A method for dyeing keratinous hair fibers comprising applying a composition comprising a (poly)carbodiimide compound, applying heat, and applying a composition comprising a (poly)carbodiimide compound.

Abstract

The present invention relates to a method for dyeing keratinous hair fibers, comprising: a) applying to said keratinous hair fibers at least one composition C comprising: at least one (poly)carbodiimide compound; at least one compound comprising at least one carboxylic acid functional group; and at least one colorant selected from pigments, direct dyes and mixtures thereof; then b) applying heat to said keratinous hair fibers at a temperature of at least 30°C; and then c) applying to said keratinous hair fibers at least one composition G comprising: at least one (poly)carbodiimide compound; at least one compound comprising at least one carboxylic acid functional group.

Description

[Technical Field]

[0001] The present invention relates to a method for dyeing keratin hair fibers, which comprises applying to the keratin hair fibers a composition C comprising a (poly)carbodiimide compound, a compound having at least one carboxylic acid functional group, and a colorant, followed by applying heat at a temperature of 30°C or higher, and then applying to the keratin hair fibers a composition G comprising a (poly)carbodiimide compound and a compound having at least one carboxylic acid functional group. [Background technology]

[0002] In the field of coloring keratinous hair fibers, it is already known to color keratinous hair fibers through various techniques using direct dyes or pigments for non-permanent coloring, or dye precursors for permanent coloring.

[0003] There are three basic processes for dyeing keratin hair fibers: a) "Permanent" dyeing: its action allows to significantly modify the original color and uses oxidative dyes that penetrate the keratin hair fiber and generate pigments through an oxidative condensation process; b) Non-permanent, semi-permanent or direct dyes: do not use the oxidative condensation process and can withstand 4-5 shampoo washes. This involves coloring keratin fibers with a coloring composition containing a direct dye; c) Temporary color: corrects the natural color of the keratin hair fiber, remains from one shampoo wash to the next, and serves to enhance or correct the shade already obtained. This may be associated with the "make-up" process.

[0004] Another dyeing method consists in using pigments. Specifically, the application of pigments to the surface of keratin fibers generally makes it possible to achieve visible coloring on dark keratin hair fibers, since the surface pigments mask the original color of the fibers. However, the colorings obtained by this dyeing method have the drawback of being less resistant to shampooing, as well as to external agents such as sebum, sweat, brushing and / or friction.

[0005] Therefore, there remains a need for a process for dyeing keratin hair fibers that has the advantage of obtaining a uniform colored coating on the keratin hair fibers without reducing the cosmetic properties of the keratin hair fibers, while at the same time forming a coating that is durable against the various stresses that the keratin hair fibers may be subjected to, such as shampooing and brushing and / or rubbing. Summary of the Invention [Problem to be solved by the invention]

[0006] The object of the present invention is therefore to develop a method for dyeing keratin hair fibers, which has the advantage of obtaining a smooth and uniform colored coating on the keratin hair fibers, while at the same time forming a coating that lasts against the various stresses to which the keratin hair fibers can be subjected, such as shampooing and brushing and / or rubbing, without degrading the keratin hair fibers. [Means for solving the problem]

[0007] One subject of the present invention is therefore a method for dyeing keratinous hair fibres, comprising: a) at least one (poly)carbodiimide compound, - at least one compound containing at least one carboxylic acid functional group; and - applying at least one composition C to the keratinous hair fibres, comprising at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; then b) subjecting the keratin hair fiber to heat at a temperature of 30°C or higher; then c) at least one (poly)carbodiimide compound, - applying at least one composition G to the keratinous hair fibres, comprising at least one compound containing at least one carboxylic acid functional group; and d) optionally subjecting the keratin hair fibers to heat at a temperature of 30°C or higher The method includes:

[0008] The method for dyeing keratin hair fibers according to the present invention allows obtaining a colored coating on the keratin hair fiber, which makes it possible to obtain a colorant that is visible on all keratin hair fiber types, is durable when washed with shampoo, and at the same time maintains the physical quality of the keratin hair fiber. Such a coating can withstand external stresses that keratin hair fibers may be subjected to, such as blow-drying and sweating. This makes it possible to obtain a particularly uniform deposit. DETAILED DESCRIPTION OF THE INVENTION

[0009] For purposes of the present invention, the term "colorant that lasts with respect to shampoo washes" means that the color obtained lasts after one shampoo wash, preferably after five shampoo washes.

[0010] The term "at least one" means one or more.

[0011] Unless otherwise specified, the boundaries of a range of values ​​are encompassed within that range, particularly expressions such as "between" and "ranging from."

[0012] The invention is not limited to the illustrated embodiments, and features of the various embodiments may in particular be combined in variations not illustrated.

[0013] For purposes of this invention, unless otherwise specified: - "Alkyl" radical refers to a straight or branched chain saturated radical containing, for example, 1 to 20 carbon atoms; - an "aminoalkyl" radical refers to an alkyl radical as defined above, wherein said alkyl radical contains an NH2 radical; - a "hydroxyalkyl" radical refers to an alkyl radical as defined above, wherein said alkyl radical contains an OH group; - an "alkylene" radical denotes a linear or branched divalent saturated C2-C4 hydrocarbon-based group, such as methylene, ethylene, or propylene; - a "cycloalkyl" or "alicycloalkyl" radical refers to a cyclic monocyclic or polycyclic, preferably monocyclic, hydrocarbon-based group containing 1 to 3 rings, preferably 2 rings, and containing 3 to 24 carbon atoms, in particular 3 to 20 carbon atoms, more particularly 3 to 13 carbon atoms, even more particularly 3 to 12 carbon atoms, preferably 5 to 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 by one or more (C1-C4)alkyl groups, such as methyl, in which case the cycloalkyl radical is preferably an isobornyl group; - "Cycloalkylene" group refers to a group having the above-defined "cycloalkyl", preferably C3-C 12 refers to a divalent cycloalkyl group; - "aryl" radical is a monocyclic, bicyclic or tricyclic, fused or unfused, unsaturated aromatic hydrocarbon-based ring radical containing 6 to 14 carbon atoms, preferably 6 to 12 carbon atoms, preferably an aryl group containing one ring having 6 carbon atoms, such as phenyl, naphthyl, phenanthryl, it being understood that the phenyl may be substituted with one or more (C1-C4) alkyl groups, such as methyl, preferably tolyl, xylyl or methylnaphthyl, preferably the aryl group represents phenyl, - an "arylene" radical is a divalent aryl radical with "aryl" as defined above, preferably arylene denotes phenylene; - "heterocyclic" group is a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based group containing one or more heteroatoms, preferably 1 to 5 atoms selected from O, S or N, and containing 3 to 20 ring members, preferably 5 to 10 ring members, such as, for example, imidazolyl, pyrrolyl, and furanyl; - a "heterocycloalkylene" radical is a divalent heterocyclic group with "heterocycle" defined above; - "aryloxy" radical refers to an aryloxy radical with "aryl" as defined above; - an "alkoxy" radical refers to an alkyl-oxy radical with "alkyl" as defined above; - an "acyloxy" group refers to an ester group RC(O)-O-, where R is an alkyl group as defined above; - A "reactive" group is a group that is capable of forming a covalent bond with another identical or different group by chemical reaction.

