Process for dyeing hair keratin fibres comprising the application of hydrogen peroxide, followed by the application of 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: a) applying to the hair keratin fibres at least one composition T comprising at least hydrogen peroxide; and then b) applying to the hair keratin fibres at least one composition C comprising: - at least one (poly)carbodiimide compound; - at least one polymer comprising at least one reactive group chosen from carboxylic acids; and - 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 hydrogen peroxide, followed by the application of 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 to the hair keratin fibres of a composition T comprising hydrogen peroxide, followed by the application of a composition C comprising a (poly)carbodiimide compound, a polymer comprising at least one reactive group chosen from carboxylic acids, and a 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 hair keratin fibres: a) “permanent” dyeing, the function of which is to afford a substantial modification to the natural colour and which uses oxidation dyes which penetrate into the hair fibre and form the dye via an oxidative condensation process; b) non-permanent, semi-permanent or direct dyeing, which does not use the oxidative condensation process and withstands four or five shampoo washes; it consists in dyeing keratin fibres with dye compositions containing direct dyes; c) temporary dyeing, which gives rise to a modification of the natural colour of the head of hair which lasts from one shampoo wash to the next, and which serves to enhance or correct a shade that has already been obtained. It may also be likened to a “makeup” process.

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

[0008] There is thus still a need for a process for dyeing hair keratin fibres which has the advantage of obtaining a uniform coloured coating on the hair keratin fibres, while at the same time 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, without degrading the cosmetic properties of the hair keratin fibres.

[0009] Thus, the aim of the present invention is to develop a process for dyeing hair keratin fibres which has the advantage of obtaining a smooth and uniform coloured coating on the hair keratin fibres, while at the same time 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, without degrading the hair keratin fibres.

[0010] Disclosure of the invention

[0011] One subject of the present invention is thus a process for dyeing hair keratin fibres comprising: a) applying to the hair keratin fibres at least one composition T comprising at least hydrogen peroxide; and then b) applying to the hair keratin fibres at least one composition C comprising:

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

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

[0014] - at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

[0015] By virtue of the process for dyeing hair keratin fibres according to the invention, coloured coatings are obtained on the hair keratin fibres that make it possible to obtain a colouring that is visible on all types of hair keratin fibres and is persistent with respect to shampoo washing, while at the same time preserving the physical qualities of the hair keratin fibres. Such a coating may be resistant to the external stresses to which the hair keratin fibres may be subjected, such as blow-drying and perspiration. It makes it possible in particular to obtain a uniform deposit.

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

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

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

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

[0020] - an “alkyl” radical denotes a linear or branched saturated radical containing, for example, from 1 to 20 carbon atoms;

[0021] - an “aminoalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an NH2 group;

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

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

[0024] - a “cycloalkyF or “alicycloalkyl” radical denotes a saturated monocyclic or polycyclic, preferably monocyclic, cyclic hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 24 carbon atoms, in particular comprising from 3 to 20 carbon atoms, more particularly from 3 to 13 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl; preferably, the cycloalkyl radical is then an isobornyl group;

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

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

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

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

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

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

[0031] - an “alkoxy” radical denotes an alkyl-oxy radical with “alkyl” as defined previously;

[0032] - an “acyloxy” radical denotes an ester radical R-C(O)-O- with R being an alkyl group as defined previously;

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

[0034] 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.

[0035] 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.

[0036] Composition T

[0037] As mentioned above, the process according to the invention comprises a) the application to the hair keratin fibres of at least one composition T comprising at least hydrogen peroxide.

[0038] Advantageously, the total amount of hydrogen peroxide ranges from 0.01% to 25% by weight, preferably from 0.1% to 20% by weight, more preferentially from 0.5% to 15% by weight, even more preferentially from 1% to 12% by weight, better still from 2% to 10% by weight, even better still from 3% to 9% by weight relative to the total weight of composition T.

[0039] Composition T may also comprise water, preferably in an amount of at least 50% by weight, more preferentially from 50% to 90% by weight, even more preferentially from 60% to 90% by weight relative to the total weight of composition T.

[0040] Composition T may also comprise at least one surfactant, preferably at least one non-ionic surfactant.

[0041] Preferably, composition T comprises at least one non-ionic surfactant. Advantageously, the non-ionic surfactant(s) are chosen from (poly)oxyalkylenated and / or (poly)glycerolated C8 to C30 fatty alcohols, linear or branched, saturated or unsaturated C8 to C30 fatty acid esters of (poly)glycerol, alkyl polyglycosides, saturated or unsaturated, linear or branched, (poly)oxyalkylenated C8 to C30 fatty acid amides and mixtures thereof, preferably polyoxyalkylenated C8 to C30 fatty alcohols, saturated or unsaturated, linear or branched, such as from adducts of ethylene oxide with cetyl alcohol, adducts of ethylene oxide with stearyl alcohol and mixtures thereof and preferably those containing from 2 to 100 oxy ethylene groups, more preferably from 2 to 20 oxyethylene groups, and mixtures thereof; (poly)oxyalkylenated C8 to C30 fatty acid amides and mixtures thereof,

[0042] More preferentially, the non-ionic surfactant(s) are chosen from ceteareth-25, trideceth-2 carboxamide monoethanolamine, steareth-20 and mixture thereof.

