one of Claims 7 to 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 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; and- E represents a group -O-R3-O- in which R3 is chosen from a C6-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.

11. Process according to any one of Claims 7 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-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.

12. Process according to any one of Claims 7 to 11, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (XII) below:(XII), 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.

13. 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 from0.2% 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 C.

14. 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.

15. 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; and b) Ci to C30, preferably Ci to C20, more preferentially Ci to C10 and even more preferentially Ci to C4 alkyl (meth)acrylate.

16. 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 C.

17. Process according to any one of the preceding claims, characterized in that the total amount of colouring agent(s) chosen from pigments, direct dyes and mixtures thereof ranges from 0.001% to 20% by weight and preferably from 0.005% to 15% by weight relative to the total weight of composition C.

18. Process according to any one of the preceding claims, characterized in that it comprises the application to the hair keratin fibres of a composition D comprising at least one acidifying agent, preferably chosen from citric acid, lactic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid and mixtures thereof.

19. Process according to any one of the preceding claims, characterized in that it comprises a step consisting in extemporaneously mixing at the time of use at least two compositions A and B in order to obtain a composition C and in applying composition C to the hair keratin fibres during step (ii), with:- composition A comprising (1) at least one (poly)carbodiimide compound as defined in any one of Claims 1 and 6 to 12;- 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 14 to 15, composition A and / or composition B comprising at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, as defined in Claim 1.

20. Device for dyeing the hair keratin fibres, comprising several compartments containing:* in a first compartment, a composition T comprising:- at least a first reducing agent ARI in dimer form, and at least a second reducing agent AR2 different from said reducing agent ARI, as defined in any one of Claims 1 to 5,* in a second compartment, a composition A comprising: (1) at least one (poly)carbodiimide compound as defined in any one of Claims 1 and6 to 12,* in a third compartment, a composition B comprising:(2) at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined in any one of Claims 1 and 14 to 15, composition A and / or composition B comprising at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, as defined in Claim 1;* optionally, in a fourth compartment, a composition D comprising at least one acidifying agent as defined in Claim 18.

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