[0014] Unless otherwise specified, when a compound is referred to in this application, this also includes its optical isomers, its geometric isomers, its tautomers, or its salts, either alone or in mixtures.

[0015] The term "hair keratin fibers" means keratin hair fibers or hair. In other words, the expressions "hair keratin fibers", "keratin hair fibers" and "hair" are equivalent in the rest of the description.

[0016] For the purposes of the present invention, the term "keratinous hair fibers" means keratinous hair fibers of the head. This term does not correspond to body hair, eyebrows or eyelashes.

[0017] Polycarbodiimide Compounds The composition C according to the invention used in the context of the method of the invention comprises at least one (poly)carbodiimide compound.

[0018] The composition may comprise at least two different (poly)carbodiimide compounds present as a mixture in the composition.

[0019] 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 does not exceed 150, more preferentially does not exceed 100.

[0020] The term "carbodiimide group" refers to a divalent, linear, three-atom moiety of the general formula -(N=C=N)-.

[0021] The (poly)carbodiimide compound according to the present invention may optionally comprise in its structure one or more reactive groups different from the carbodiimide group selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, such as propylepoxide or butylepoxide, and azacyclopropane groups.

[0022] The reactive group other than the carbodiimide group may be a side group or a terminal group. Preferably, the (poly)carbodiimide compound comprises one or more terminal groups, preferably one or more terminal groups, different from the carbodiimide group, selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, such as propylepoxide or butylepoxide, and azacyclopropane group.

[0023] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (I): [ka] (In the formula, X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; R1 and R2 independently represent hydrocarbon-based groups optionally interrupted by one or more heteroatoms, preferably groups selected from alkyl, alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxides, such as propylepoxide or butylepoxide, and azacyclopropane groups, and represents a hydrocarbon-based group, preferably a group selected from alkyl, optionally interrupted by one or more heteroatoms and one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide, such as propyl epoxide or butyl epoxide, and azacyclopropane groups; - n represents an integer ranging from 1 to 1000; and A is one of the following compounds: [ka] (selected from The compound is selected from the group consisting of:

[0024] According to another embodiment, the (poly)carbodiimide compound has the following formula (I'): [ka] (In the formula, X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; Y1 and Y2 are independently saturated C1 to C 36 Aliphatic group or C6~C 24 represents a divalent organic group selected from an aromatic or alkylaromatic group, wherein the aliphatic or aromatic group optionally contains one or more non-pendant heteroatoms such as nitrogen atoms, oxygen atoms, sulfur atoms, or combinations thereof; Z1 and Z2 independently represent a reactive end group or an inactive end group; As inert end groups, Z1 and Z2 are independently saturated, linear or branched or cyclic C1-C 50 Aliphatic group, or C6~C 18 may represent an aromatic group, said aliphatic and aromatic groups optionally containing 1 to 10 heteroatoms selected from nitrogen, oxygen, sulfur and combinations thereof, and wherein the aliphatic or aromatic group may be partially or fully fluorinated; in this variation, Z1 and Z2 comprise a linking group CG connecting Z1 to Y1 and Z2 to Y2, wherein the group CG is optionally 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; as reactive end groups, Z1 and Z2 may be selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxides such as propylepoxide or butylepoxide and azacyclopropane groups; - Q represents an organic polymer or oligomer comprising repeating units of saturated, linear or branched or cyclic aliphatic groups, or aromatic or alkylaromatic groups, linked via carbonate, ester, ether, amide, urethane or urea repeating bonds or combinations thereof; - A represents a divalent aliphatic, aromatic, alkylaromatic or straight-chain, saturated, branched or cyclic group containing 2 to 30 carbon atoms, which may optionally contain one or more non-pendant heteroatoms in the aliphatic or aromatic chain, such as nitrogen atoms, oxygen atoms, sulfur atoms or combinations thereof; - r represents an integer equal to 0 or 1; m represents an integer ranging from 0 to 1000, preferably equal to 0 or 1, m' represents an integer ranging from 0 to 1000, preferably equal to 0 or 1, - n denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1, and m+(m'*n)≧2. The compound is selected from the group consisting of:

[0025] Preferably, Z1 and Z2 independently represent a reactive end group, and more preferentially, Z1 and Z2 may be independently selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, such as propylepoxide or butylepoxide, and azacyclopropane groups.

[0026] Such (poly)carbodiimide compounds are sold, for example, by Stahl BV under the names Permutex XR, RelcaLink 10, Picassian XL, and by Nisshinbo Chemicals 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.

[0027] Preferably, the (poly)carbodiimide compound is represented by the following formula (II): [ka] (In the formula, X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; - R1 and R2 independently represent a hydrocarbon-based group optionally interrupted by one or more heteroatoms; - n and z represent integers ranging from 1 to 20, where n+z≧2, and w represents an integer ranging from 1 to 3; L1 is independently a divalent C1 to C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 arylene groups and mixtures thereof; - E independently a group selected from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms. The compound is selected from the group consisting of:

[0028] The term "hydrocarbon-based group" means a saturated or unsaturated, straight-chain or branched group containing 1 to 300 carbon atoms, preferably 1 to 250 carbon atoms, more preferentially 1 to 200 carbon atoms. Preferably, the hydrocarbon-based radical is a saturated straight-chain radical.

[0029] The hydrocarbon-based group can contain one or more cyclic groups.

[0030] The hydrocarbon-based group may be interrupted by one or more heteroatoms selected in particular from O, S or N, and / or may be 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 may contain metal ions that can be incorporated in the form of salts.

[0031] The term "heteroatom" means an oxygen O, sulfur S or nitrogen N atom as well as a halogen atom such as Cl, F, Br and I. If a heteroatom is contained in the chain of a hydrocarbon-based radical, this heteroatom is preferably chosen from an oxygen O, sulfur S or nitrogen N atom.

[0032] Preferably, X1 and X2 independently represent an oxygen atom.

[0033] Preferably, R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, from which the hydroxyl groups have been removed, and mixtures thereof.