[0043] Advantageously, when they are present, the total content of non-ionic surfactant(s) ranges from 0.1% to 20% by weight, preferably from 0.5% to 15% by weight, more preferably from 1% to 10% by weight, even more preferably from 2% to 6% by weight relative to the total weight of the composition T.

[0044] Composition T may also comprise at least one fatty substance, preferably chosen from solid fatty alcohols, liquid hydrocarbons comprising more than 16 carbon atoms, and mixtures thereof.

[0045] The term “fatty alcohol” means a long-chain aliphatic alcohol comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms, and comprising at least one hydroxyl group OH. These fatty alcohols are neither oxyalkylenated nor glycerolated.

[0046] The solid fatty alcohols that may be used are preferably chosen from saturated, and linear or branched, preferably linear and saturated, (mono)alcohols including from 8 to 40 carbon atoms, preferably from 10 to 30, more preferably from 12 to 24 atoms and even more preferably from 14 to 22 carbon atoms.

[0047] Preferentially, the solid fatty alcohol is chosen from cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, arachidyl alcohol, and mixtures thereof, such as cetylstearyl or cetearyl alcohol. Particularly preferably, the solid fatty alcohol is cetearyl alcohol.

[0048] The liquid hydrocarbons comprising more than 16 carbon atoms may be linear or branched, and of mineral or synthetic origin, and are preferably chosen from liquid paraffins, in particular mineral oil, or liquid petroleum jelly, poly decenes, hydrogenated polyisobutene such as Parleam®, and mixtures thereof, more preferably from mineral oil.

[0049] Advantageously, when they are present, the total content of fatty substance(s) ranges from 5% to 35% by weight, preferably from 10% to 30% by weight, more preferably from 15% to 25% by weight relative to the total weight of the composition T.

[0050] Composition T may also at least one cationic polymer, preferably chosen from cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium.

[0051] Mention may be made more particularly of the homopolymer of dimethyldiallylammonium salts (for example chloride) (INCI name polyquaternium- 6) for example sold under the name Merquat 100 by the company Nalco.

[0052] Advantageously, when they are present, the total content of cationic polymer(s) ranges from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, more preferably from 0.1% to 1% by weight relative to the total weight of the composition T.

[0053] Polycarbodiimide compound

[0054] Composition C used in the context of the process according to the invention comprises at least one (poly)carbodiimide compound.

[0055] The term “(poly)carbodiimide”, in the meaning of the present invention and in a manner known per se, designates carbodiimides and polycarbodiimides.

[0056] The composition may comprise at least two different (poly)carbodiimide compounds, present as a mixture in the composition.

[0057] 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.

[0058] The term “ carbodiimide group"" means a divalent linear triatomic fraction of general formula -(N=C=N)-.

[0059] The (poly)carbodiimide compound(s) according to the invention may optionally comprise in their structure one or more reactive groups different from carbodiimide groups, chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.

[0060] 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, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.

[0061] According to a particular embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) below:

[0062] (I), in which:

[0063] - Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0064] - Ri and R2 independently represent a group chosen from a hydrocarbon-based radical, preferably alkyl, optionally interrupted with one or more heteroatoms, a group chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups, and a hydrocarbon-based radical, preferably alkyl, optionally interrupted with one or more heteroatoms and with one or more groups chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups;

[0065] - n denotes an integer ranging from 1 to 1000; and - A is a monomer chosen from the compounds below:

[0066] According to another embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I’) below: in which:

[0067] - Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0068] - Yi and Y2 independently represent a divalent organic radical chosen from a saturated Ci to C36 aliphatic group or a Ce to C24 aromatic or alkylaromatic group, the aliphatic or aromatic group optionally comprising one or more non-pendent heteroatoms, such as a nitrogen atom, an oxygen atom, a sulfur atom, or combinations thereof;

[0069] - Zi and Z2 independently represent a reactive end group or an inert end group;

[0070] - as inert end group, Zi and Z2 may represent, independently, a saturated, linear or branched or cyclic Ci to C50 aliphatic group, or a Ce to Cis aromatic group, said aliphatic and aromatic groups optionally comprising from 1 to 10 heteroatoms chosen from nitrogen, oxygen, sulfur and combinations thereof, and the aliphatic or aromatic group may be partially or totally fluorinated; in this variant, Zi and Z2 comprise a bonding group CG connecting Zi to Yi and Z2 to Y2, the group CG possibly being a single covalent bond, a saturated C-C bond, an unsaturated covalent C-C bond, an amide group, an ester group, a carbonate group, a thioester group, an ether group, a urethane group, a thiourethane group or a urea group;

[0071] - as reactive end group, Zi and Z2 may be chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryl alkyl silyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups;

[0072] - 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;

[0073] - 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;

[0074] - r denotes an integer equal to 0 or 1;

[0075] - m denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0076] - m’ denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0077] - n denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1, with m + (m’*n ) > 2.