[0034] In a preferred embodiment, R1 and R2 are selected from the following groups (i) to (iv): (i) Formula (III): R7-OC(O)-C(R8)(H)- (III) (wherein R7 represents a C1-C3 alkyl group, and R8 represents a hydrogen atom or a C1-C3 alkyl group, preferably R7 is methyl, and R8 is a hydrogen atom or methyl). The compound (ii) Formula (IV): R9-[O-CH2-C(H)(R 10 )] p - (IV) (wherein R9 represents a C1-C4 alkyl group, R 10 represents a hydrogen atom or a C1-C4 alkyl group, p represents an integer ranging from 1 to 3, preferably R9 is methyl, ethyl or butyl, and R 10 is a hydrogen atom or methyl, and p is equal to 1. The compound (iii) Formula (V): (R 11 )2N-CH2-C(H)(R 12 )- (V) (In the formula, R 11 represents a C1-C4 alkyl group, and R 12 represents a hydrogen atom or a C1-C4 alkyl group; preferably, R 11 is methyl, ethyl or butyl, and R 12 is a hydrogen atom or methyl) The compound (iv) Formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) (In the formula, R 13 represents a C1-C4 alkyl group, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, q represents an integer ranging from 4 to 30, and preferably, R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl) Compounds of are independently selected from

[0035] Preferably, R1 and R2 independently represent a compound of formula (VI), R13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; and q represents an integer in the range of 4-30.

[0036] According to an alternative embodiment, R1 and R2 are different, and one of the R1 or R2 groups represents a compound of formula (IV) as described above, and the other of the R1 or R2 groups represents a compound of formula (VI) as described above.

[0037] Preferably, in formula (IV), R is methyl, ethyl or butyl, and R 10 is a hydrogen atom or methyl, and p is equal to 1.

[0038] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl, and q is an integer ranging from 4 to 30.

[0039] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), wherein R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; and q represents an integer in the range of 4-30.

[0040] Preferably, n represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0041] Preferably, z represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0042] Preferably, w is equal to one.

[0043] Preferably, w is equal to 1 and n+z represents an integer in the range 4-10.

[0044] Preferably, L1 is a divalent C1-C alkyl group such as methylene, ethylene, and propylene. 18 Aliphatic hydrocarbon radicals, C3-C such as cyclopentylene, cycloheptylene, and cyclohexylene 15 C3-C such as cycloalkylene radicals, imidazolene, pyrrolene, and furanylene 12 C6-C such as heterocycloalkylene group or phenylene 14 The arylene group is selected from arylene groups and mixtures thereof.

[0045] For example, L1 may be selected from radicals derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-1,3-dioctylcyclobutane, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-napthethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate and phenylene diisocyanate, and mixtures thereof.

[0046] Preferably, L1 is C3 to C 15 Cycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, such as those of the following formula (VII): [ka]

[0047] Preferably, L1 is represented by the following formula (VIII): [ka] The corresponding 4,4-dicyclohexylenemethane is

[0048] According to another embodiment, L1 is C6 to C14 When L1 is an arylene group, it is represented by the following formula (IX): [ka] It is not m-tetramethylxylylene, which is represented by

[0049] As mentioned earlier, E is independently - represents a group selected from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; and R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms.

[0050] Preferably, R3 and R4 are C6-C alkyl groups, such as phenylene, optionally interrupted by one or more heteroatoms. 14 C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 alkylene groups as well as mixtures thereof.

[0051] More preferentially, R3 and R4 are linear or branched C1-C6 alkylenes, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms. 18 alkylene groups.

[0052] Preferably, when R5 is not a covalent bond, R5 is a C6-C6 alkyl group, such as phenylene, optionally interrupted by one or more heteroatoms. 14 C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene18 The alkylene groups are selected from alkylene groups as well as mixtures thereof.

[0053] Preferably, R6 is a C6-C, such as phenylene, optionally interrupted by one or more heteroatoms. 14 C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 The alkylene groups are selected from alkylene groups as well as mixtures thereof.

[0054] Preferably, E represents a -O-R-O- group, where R is a C-C alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 The alkylene group is selected from alkylene groups and mixtures thereof.

[0055] More preferentially, E represents a -O-R3-O- group, where R3 is a linear or branched C1-C6 alkyl group, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms. 18 Represents an alkylene group.

[0056] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (X): [ka] (wherein R independently represents an alkyl group containing 1 to 24 carbon atoms, a cycloalkyl group containing 3 to 24 carbon atoms, or an aryl group containing 6 to 24 carbon atoms; and n represents an integer ranging from 2 to 100. It is a copolymer derived from α-methylstyryl isocyanate.

[0057] The term "alkyl group" in this embodiment is as defined above.

[0058] The term "cycloalkyl group" in this embodiment is as defined above.

[0059] In this embodiment, n may represent an integer ranging from 2 to 50, preferably from 3 to 30, and even more preferentially from 5 to 10.

[0060] According to another particular embodiment, the (poly)carbodiimide compound has the following formula (XI): [ka] (wherein R independently represents an alkyl group containing 1 to 24 carbon atoms, a cycloalkyl group containing 3 to 24 carbon atoms, or an aryl group containing 6 to 24 carbon atoms). is a compound of

[0061] The "alkyl group", "cycloalkyl group" and "aryl group" are as defined above.

[0062] According to a preferred embodiment, the (poly)carbodiimide compound is selected from compounds of formula (I) or formula (II), wherein: X1 and X2 independently represent an oxygen atom; R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed, and more preferentially R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30; - n and z, if present, represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - If L1 is present, it is a divalent C1-C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, preferably C3-C 15 cycloalkylene groups; - If A is present, it is a divalent C1-C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, preferably C3-C 15 cycloalkylene groups; - E, if present, is independently - O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently a C6-C alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; - R5 is not a covalent bond, and if R5 is present, it is a C6-C6 bond optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; and - When R6 is present, it is a C-C bond optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof) represents a group selected from

[0063] Preferably, the (poly)carbodiimide compound has the formula (II): (-X1 and X2 independently represent an oxygen atom; - R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, from which the hydroxyl groups have been removed, and mixtures thereof; - n and z represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L1 is divalent C1 to C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 arylene groups and mixtures thereof; - E independently - O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently a C6-C alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; When R5 is not a covalent bond, R5 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; and R6 is a C-C group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof) The compound is selected from the group consisting of:

[0064] More preferentially, the (poly)carbodiimide compound has formula (II) (Wherein, -X1 and -X2 independently represent an oxygen atom; - R1 and R2 are independently a monoalkyl ether of a (poly)alkylene glycol from which the hydroxyl group has been removed; - n and z represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L1 is C3~C 15 is a cycloalkylene group; - E independently - represents a group selected from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently a C-C alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; When R5 is not a covalent bond, R5 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; and R6 is a C-C group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof) The compound is selected from the group consisting of:

[0065] Even more preferentially, the (poly)carbodiimide compound has formula (II) (Wherein, -X1 and -X2 independently represent an oxygen atom; R1 and R2 are independently represented by the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI), where R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30; - n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10 and w is equal to 1; - L1 is a C3-C alkyl group such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane. 15 is a cycloalkylene radical, E is an —O—R—O— group, where R is a C-C alkyl group optionally interrupted by one or more heteroatoms; 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof).