[0078] Preferably, Zi and Z2 independently represent a reactive end group; more preferentially, Zi and Z2 independently represent a group chosen from alkoxy silyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups.

[0079] 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.

[0080] Preferably, the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) below:

[0081] (II), in which:

[0082] - Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0083] - Ri and R2 independently represent a hydrocarbon-based radical optionally interrupted with one or more heteroatoms;

[0084] - 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;

[0085] - Li independently represents a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof;

[0086] - E independently represents a group chosen from:

[0087] -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;

[0088] - Rs independently represents a covalent bond or a saturated divalent hydrocarbonbased radical, optionally interrupted with one or more heteroatoms;

[0089] - Re independently represents a hydrogen atom or a hydrocarbon-based radical, optionally interrupted with one or more heteroatoms. 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.

[0090] The hydrocarbon-based radical may comprise one or more cyclic groups.

[0091] 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.

[0092] The term “heteroatom(s)” means an oxygen O, sulfur S or nitrogen N atom, and also halogen atoms such as Cl, F, Br and I. If the heteroatom is included in the chain of the hydrocarbon-based radical, the heteroatom is preferably chosen from oxygen O, sulfur S or nitrogen N atoms.

[0093] Preferably, Xi and X2 independently represent an oxygen atom.

[0094] Preferably, Ri and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxy carboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, and mixtures thereof.

[0095] According to a preferred embodiment, Ri and R2 are independently chosen from groups (i) to (iv) below:

[0096] (i) the compound of formula (III) below:

[0097] R7-O-C(O)-C(R8)(H)- (III), in which R7 represents a C1-C3 alkyl group, and Rs represents a hydrogen atom or a C1-C3 alkyl group; preferably, R7 is a methyl and Rs is a hydrogen atom or a methyl.

[0098] (ii) the compound of formula (IV) below:

[0099] 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.

[0100] (iii) the compound of formula (V) below:

[0101] (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.

[0102] (iv) 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, 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.

[0103] Preferably, Ri and R2independently represent a compound of formula (VI) in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.

[0104] According to an alternative embodiment, Ri and R2are different and one of the radicals Ri or R2represents a compound of formula (IV) as described above and the other radical Ri or R2represents a compound of formula (VI) as described above.

[0105] 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.

[0106] 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.

[0107] According to another alternative embodiment, Ri and R2are identical and represent a compound of formula (VI) in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.

[0108] Preferably, n denotes an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0109] Preferably, z denotes an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0110] Preferably, w is equal to 1.

[0111] Preferably, w is equal to 1, n+z denotes an integer ranging from 4 to 10.

[0112] 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-Ci2heterocycloalkylene group such as imidazolene, pyrrolene and furanylene, or a Ce-Cu arylene group such as phenylene, and mixtures thereof.

[0113] For example, Li may be chosen from a radical derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4- trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-l,3-dioctylcyclobutane, 4,4’- dicyclohexylmethane dnsocyanate, tetramethylxylylene dnsocyanate, isophorone diisocyanate, 1,5-napththylene diisocyanate, 4,4’-diphenylmethane diisocyanate, 4, d’diphenyldimethylmethane diisocyanate and phenylene diisocyanate, and mixtures thereof.

[0114] 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:

[0115] Preferably, Li is 4,4-dicyclohexylenemethane corresponding to formula (VIII) below:

[0116] (VIII).

[0117] According to another embodiment, when LI is a Ce-Cu arylene group, Li is not the m-tetramethylxylylene radical represented by formula (IX) below:

[0118] (IX).

[0119] 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;

[0120] - Rs independently represents a covalent bond or a saturated divalent hydrocarbonbased radical, optionally interrupted with one or more heteroatoms; and

[0121] - Re independently represents a hydrogen atom or a hydrocarbon-based radical, optionally interrupted with one or more heteroatoms.

[0122] Preferably, R3 and R4 are independently chosen from a Ce-Cu arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Cis alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatom(s), and mixtures thereof.

[0123] 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.

[0124] Preferably, when R5 is not a covalent bond, R5 is chosen from a Ce-Cu arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Cis alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatom(s), and mixtures thereof.

[0125] Preferably, Re is chosen from a Ce-Cu arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Cis alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatom(s), and mixtures thereof.

[0126] 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.

[0127] 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.

[0128] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from a-methyl styryl isocyanates of formula (X) below:

[0129] (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.

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

[0131] In this embodiment, the term “cycloalkyl group” is as defined previously.

[0132] 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.

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

[0134] (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.

[0135] The “alkyl group”, the “cycloalkyl group” and the “aryl group” are as defined previously.