[0066] Even more preferentially, the (poly)carbodiimide compound has formula (II) (Wherein, -X1 and -X2 independently represent an oxygen atom; R1 and R2 independently represent the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI), In the formula, R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30; - n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10 and w is equal to 1; L1 is a C3-C alkyl group such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane. 15a cycloalkylene group, preferably 4,4-dicyclohexylenemethane; E is a -O-R-O- group, where R is a linear or branched C-C alkyl group, such as methylene, propylene, butylene, or ethylene, optionally interrupted by one or more heteroatoms; 18 The compound is selected from the group consisting of the compounds of formula (1) and (2),

[0067] According to a preferred embodiment, the (poly)carbodiimide compound has the following formula (XII): [ka] wherein L1 is 4,4-dicyclohexylenemethane, n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10, and E is an -O-R3-O group, where R3 is a linear or branched C1-C alkyl group, such as methylene, propylene, butylene, or ethylene, optionally interrupted by one or more heteroatoms. 18 an alkylene group), and r and s represent integers ranging from 4 to 30. is a compound of

[0068] Advantageously, the total amount of (poly)carbodiimide compounds 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.

[0069] Compounds containing at least one carboxylic acid functional group Composition C used in the context of the method according to the invention comprises at least one compound containing at least one carboxylic acid function.

[0070] Preferably, the compound containing at least one carboxylic acid functional group is selected from silicone compounds, polyurethanes, acrylic polymers and mixtures thereof, which contain at least one carboxylic acid group.

[0071] Polyurethane and acrylic polymers According to a preferred embodiment, composition C comprises at least one compound containing at least one carboxylic acid functional group chosen from polyurethanes, acrylic polymers and mixtures thereof.

[0072] Preferably, the compound containing at least one carboxylic acid functional group is in the form of an aqueous dispersion of particles of a polymer selected from polyurethanes, acrylic polymers and mixtures thereof.

[0073] Preferably, composition C comprises at least one compound containing at least one carboxylic acid functional group in the form of an aqueous dispersion of particles of polyurethanes, acrylic polymers and mixtures thereof.

[0074] The dispersion may be a simple dispersion of the cosmetic composition in an aqueous medium. A particular example of a dispersion is a latex.

[0075] The aqueous dispersion of polymer particles may be selected from aqueous dispersions of polyurethane particles.

[0076] More particularly, the polyurethanes present in the aqueous dispersions used in the present invention are: - the following formula (A): [ka] (In the formula, R1 represents a divalent radical of a dihydroxylated compound, R2 represents the radical of an aliphatic or cycloaliphatic polyisocyanate, R3 represents a radical of a low molecular weight diol optionally substituted with one or more ionic groups, n represents an integer ranging from 1 to 5, and - m is greater than 1) and a prepolymer of; - the following formula (B): H2N-R4-NH2(B) wherein R4 represents an alkylene or alkylene oxide group that is not substituted with one or more ionic or potentially ionic groups. with at least one chain extender according to the formula: - the following formula (C): H2N-R5-NH2(C) wherein R5 represents an alkylene group substituted with one or more ionic or potentially ionic groups. and at least one chain extender according to It is obtained by the reaction:

[0077] Among the dihydroxylated compounds that can be used according to the present invention, mention may be made in particular of compounds containing two hydroxyl groups and having a number average molecular weight of about 700 to about 16,000, preferably about 750 to about 5,000. Examples of dihydroxylated compounds having high molecular weights include polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadiene, polyhydroxylated polythioethers, and mixtures thereof. Preferably, the hydroxylated compound is selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0078] The polyisocyanates that can be used according to the invention are chosen in particular from organic diisocyanates having a molecular weight of about 112 to 1000, preferably about 140 to 400.

[0079] Preferably, the polyisocyanate is selected from diisocyanates, more particularly from those represented by the general formula R2(NCO)2, where R2 represents a divalent aliphatic hydrocarbon group containing 4 to 18 carbon atoms, a divalent alicyclic hydrocarbon group containing 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group containing 7 to 15 carbon atoms, or a divalent aromatic hydrocarbon group containing 6 to 15 carbon atoms.

[0080] Preferably, R2 represents an organic diisocyanate. Examples of organic diisocyanates may be selected in particular from: tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isomethyl)cyclohexane. bis(4-isocyanatomethyl)cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)methane, isomers of toluene diisocyanate (TDI), such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, diphenylmethane 4,4'-diisocyanate and mixtures of its diphenylmethane 2,4-diisocyanate isomers, optionally with diphenylmethane 2,2'-diisocyanate, naphthalene 1,5-diisocyanate and mixtures thereof.

[0081] Preferably, the diisocyanates are aliphatic and cycloaliphatic diisocyanates, more preferentially chosen from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate and mixtures thereof.

[0082] The term "low molecular weight diols" according to the present invention refers to diols having a molecular weight of about 62 to 700, preferably 62 to 200. These diols may contain aliphatic, cycloaliphatic or aromatic groups. Preferably, they contain only aliphatic groups.

[0083] Preferably, R3 represents a low molecular weight diol containing more than 20 carbon atoms and is more preferentially selected from ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, neopentyl glycol, butylethylpropanediol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane) and mixtures thereof.

[0084] The low molecular weight diols may optionally contain ionic or potentially ionic groups. Examples of low molecular weight diols containing ionic or potentially ionic groups are described, inter alia, in patent US 3,412,054. Compounds of this type are preferably selected from dimethylol butanoic acid, dimethylol propionic acid, polycaprolactone diols containing carboxyl groups, and mixtures thereof.

[0085] When low molecular weight diols containing ionic or potentially ionic groups are used, they are preferably used in an amount such that less than 0.30 meq of COOH per gram of polyurethane is present in the polyurethane dispersion.

[0086] The prepolymers are extended by two families of chain extenders: The first group of chain extenders corresponds to compounds of general formula (B):

[0087] The chain extender of formula (B) is preferably an alkylenediamine, such as hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine; an alkylenediamine oxide, such as 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine (also known as dipropylamine diethylene glycol or DPA-DEG, available from Tomah Products, Milton, Wis.), 2-methyl-1,5-pentanediamine (Dytec A from DuPont), hexanediamine, isophoronediamine, 4,4-methylenedi(cyclohexylamine), Tomah and mixtures thereof.