[0136] According to a preferred embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) or of formula (II) in which:

[0137] - Xi and X2 independently represent an oxygen atom;

[0138] - Ri and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, more preferentially the compound of formula (VI) as described previously in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q denotes an integer ranging from 4 to 30;

[0139] - 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;

[0140] - Li, when it is present, is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical;

[0141] - A, when it is present, is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical;

[0142] - E, when it is present, independently represents a group chosen from:

[0143] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;

[0144] - when R5 is not a covalent bond, R5, when it is present, is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatom(s), and mixtures thereof; and

[0145] - Re, when it is present, is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatom(s), and mixtures thereof.

[0146] Preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0147] - Xi and X2 independently represent an oxygen atom;

[0148] - 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;

[0149] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0150] - Li is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof;

[0151] - E independently represents a group chosen from:

[0152] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;

[0153] - when R5 is not a covalent bond, R5 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof; and

[0154] - 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.

[0155] More preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0156] - Xi and X2 independently represent an oxygen atom;

[0157] - Ri and R2 are, independently, monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed;

[0158] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0159] - Li is a C3-C15 cycloalkylene radical;

[0160] - E independently represents a group chosen from:

[0161] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-RS-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;

[0162] - when Rs is not a covalent bond, Rs is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof; and

[0163] - 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.

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

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

[0166] - Ri and R2 independently represent the compound of formula (VI) below:

[0167] 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;

[0168] - 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;

[0169] - Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4, 4-di cyclohexylenemethane; and

[0170] - E represents a group -O-R3-O- in which R3 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

[0171] Even 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 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;

[0174] - 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;

[0175] - Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylenemethane, preferably 4,4- dicyclohexylenemethane; and

[0176] - 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.

[0177] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of formula (XII) below:

[0178] 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.

[0179] 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.

[0180] Polymer comprising at least one reactive group chosen from carboxylic acids

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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).

[0188] 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.

[0189] 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.

[0190] Among the hydroxyalkyl (meth)acrylates that may be mentioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2- hydroxypropyl methacrylate.

[0191] Among the aryl (meth)acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.

[0192] 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.

[0193] As (meth)acrylic acid amides, examples that may be mentioned include (meth)acrylamides and also N-alkyl(meth)acrylamides, in particular N-(C2 to C12 alkyl)(meth)acrylamides. Among the N-alkyl(meth)acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and N- undecylacrylamide.

[0194] 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.

[0195] Preferably, the acrylic polymer(s) according to the invention comprise one or more units derived from the following monomers: a) (meth)acrylic acid; and b) Ci to C30, more preferentially Ci to C20, better still Ci to C10, and even more particularly Ci to C4, alkyl (meth)acrylate.

[0196] 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.

[0197] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and of methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and of ethyl acrylate such as the compound sold under the trade name Luvimer MAE by the company BASF, or the compound Polyacrylate- 2 Crosspolymer sold under the trade name Fixate Superhold Polymer by the company Lubrizol, or the compound Acrylate Copolymer sold under the trade name Daitosol 3000VP3 by the company Daito Kasei Kogyo, or the compound Acrylate Copolymer sold under the trade name Daitosol 3000 SLPN-PE1 by the company Daito Kasei Kogyo.

[0198] 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.

[0199] As additional monomer, mention will be made, for example, of styrene monomers, in particular styrene and a-m ethyl styrene, and preferably styrene.

[0200] 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.

[0201] 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.

[0202] 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.

[0203] 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 preferentially Ci to C4 alkyl (meth)acrylate.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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

[0208] 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.

[0209] Preferably, composition C used in the context of the process according to the invention comprises at least one pigment.

[0210] 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%.

[0211] 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.

[0212] They may be natural, of natural origin, or non-natural.

[0213] These pigments may be in pigment powder or paste form. They may be coated or uncoated.

[0214] 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.

[0215] 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.

[0216] 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.

[0217] 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.

[0218] 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.

[0219] Examples that may also be mentioned include pigment pastes of organic pigments, such as the products sold by the company Hoechst under the names:

[0220] - Cosmenyl Yellow 10G: Yellow 3 pigment (CI 11710);

[0221] - Cosmenyl Yellow G: Yellow 1 pigment (CI 11680);

[0222] - Cosmenyl Orange GR: Orange 43 pigment (CI 71105);

[0223] - Cosmenyl Red R: Red 4 pigment (CI 12085);

[0224] - Cosmenyl Carmine FB: Red 5 pigment (CI 12490);

[0225] - Cosmenyl Violet RL: Violet 23 pigment (CI 51319);

[0226] - Cosmenyl Blue A2R: Blue 15.1 pigment (CI 74160);

[0227] - Cosmenyl Green GG: Green 7 pigment (CI 74260);

[0228] - Cosmenyl Black R: Black 7 pigment (CI 77266).

[0229] 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.

[0230] 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.

[0231] The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

[0232] 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 42 090).

[0233] 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).

[0234] 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.

[0235] 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.

[0236] 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-TiCh-lake), Prestige sold by Eckart (mica-TiCE), Prestige Bronze sold by Eckart (mica-Fe2O3) and Colorona sold by Merck (mica-TiO2-Fe2O3).