[0088] The second group of chain extenders corresponds to compounds of general formula (C). Compounds of this type preferably have an ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Compounds of this type can optionally contain two groups that react with isocyanate groups and one group that is ionic or capable of forming an ionic group.

[0089] The ionic or potentially ionic groups may preferably be selected from tertiary or quaternary ammonium groups or groups that can be converted into such groups, carboxyl groups, carboxylate groups, sulfonic acid groups and sulfonate groups. The conversion of at least a portion of the groups that can be converted into salts of tertiary or quaternary ammonium groups can be carried out before or during mixing with water.

[0090] The chain extender of formula (C) is preferably selected from diaminosulfonates, such as the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid, and mixtures thereof.

[0091] The polyurethanes that can be used according to the invention can also optionally contain compounds (chain terminators) located at each chain end and terminating said chains. Compounds of this type are described, in particular, in US Pat. No. 7,445,770 and / or US Pat. No. 7,452,770.

[0092] Preferably, the viscosity of the aqueous dispersion of polyurethane particles is less than 2000 mPa.s at 23°C, more preferentially less than 1500 and better still less than 1000. Even more preferably, the glass transition temperature of the aqueous dispersion of polyurethane particles is less than 0°C.

[0093] Also preferably, the polyurethane (or active substance or solids) content of the aqueous polyurethane dispersion is from 20% to 60% by weight, more preferentially from 25% to 55% by weight, and even better from 30% to 50% by weight, based on the weight of the dispersion. This is intended to mean that the polyurethane content (dry matter) of the aqueous dispersion is preferably from 20% to 60% by weight, more preferentially from 25% to 55% by weight, and even better from 30% to 50% by weight, relative to the total weight of the dispersion.

[0094] Also preferably, the glass transition temperature (Tg) of the aqueous dispersion of polyurethane particles is less than or equal to -25°C, preferably less than -35°C and more preferentially less than -40°C.

[0095] The average diameter of the polyurethane particles can be up to about 1000 nm, for example, in the range of about 50 nm to about 800 nm, and better still, about 100 nm to about 500 nm. These particle sizes can be measured using a laser particle size distribution analyzer (e.g., Brookhaven BI90).

[0096] Non-limiting examples of aqueous polyurethane dispersions include those sold by Bayer under the Baycusan® name, such as Baycusan® C1000 (INCI name: Polyurethane-34), Baycusan® C1001 (INCI name: Polyurethane-34), Baycusan® C1003 (INCI name: Polyurethane-32), Baycusan® C1004 (INCI name: Polyurethane-35) and Baycusan® C1008 (INCI name: Polyurethane-48).

[0097] Mention may also be made of aqueous polyurethane dispersions of isophthalic acid / adipic acid copolymer / hexylene glycol / neopentyl glycol / dimethylol acid / isophorone diisocyanate (INCI name: Polyurethane-1, for example Luviset® PUR from BASF), polyurethanes of polycarbonate, polyurethanes of aliphatic polyesters and aliphatic polyurethanes (for example the Neorez® or DSM series, for example Neorez® R989 and Neorez® R-2202).

[0098] According to a preferred embodiment, the aqueous dispersion of polyurethane particles may be chosen from aqueous dispersions of particles of a compound having the INCI name Polyurethane-35 or of a compound having the INCI name Polyurethane-34.

[0099] Preferably, the compound containing at least one carboxylic acid function is in the form of an aqueous dispersion of particles of an acrylic polymer, more preferentially in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0100] For the purposes of the present invention, the term "polymer" refers to a compound corresponding to the repetition of one or more units (these units are derived from compounds known as monomers), where this or these units are repeated at least twice, preferably at least three times.

[0101] The term "film-forming polymer" refers to a polymer that is capable of forming a macroscopically continuous, preferably a coherent, film on a substrate, in particular keratin hair fibers, either alone or in the presence of an auxiliary film-forming agent.

[0102] For the purposes of the present invention, the term "acrylic polymer" means a polymer synthesized from at least one monomer selected from (meth)acrylic acid and / or (meth)acrylic acid esters and / or (meth)acrylic acid amides.

[0103] The units of the polymer derived from (meth)acrylic acid monomers may optionally be in the form of a salt, in particular an alkali metal salt, an alkaline earth metal salt or an ammonium salt, or an organic base salt.

[0104] The (meth)acrylic acid esters (also known as (meth)acrylates) are advantageously alkyl (meth)acrylates, in particular C1-C 30 , preferably C1 to C 20 , or better C1 to C 10 Alkyl (meth)acrylates, aryl (meth)acrylates, especially C6-C 10 It is selected from aryl (meth)acrylates and hydroxyalkyl (meth)acrylates, in particular C2 to C6 hydroxyalkyl (meth)acrylates.

[0105] Among the alkyl (meth)acrylates, mention may be made of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and cyclohexyl (meth)acrylate.

[0106] Among the hydroxyalkyl(meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0107] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0108] Particularly preferred (meth)acrylic acid esters are alkyl, preferably C1-C 30 , and more preferentially C1~C 20 , and even better C1 to C 10 More specifically, it is a C1 to C4 alkyl (meth)acrylate.

[0109] According to the present invention, the alkyl group of the ester may be fluorinated or even perfluorinated, ie some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

[0110] Examples of (meth)acrylic acid amides include (meth)acrylamides as well as N-alkyl(meth)acrylamides, particularly N-(C-C 12 Mention may also be made of N-alkyl(meth)acrylamides. Among the N-alkyl(meth)acrylamides, mention may be made of N-ethylacrylamide, Nt-butylacrylamide, Nt-octylacrylamide and N-undecylacrylamide.

[0111] 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 a (meth)acrylic acid ester.

[0112] Preferably, the acrylic polymer according to the present invention comprises the following monomers: a) (meth)acrylic acid; and b) C1~C 30 , and more preferentially C1~C 20 , or better C1 to C 10 More particularly, it contains one or more units derived from a C1 to C4 alkyl (meth)acrylate.

[0113] Preferably, the aqueous dispersion of acrylic polymer particles is surfactant-free.

[0114] The term "surfactant" refers to any agent that can modify the surface tension between two surfaces.

[0115] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and ethyl acrylate, such as the compound sold by BASF under the trade name Luvimer MAE, or the compound sold by Lubrizol under the trade name Fixate Superhold Polymer, such as polyacrylate-2 crosspolymer, or the compound sold by Daito Chemical Industry Co., Ltd. under the trade name Daitosol 3000VP3, or the compound sold by Daito Chemical Industry Co., Ltd. under the trade name Daitosol 3000 SLPN-PE1, such as acrylate copolymer.

[0116] The acrylic polymer may optionally contain one or more additional monomers other than (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide monomers.