[0237] 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 CL4509 (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.

[0238] Still as examples of nacres, mention may also be made of particles including a borosilicate substrate coated with titanium oxide.

[0239] Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.

[0240] 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.

[0241] Preferably, the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments.

[0242] 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.

[0243] 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.

[0244] Direct dye

[0245] Composition C used in the context of the process according to the invention may comprise one or more direct dyes.

[0246] 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.

[0247] 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.

[0248] 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.

[0249] 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.

[0250] 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.

[0251] As examples of nitro dyes, mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XXIF), mention may be made of: Acid Yellow 1, the sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid, 2-piperidino-5- nitrobenzenesulfonic acid, 2-(4’-N, N-(2” -hydroxy ethyl)amino-2’- nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7. 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.

[0252] 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.

[0253] As examples of indole dyes, mention may be made of: Acid Blue 74.

[0254] As examples of quinoline dyes, mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0255] 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.

[0256] 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.

[0257] 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.

[0258] 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.

[0259] Associative polymers

[0260] 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.

[0261] As recalled above, “associative polymers” are polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

[0262] 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.

[0263] 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.

[0264] 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.

[0265] The associative polymers may be of nonionic, anionic, cationic or amphoteric nature. Preferably, the associative polymer(s) are chosen from anionic associative polymers.

[0266] 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.

[0267] Preferentially, these compounds also comprise, as monomer, an ester of an a,P-monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.

[0268] 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.

[0269] 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.

[0270] 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.

[0271] Organic solvents

[0272] Composition C used in the context of the process according to the invention may comprise one or more organic solvents.

[0273] Examples of organic solvents that may be mentioned include C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, for instance 2- butoxy ethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols, notably aromatic monoalcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0274] The organic solvents may be present in a total content of between 10% and 80% by weight, preferably between 25% and 70% by weight and more preferentially between 35% and 65% by weight relative to the total weight of composition C.

[0275] Composition C used in the context of the process according to the invention may be aqueous. The water content may range from 1% to 90% by weight, preferably from 10% to 80% by weight and more preferentially from 20% to 70% by weight relative to the total weight of composition C.

[0276] Additives

[0277] Composition C used in the context of the process according to the invention may contain any adjuvant or additive usually used.

[0278] Among the additives that may be contained in the composition, mention may be made of reducing agents, softeners, antifoams, moisturizers, clays, mineral fillers, UV-screening agents, peptizers, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers described previously, preserving agents, amino and / or non-amino silicones, oils, waxes other than silicones in wax form, and mixtures thereof.

[0279] 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.

[0280] Those skilled in the art may select the appropriate presentation form, and also the method for preparing it, on the basis of their 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.

[0281] The above additives may generally be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of composition C. Application of composition D

[0282] 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 acidifying agent.

[0283] Preferably, the acidifying agent is chosen from citric acid, lactic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid and mixtures thereof.

[0284] Advantageously, composition D has a pH ranging from 1 to 6, preferably from 1.5 to 5, more preferentially from 2 to 4.

[0285] According to a preferred embodiment, composition D is applied to the hair keratin fibres after applying composition C to the hair keratin fibres.

[0286] According to yet another preferred embodiment, composition D is applied to the hair keratin fibres before applying composition C to the hair keratin fibres.

[0287] According to a particularly preferred embodiment, composition D is applied to the hair keratin fibres after applying composition C to the hair keratin fibres.

[0288] Process

[0289] The application to the hair keratin fibres of the composition T comprising at least hydrogen peroxide as defined previously can be carried out on dry or wet hair keratin fibres, and also on all types of hair keratin fibres, whether fair or dark, natural or dyed, permanent-waved, bleached or relaxed.

[0290] According to a particular embodiment of the invention, the hair keratin fibres are rinsed with water or washed after treatment with a composition T comprising at least hydrogen peroxide as defined previously.

[0291] Preferably, a washing or rinsing, wringing or drying step is performed after treatment with a composition T comprising at least hydrogen peroxide as defined previously.

[0292] More preferentially, a drying step is performed after treatment with said composition T.

[0293] The treatment with said composition T can be carried out between 15°C and 40°C.

[0294] After applying composition T comprising at least hydrogen peroxide as defined previously, a waiting time of between 1 minute and 12 hours, in particular between 1 minute and 10 hours, more particularly between 1 minute and 7 hours, more preferentially between 1 minute and 6 hours, may be observed before applying composition C to the hair keratin fibres. Preferably, the time between rinsing the composition T and applying the composition C is between 1 minute and 5 hours.

[0295] 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.

[0296] According to a preferred embodiment of the invention, the hair keratin fibres are rinsed after applying composition T and before applying composition C and composition D.

[0297] Preferably, a rinsing, wringing and / or drying step is performed after applying composition C and before applying the optional composition D to the hair keratin fibres.

[0298] 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.

[0299] 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.

[0300] The application of composition C and of the optional composition D to the hair keratin fibres is generally performed at room temperature (between 15°C and 25°C).

[0301] 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.

[0302] 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.