[0117] Additional monomers may include, for example, styrene monomers, particularly styrene and alpha-methylstyrene, preferably styrene.

[0118] In particular, the acrylic polymer is a styrene / (meth)acrylate copolymer, in particular a copolymer of at least one styrene monomer and at least one C1-C6 (meth)acrylate copolymer. 20 , preferably C1 to C 10 The polymer may be a copolymer selected from copolymers obtained by polymerizing alkyl (meth)acrylate monomers.

[0119] C1~C 10 The alkyl (meth)acrylate monomer may be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate.

[0120] Acrylic polymers include styrene / (meth)acrylate copolymers sold under the name Joncryl 77 by BASF, Yodosol GH41F by Akzo Nobel and Syntran 5760 CG by Interpolymer.

[0121] Preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles.

[0122] More preferentially, composition C comprises the following monomers: a) (meth)acrylic acid; and b) C1~C 30 , and more preferentially C1~C 20 , or better C1 to C 10 , more particularly at least one aqueous dispersion of acrylic polymer particles comprising one or more units derived from C1-C4 alkyl (meth)acrylates. Includes.

[0123] Preferably, the acrylic polymer (or active substance or solids) content of the aqueous dispersion of acrylic polymer particles is between 20% and 60% by weight, more preferentially between 22% and 55% by weight, and even better still between 25% and 50% by weight, based on the weight of the dispersion.

[0124] Silicone Acrylic Copolymer According to a particular embodiment, the silicone compound comprising at least one carboxylic acid group is chosen from silicone acrylic copolymers.

[0125] Thus, according to a particular embodiment, the compound containing at least one carboxylic acid functional group is chosen from silicone acrylic copolymers.

[0126] Preferably, the silicone acrylic copolymer comprises: - at least one acrylic, methacrylic or crotonic unit; and - comprising at least one polydimethylsiloxane (PDMS).

[0127] For the purposes of the present invention, the term "polydimethylsiloxane" (also abbreviated as PDMS) denotes, according to generally accepted practice, any organosilicon polymer or oligomer of linear structure of variable molecular weight, obtained by polymerization and / or polycondensation of appropriately functionalized silanes, and consisting essentially of repeating main units in which silicon atoms are bonded to one another through oxygen atoms (siloxane bonds Si-O-Si), containing methyl radicals directly bonded to said silicon atoms through carbon atoms.

[0128] The PDMS chains that can be used to obtain the copolymers used according to the invention preferably contain at least one polymerizable radical group located at at least one of the ends of the chain, i.e., the PDMS can have, for example, a polymerizable radical group at each of the two ends of the chain, or one polymerizable radical group at one end of the chain and one trimethylsilyl end group at the other end of the chain.

[0129] The term "polymerizable radical group" means a radical that can polymerize with other polymerizable radical groups or monomers. Preferably, the polydimethylsiloxane unit comprises at least one polymerizable radical group.

[0130] Preferably, the polymerizable radical group comprises at least one vinyl group.

[0131] Preferably, the polydimethylsiloxane (PDMS) unit comprises at least one polymerizable radical group comprising at least one vinyl group, preferably at least two polymerizable radical groups comprising at least one vinyl group, preferably located at at least one of the chain ends.

[0132] As previously mentioned, the silicone acrylic copolymer comprises at least one acrylic or methacrylic or crotonic unit, i.e., at least one unit containing a carboxylic acid group.

[0133] The term "carboxyl group" refers to COOH or COO - It means functional group, COO - The counterions of the groups can be selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0134] Preferably, the silicone acrylic copolymer is: - at least one acrylic, methacrylic or crotonic unit and at least one acrylic ester, methacrylic ester or vinyl ester unit; and - comprising at least one polydimethylsiloxane (PDMS).

[0135] More preferentially, the composition comprises: - at least one unit selected from at least one croton unit and an alkyl crotonate unit, wherein the alkyl radical is a linear or branched saturated radical containing from 1 to 20 carbon atoms; vinyl acetate units; vinyl alkyl ester units, wherein the alkyl radical is a linear or branched saturated radical containing from 2 to 20 carbon atoms; and mixtures thereof; and - one or more silicone acrylic copolymers, including at least one polydimethylsiloxane (PDMS) Includes.

[0136] The term "crotonic unit" means a unit derived from a crotonic acid monomer or a salt thereof.

[0137] The term "alkyl crotonate unit" means a unit derived from a crotonic acid ester monomer containing a saturated, linear or branched alkyl group containing from 1 to 20 carbon atoms.

[0138] The term "vinyl alkyl ester unit" means a unit derived from a vinyl ester monomer containing a saturated, linear or branched alkyl group containing from 2 to 20 carbon atoms.

[0139] The term "vinyl acetate units" means units derived from vinyl acetate monomer.

[0140] According to a preferred embodiment, the silicone acrylic copolymer comprises: - at least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a saturated, linear or branched radical containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms, and - preferably at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable radical group containing at least one vinyl group; Includes.

[0141] According to a particularly preferred embodiment, the silicone acrylic copolymer comprises - at least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, wherein the alkyl radical is a linear or branched saturated radical containing from 6 to 16 carbon atoms, and - at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable radical group containing at least one vinyl group; Includes.

[0142] More preferentially, the composition comprises: - at least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a saturated, linear or branched radical containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms, and - one or more silicone acrylic copolymers comprising at least one polydimethylsiloxane (PDMS) unit comprising at least one polymerizable radical group comprising at least one vinyl group; Includes.

[0143] Even more preferentially, the composition comprises: - at least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, wherein the alkyl radical is a saturated, linear or branched chain radical containing from 6 to 16 carbon atoms, and - one or more silicone acrylic polymers comprising at least one polydimethylsiloxane (PDMS) unit comprising at least one polymerizable radical group comprising at least one vinyl group; Includes.

[0144] Among the silicone acrylic copolymers that may be used in connection with the present invention, mention may be made of the compound sold by Wacker Chemie AG under the trade name Belsil® P1101, which has the INCI name Crotonic Acid / Vinyl C8-12 Isoalkyl Ester / VA / Bis-Vinyl Dimethicone Crosspolymer.

[0145] The total amount of compounds containing at least one carboxylic acid functional group is preferably in the range of 0.1% to 30% by weight, more preferentially 0.5% to 20% by weight, even more preferably 1% to 15% by weight, and even more preferentially 2% to 10% by weight, relative to the total weight of composition C.

[0146] The total amount of aqueous dispersion of particles of polymer chosen from polyurethanes, acrylic polymers and mixtures thereof preferably ranges from 0.1% to 40% by weight, more preferentially from 0.5% to 30% by weight, even more preferentially from 1% to 25% by weight, and even more preferentially from 2% to 20% by weight, relative to the total weight of composition C.