[0303] 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.

[0304] The process according to the invention may thus comprise a step of applying heat to the keratin fibres using a heating tool.

[0305] 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, etc. Preferably, the heat application step of the process of the invention is performed using a hairdryer.

[0306] 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.

[0307] 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.

[0308] When the step of applying heat to the hair keratin fibres is performed using a hood or a hairdryer, the temperature is preferably between 30°C and 110°C, preferentially between 50°C and 90°C.

[0309] Preferably, if the hair keratin fibres are dried, they are dried, in addition to a supply of heat, with a flow of air. This flow of air during drying makes it possible to improve the strand separation of the coating.

[0310] Preferably, the invention is a process for dyeing hair keratin fibres comprising the following steps:

[0311] (i) applying to the hair keratin fibres at least one composition T comprising at least hydrogen peroxide as defined previously; and then

[0312] (ii) a step of washing, rinsing or wringing said hair keratin fibres; and then

[0313] (iii) applying to the hair keratin fibres at least one composition C comprising:

[0314] - at least one (poly)carbodiimide compound as described previously;

[0315] - at least one polymer comprising at least one reactive group chosen from carboxylic acids; and

[0316] - at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; and then

[0317] (iv) optionally a step of washing, rinsing, wringing or drying the hair keratin fibres;

[0318] (v) optionally applying to the hair keratin fibres at least one composition D comprising at least one acidifying agent as described previously; and then

[0319] (vi) optionally a leave-on time of said composition D on the hair keratin fibres of from 1 minute to 30 minutes, preferably from 1 to 20 minutes; and then

[0320] (vii) optionally a step of washing, rinsing, wringing and / or drying the hair keratin fibres.

[0321] Preferably, composition C also comprises at least one associative polymer as described above, different from the polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously. Advantageously, in the dyeing process according to the invention, step b) consists in extemporaneously mixing, at the time of use, at least two compositions A and B to obtain a composition C for dyeing hair keratin fibres and in applying composition C to the hair keratin fibres, with:

[0322] - composition A comprising at least one (poly)carbodiimide compound as defined previously;

[0323] - 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.

[0324] More preferentially, in the dyeing process according to the invention, step b) consists in extemporaneously mixing, at the time of use, at least two compositions A and B to obtain a composition C for dyeing hair keratin fibres and in applying the composition C for dyeing hair keratin fibres to the hair keratin fibres, with:

[0325] - composition A comprising at least one (poly)carbodiimide compound as defined previously;

[0326] - composition B comprising at least one colouring agent as defined previously, and at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously.

[0327] According to a preferred embodiment, the dyeing process according to the invention is a process for dyeing hair keratin fibres comprising:

[0328] (i) applying to the hair keratin fibres at least one composition T comprising at least hydrogen peroxide as defined previously, and then

[0329] (ii) a step of washing, rinsing, wringing and / or drying the hair keratin fibres; and then

[0330] (iii) a step consisting 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, with:

[0331] - composition A comprising at least one (poly)carbodiimide compound as defined previously;

[0332] - composition B comprising at least one colouring agent as defined previously and at least one polymer comprising at least one reactive group chosen from the carboxylic acids as defined previously; and then

[0333] (iv) optionally a step of washing, rinsing, wringing and / or drying said hair keratin fibres; and then (v) applying to the hair keratin fibres at least one composition D comprising at least one acidifying agent as described previously; and then

[0334] (vi) optionally a leave-on time of said composition D on the hair keratin fibres of from 1 minute to 30 minutes, preferably from 1 to 20 minutes; and then

[0335] (vii) optionally a step of washing, rinsing, wringing and / or drying the hair keratin fibres.

[0336] Preferably, the polymer comprising at least one reactive group chosen from carboxylic acids is chosen from acrylic polymers.

[0337] Preferably, composition A does not comprise any colouring agent as defined previously.

[0338] 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.

[0339] 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.

[0340] 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.

[0341] 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.

[0342] 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. Multi-compartment device (kit)

[0343] The present invention also relates to a device for dyeing the hair keratin fibres, comprising several compartments containing:

[0344] * in a first compartment, a composition T comprising at least hydrogen peroxide as defined previously,

[0345] * in a second compartment, a composition A comprising at least one (poly)carbodiimide compound as defined previously;

[0346] * 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;

[0347] * optionally, in a fourth compartment, a composition D comprising at least one acidifying agent as defined previously.

[0348] 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.

[0349] EXAMPLES

[0350] 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.

[0351] More particularly, the process for preparing the (poly)carbodiimides of the invention involves, in a first step, a diisocyanate reagent (1):

[0352] O=C=N-Li-N=C=O (1), in which formula (1) Li is as defined previously, which reacts in the presence of a carboimidation catalyst (2) such as those described in US 4 284 730, notably phosphorus-based catalysts particularly chosen from phospholene oxides and phospholene sulfoxides, diaza- and oxaza-phospholanes, preferably under an inert atmosphere (nitrogen or argon), and in particular in a polar solvent which is preferably aprotic such as THF, glyme, diglyme, 1,4-di oxane or DMF, at a temperature between room temperature and the reflux temperature of the solvent, preferably at about 140°C; to give the carbodiimide diisocyanate compound (3):

[0353] 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.