[0147] According to a particular embodiment, the total amount of the aqueous dispersion of acrylic polymer particles preferably ranges from 0.1% to 40% by weight, more preferentially from 0.5% to 30% by weight, even better from 1% to 25% by weight and even more preferentially from 2% to 20% by weight relative to the total weight of composition C.

[0148] Advantageously, the total amount of silicone acrylic copolymer ranges from 0.1% to 30% by weight, more preferably from 0.5% to 20% by weight, even more preferentially from 1% to 15% by weight, and even more preferentially from 2% to 10% by weight relative to the total weight of composition C.

[0149] coloring agent Composition C used in the context of the method of the present invention comprises one or more colorants chosen from pigments, direct dyes and mixtures thereof.

[0150] Preferably, composition C used in the context of the method according to the invention comprises one or more pigments.

[0151] The term "pigment" refers to any pigment that colors keratinous materials, the solubility of which in water at 25°C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, preferably less than 0.01% by weight.

[0152] Pigments that can be used are chosen in particular from organic and / or mineral pigments known in the art, in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and Ullmann's Encyclopedia of Industrial Chemistry.

[0153] These may be natural products of natural origin or non-natural products.

[0154] These pigments may be in the form of pigment powders or pastes. They may be coated or uncoated.

[0155] The pigments may be selected, for example, from mineral pigments, organic pigments, special effect pigments such as lakes, pearlescent agents or glitter flakes, and mixtures thereof.

[0156] The pigment may be a mineral pigment. The term "mineral pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann's encyclopedia. Among the mineral pigments useful in the present invention are iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium oxide.

[0157] The pigment may be an organic pigment. The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann's Encyclopaedia.

[0158] The organic pigments may be chosen in particular from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal complexes, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

[0159] In particular, white or colored organic pigments are carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments classified in the Color Index under the reference numbers CI 42090, 69800, 69825, 74100, 74160, yellow pigments classified in the Color Index under the reference numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, green pigments classified in the Color Index under the reference numbers CI 61565, 61570, 74260, orange pigments classified in the Color Index under the reference numbers CI 11725, 45370, 71105, red ... The pigments may be selected from the red pigments classified under the reference numbers 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, and from the pigments obtained by oxidative polymerization of indole or phenol derivatives described in French Patent No. 2 679 771.

[0160] Examples of pigment pastes with organic pigments include those sold by Hoechst under the following names: - Cosmenyl Yellow 10G:Yellow 3 pigment (CI 11710); - Cosmenyl Yellow G:Yellow 1 pigment (CI 11680); - Cosmenyl Orange GR: Orange 43 pigment (CI 71105); - Cosmenyl Red R: Red 4 pigment (CI 12085); - Cosmenyl Carmine FB: Red 5 pigment (CI 12490); - Cosmenyl Violet RL: Violet 23 pigment (CI 51319); - Cosmenyl Blue A2R; Blue 15.1 pigment (CI 74160); - Cosmenyl Green GG: Green 7 pigment (CI 74260); - Cosmenyl Black R: Black 7 pigment (CI 77266).

[0161] The pigments according to the invention may also be in the form of composite pigments, as described in EP 1 184 426. These composite pigments may in particular consist of particles comprising an inorganic core, at least one binder binding an organic pigment to the core, and at least one organic pigment covering at least a part of the core.

[0162] The organic pigment may be a lake, the term "lake" referring to a dye adsorbed onto insoluble particles so that the resulting composite remains insoluble during use.

[0163] The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

[0164] 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).

[0165] An example of a lake is the product known by the following name: D&C Red 7 (CI 15 850:1).

[0166] Pigments can also be special effect pigments. The term "special effect pigments" means pigments that generally produce a colored appearance (characterized by a particular hue, a particular saturation, and a particular level of brightness) that is non-uniform and changes depending on the conditions of observation (light, temperature, angle of observation, etc.), thereby differing from colored pigments that exhibit standard uniform opaque, translucent, or transparent shades.

[0167] There are several types of special effect pigments: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a high refractive index, such as pearlescent agents, interference pigments or glitter flakes.

[0168] Examples of special effect pigments that may be mentioned include pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxide, mica coated with iron oxide, mica coated with titanium, in particular with ferric blue or chromium oxide, mica coated with titanium and coated with the organic pigments defined above, and pearlescent pigments based on bismuth oxychloride. Pearlescent pigments include pearlescent agents such as Cellini (mica-TiO2-lake) sold by BASF, Prestige (mica-TiO2) sold by Eckart, Prestige Bronze (mica-Fe2O3) sold by Eckart, or Colorona (mica-TiO2-Fe2O3) sold by Merck.

[0169] Gold pearlescent agents, in particular those sold by BASF under the names Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); bronze pearlescent agents, in particular those sold by Merck under the names Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super Bronze (Cloisonne); orange pearlescent agents, in particular those sold by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion Orange (Colorona) and Matte Orange (17449) (Microna); brown pearlescent agents, in particular those sold by BASF under the names Nu-antique Copper copper-tinted pearlescent agents, in particular those sold by BASF under the name Copper 340A (Timica); red-tinted pearlescent agents, in particular those sold by Merck under the name Sienna Fine (17386) (Colorona); yellow-tinted pearlescent agents, in particular those sold by BASF under the name Yellow (4502) (Chromalite); gold-tinted red pearlescent agents, in particular those sold by BASF under the name Sunstone G012 (Gemtone); pink-tinted pearlescent agents, in particular those sold by BASF under the name Tan opale G005 (Gemtone); gold-tinted black pearlescent agents, in particular those sold by BASF under the name Nu antique Bronze 240 blue pearlescent agents, in particular those sold by Merck under the name Matte Blue (17433) (Microna); silvery white pearlescent agents, in particular those sold by Merck under the name Xirona Silver;Mention may also be made of gold-green to pink to orange-shifting pearlescent agents, in particular those sold under the name Indian Summer (Xirona) by Merck; and mixtures thereof.

[0170] Further examples of pearlescent agents include particles comprising a borosilicate substrate coated with titanium oxide.

[0171] Particles comprising a glass substrate coated with titanium oxide are sold in particular under the name Metashine MC1080RY by the company Toyal.

[0172] Finally, examples of pearlescent agents that may be mentioned include polyethylene terephthalate glitter flakes, in particular those sold under the name Silver 1P 0.004X0.004 (silver glitter flakes) by Meadowbrook Inventions, Inc. Multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate, and aluminum may also be envisaged.

[0173] The special effect pigments can also be chosen from reflective particles, i.e. particles that, due to their size, structure, in particular the thickness of the layer of which they are composed, as well as their physical and chemical properties and surface condition, are able to reflect incident light, where appropriate, this reflection can be strong enough to produce, when applied to the support to be made up, a bright spot visible to the naked eye on the surface of the composition or mixture, i.e. a brighter spot that appears to be noticeably brighter than its surroundings.