[0354] 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:

[0355] [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.

[0356] 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):

[0357] 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.

[0358] 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.

[0359] During a third step, compound (5) reacts with 1 eq. of compound (6)

[0360] R2-X2-C(O)-NH-LI-(N=C=N-LI)Z-N=C=O (6), said compound (6) is prepared beforehand from compound (3’):

[0361] 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, X2and z as defined previously, to give the dissymmetrical compound (7):

[0362] 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. 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):

[0363] 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.

[0364] This last compound (8) can then react with 1 eq. of compound (4’):

[0365] Ri-Xi-C(O)-NH-Li-(N=C=N-Li)n-N=C=O (4’), (said compound (4’) being able to be synthesized by reaction of 0.5 eq. of nucleophilic reagent R1-X1-H with 1 equivalent of compound (3)), to give the (poly)carbodiimide (9) of the invention:

[0366] 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.

[0367] 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.

[0368] Example 1: Process for synthesizing the (poly)carbodiimide compound

[0369] 50 g of 4,4’ -di cyclohexylmethane 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.

[0370] 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.

[0371] 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.

[0372] 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. Example 2

[0373] Compositions T1 and T2 as described in Tables 1 and 2 below were prepared: the amounts are expressed as g of raw material as obtained / 100 g, unless otherwise mentioned. Thus, the amounts may be expressed in g of active material (a.m.) / 100 g.

[0374] [Table 1]

[0375] (1) non-ionic surfactants: ceteareth-25 and trideceth-2-carboxamide MEA for composition Tl; steareth-20 for composition T2.

[0376] (2) Cetearyl alcohol.

[0377] Compositions A and B as described in Tables 2 and 3 below were also prepared: the amounts are expressed as g of raw material as obtained / 100 g, unless otherwise mentioned. [Table 2]

[0378] (3) synthesized according to the synthetic process described in Example 1 (containing 40% active material in water). [Table 3]

[0379] (4) sold by the company Daito Kasei Kogyo under the trade name Daitosol 3000SLPN- PE1 (aqueous dispersion containing 30% active material);

[0380] (5) sold by the company Dow Corning under the trade name Dow Coming HMW 2220 Non-ionic Emulsion (divinyl dimethicone / dimethicone block copolymer as an aqueous emulsion) (containing 60% active material);

[0381] (6) sold by the company Rohm & Haas under the trade name Aculyn 22® (methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer containing 30% active material).

[0382] Composition A was then mixed with composition B in a 50 / 50 mass ratio to obtain a composition C according to the invention.

[0383] Next, composition D as described in Table 4 below was prepared: the amounts are expressed as g of raw material as obtained / 100 g.

[0384] [Table 4]

[0385] Protocols

[0386] Three application processes were used.

[0387] According to the first and second processes, the compositions Tl, for the first process, or T2, for the second process, were first applied with a wooden spatula over the entire length of locks of natural dry hair keratin fibres containing 90% grey hairs, in a proportion of 5 g of composition per gram of lock. The locks of hair keratin fibres were then left in the open air for between 10 and 20 minutes. The locks of hair keratin fibres were then rinsed with water, before being dried with a hairdryer.

[0388] Composition C was then applied to the locks previously treated with composition Tl or composition T2, in a proportion of 0.8 g of composition per gram of lock. The locks of hair keratin fibres were then disentangled and dried with a hairdryer.

[0389] Next, composition D was applied to the locks of hair keratin fibres previously treated with composition Tl or composition T2, and composition C, in a proportion of 0.5 g of composition per gram of lock. The locks of hair keratin fibres were then disentangled and dried with a hairdryer.

[0390] The first and second processes are therefore processes according to the invention. In the text hereinbelow, they are referred to as processes Pl and P2, respectively.

[0391] According to the third process, no application of composition Tl or composition T2 was performed. Only compositions C and D were applied to locks of natural dry hair keratin fibres containing 90% grey hairs. In particular, composition C was applied in a proportion of 0.8 g of composition per gram of lock. The locks of hair keratin fibres were then disentangled and dried with a hairdryer. Next, composition D was applied to the locks of hair keratin fibres previously treated with composition C, in a proportion of 0.5 g of composition per gram of lock. The locks of hair keratin fibres were then disentangled and dried with a hairdryer.

[0392] This process is thus a comparative process, referred to hereinbelow as process P3.

[0393] The processes applied are summarized in Table 5 below: [Table 5]

[0394] The various locks of hair keratin fibres treated via processes Pl to P3 were then subjected to a test consisting of several repeated shampoo washes in order to evaluate the resistance (persistence) of the colouring obtained with respect to shampoo washing, according to the shampoo washing protocol described below.

[0395] Shampoo washing protocol:

[0396] 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.

[0397] A standard shampoo (Garnier Ultra Doux) is applied uniformly to the dyed locks, in a proportion of 0.4 g of standard shampoo per gram of locks, the locks of hair keratin fibres being massaged gently along their length (6 passes) for 15 seconds, from the root to the end.

[0398] The locks of hair keratin fibres are then placed on a watch glass and left to stand for 1 minute.

[0399] 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.

[0400] Once the tests of several shampoo washes have been performed, the locks of hair keratin fibres are combed and dried with a hairdryer.

[0401] Results

[0402] The persistence of the colour of the locks was evaluated in the CIE L*a*b* system, using a Konica Minolta CM3600A spectrophotometer (illuminant D65, angle 10°, specular component included).

[0403] 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.

[0404] The persistence of the colouring is evaluated by the colour difference AE between the measurements taken on the dyed locks before shampoo washing, then after having undergone five shampoo washes according to the protocol described above. The lower the AE value, the more persistent the colour with respect to shampoo washing.

[0405] The AE value is calculated according to the following equation:

[0406] In this equation, L*, a* and b* represent the values measured after dyeing the hair keratin fibres and after performing shampoo washes, and Lo*, ao* and bo* represent the values measured after dyeing the hair keratin fibres but before shampoo washing.

[0407] The results are summarized in Table 6 below.

[0408] [Table 6]

[0409] The locks of hair keratin fibres treated by means of the processes Pl and P2 according to the invention and washed with five shampoo washes have lower AE values than those of the locks of hair keratin fibres treated by means of the comparative process P3.

[0410] Thus, the coloured coating that is obtained by means of the process according to the invention shows improved persistence with respect to shampoo washing.

Claims

CLAIMS1. Process for dyeing hair keratin fibres comprising: a) applying to the hair keratin fibres at least one composition T comprising at least hydrogen peroxide; and then b) applying to the hair keratin fibres at least one composition C comprising:- at least one (poly)carbodiimide compound;- at least one polymer comprising at least one reactive group chosen from carboxylic acids; and- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

2. Process according to Claim 1, characterized in that the total amount of hydrogen peroxide ranges from 0.01% to 25% by weight, preferably from 0.1% to 20% by weight, more preferentially from 0.5% to 15% by weight, even more preferentially from 1% to 12% by weight, better still from 2% to 10% by weight, even better still from 3% to 9% by weight relative to the total weight of composition T.

3. Process according to Claim 1 or 2, characterized in that the (poly)carbodiimide compound(s) is (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, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups, and a hydrocarbon-based radical, preferably alkyl, optionallyinterrupted with one or more heteroatoms and with one or more groups chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxy alkyl silyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups;- n denotes an integer ranging from 1 to 1000; and- A is a monomer chosen from the compounds below:

4. Process according to Claim 1 or 2, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) 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 hydrocarbon-based radical optionally interrupted with one or more heteroatoms;- n and z denote an integer ranging from 1 to 20, with n+z > 2 and w denotes an integer ranging from 1 to 3;- Li independently represents a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof;- E independently represents a group chosen from:-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;- Re independently represents a hydrogen atom or a hydrocarbon-based radical, optionally interrupted with one or more heteroatoms.

5. Process according to Claim 4, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) in which:- Xi and X2 independently represent an oxygen atom;- Ri and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, and mixtures thereof;- n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;- LI is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof;- E independently represents a group chosen from:-O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;- when R5 is not a covalent bond, R5 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof; and- Re is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

6. Process according to Claim 4 or 5, 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)-RS-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;- when Rs is not a covalent bond, Rs is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof; and- Re is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

7. Process according to any one of Claims 4 to 6, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) in which:- Xi and X2 independently represent an oxygen atom;- Ri and R2 independently represent the compound of formula (VI) below: Ri3-[O-CH2-C(H)(Ri4)]q- (VI), in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;- n and z denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10 and w is equal to 1;- Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4, 4-di cyclohexylenemethane; and- E represents a group -O-R3-O- in which R3 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

8. Process according to any one of Claims 4 to 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 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.

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

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

11. 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.

12. 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.

13. 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, preferably from 0.5% to 30% by weight, more preferentially from 1% to 20% by weight, and even more preferentially from 3% to 15% by weight relative to the total weight of composition C.

14. 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.

15. Process according to any one of the preceding claims, characterized in that it also comprises c) 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.

16. Process according to any one of the preceding claims, characterized in that step b) consists in extemporaneously mixing, at the time of use, at least two compositions A and B to obtain a composition C and in applying composition C to the hair keratin fibres, with:- composition A comprising at least one (poly)carbodiimide compound as defined in any one of Claims 1 and 3 to 9;- 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 11 to 12, 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.

17. Device for dyeing the hair keratin fibres, comprising several compartments containing:* in a first compartment, a composition T comprising at least hydrogen peroxide as defined in Claim 1 or 2, * in a second compartment, a composition A comprising:(1) at least one (poly)carbodiimide compound as defined in any one of Claims 1 and 3 to 9,* 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 11 to 12, 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 15.

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