[0174] The reflective particles may be selected so as not to significantly alter the color effect produced by the colorant with which they are combined, and more particularly to optimize this effect in terms of color rendering, which may more particularly have yellow, pink, red, bronze, orange, brown, gold and / or copper colors or shades.

[0175] These particles may have various morphologies, in particular in the form of platelets or spheres, in particular in the form of spheres.

[0176] Regardless of their morphology, the reflective particles may or may not have a multi-layer structure, and if multi-layered, may have at least one layer of a particularly reflective material, for example of uniform thickness.

[0177] If the reflective particles do not have a multilayer structure, they may consist of metal oxides, in particular synthetically obtained titanium oxide or iron oxide.

[0178] If the reflective particles have a multilayer structure, they may comprise, for example, a natural or synthetic substrate, in particular a synthetic substrate, at least partially coated with at least one layer of a reflective material, in particular at least one metal or metallic material. The substrate can be made from one or more organic and / or mineral materials.

[0179] More particularly, it can be chosen from glass, ceramic, graphite, metal oxides, alumina, silica, silicates, especially aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, without being limited to this list.

[0180] The reflective material may include a metal or a layer of metallic material.

[0181] Reflective particles are described in particular in JP-A-09-188830A, JP-A-10-158450A, JP-A-10-158541A, JP-A-07-258460A and JP-A-05-017710A.

[0182] Further examples of reflective particles comprising an inorganic substrate coated with a metal layer include particles comprising a borosilicate substrate coated with silver.

[0183] Silver-coated glass-based particles in platelet form are sold by Toyal under the name Microglass Metashine REFSX 2025 PS. Nickel / chromium / molybdenum alloy-coated glass-based particles are sold by the same company under the names Crystal Star GF 550 and GF 2525.

[0184] Particles comprising a metal substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium may also be utilized, said substrate being coated with at least one layer of at least one metal oxide such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxide and mixtures thereof.

[0185] Examples include SiO2 coated aluminum, bronze or copper powders sold under the name Visionaire by the company Eckart.

[0186] Also included are interference pigments that are not bound to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic bright flakes (Geometric Pigments or Spectra f / x from Spectratek).Special effect pigments also include fluorescent pigments (which are either materials that fluoresce in daylight or that exhibit ultraviolet fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, such as those sold by Quantum Dots Corporation.

[0187] The variety of pigments that can be used in the present invention makes it possible to obtain a wide range of colors and also to obtain specific optical effects such as metallic or interference effects.

[0188] The size of the pigments used in the composition according to the invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm, and more preferentially between 30 nm and 50 μm.

[0189] The pigment may be dispersed in the composition with a dispersant.

[0190] Dispersants protect dispersed particles from agglomeration or aggregation. They can be surfactants, oligomers, polymers, or mixtures of several of these, each containing one or more functional groups with a strong affinity for the surface of the particles to be dispersed. In particular, they can be physically or chemically bonded to the pigment surface. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid, especially C8-C20 fatty acids, and polyols such as glycerol or diglycerol, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g / mol, such as the product sold by Avecia under the name Solsperse 21000, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold by Henkel under the trade name Dehymyls PGPH, or other polyhydroxystearic acids, such as the product sold by Uniqema under the trade name Arlacel P100, and mixtures thereof, are used.

[0191] Other dispersants that may be used in the compositions of the invention include quaternary ammonium derivatives of polycondensed fatty acids, such as Solsperse 17000 sold by Avecia, and polydimethylsiloxane / oxypropylene mixtures, such as those sold by Dow Corning under the references DC2-5185 and DC2-5225 C.

[0192] The pigment used in the composition may be surface-treated with an organic agent.

[0193] Thus, pre-surface-treated pigments useful in the present invention are pigments that have been completely or partially surface-treated with organic agents of a chemical, electronic, electrochemical, mechanochemical, or mechanical nature, such as those described in Cosmetics and Toiletries, February 1990, Vol. 105, pp. 53-64, and then dispersed in the compositions of the present invention. These organic agents can be selected from waxes such as carnauba wax and beeswax; fatty acids, fatty alcohols, and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, and lauric acid and their derivatives; anionic surfactants; lecithin; sodium, potassium, magnesium, iron, titanium, zinc, or aluminum salts of fatty acids, such as aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, such as silicones, especially polydimethylsiloxane; organic fluorine compounds, such as perfluoroalkyl ethers; and fluorosilicone compounds.

[0194] The surface-treated pigments useful in the present compositions may be treated with mixtures of these compounds and / or may have been subjected to several surface treatments.

[0195] Surface-treated pigments useful in connection with the present invention can be prepared according to surface treatment techniques well known to those skilled in the art, or can be commercially available as is.

[0196] Preferably, the surface-treated pigment is coated with an organic layer.

[0197] The organic agent with which the pigment is treated may be deposited on the pigment by evaporating the solvent, by chemical reaction between molecules of the surface treatment agent, or by forming a covalent bond between the surface treatment agent and the pigment.

[0198] Thus, the surface treatment can be carried out, for example, by chemically reacting a surface treatment agent with the pigment surface to form a covalent bond between the surface treatment agent and the pigment or filler, as described, inter alia, in U.S. Pat. No. 4,578,266.

[0199] Organic agents that are covalently bonded to the pigment are preferably used.

[0200] The agent used for the surface treatment can account for 0.1% to 50% by mass, preferably 0.5% to 30% by mass, and more preferentially 1% to 20% by mass of the total mass of the pigment to be surface treated.

[0201] Preferably, the surface treatment of the pigment is one of the following treatments: - PEG-silicone treatments, such as the AQ surface treatment sold by LCW; - methicone treatments, such as the SI surface treatment sold by LCW; - dimethicone treatments, such as Covasil 3.05 surface treatment sold by LCW; - dimethicone / trimethylsiloxysilicate treatments, such as Covasil 4.05 surface treatment sold by LCW; - magnesium myristate treatments, such as the MM surface treatment sold by LCW; - aluminum dimyristate treatments, such as the MI surface treatment sold by Miyoshi; - perfluoropolymethyl isopropyl ether treatments, such as the FHC surface treatment sold by LCW; - isostearyl sebacate treatment agents, such as the HS surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - perfluoroalkylphosphate treatment agents, such as the PF surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - acrylate / dimethicone copolymer and perfluoroalkylphosphate treatment agents, such as the FSA surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - polymethylhydrogenosiloxane / perfluoroalkylphosphate treatment agents, such as the FS01 surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - acrylate copolymer / dimethicone treatment agents, such as the ASC surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - isopropyl titanium triisostearate treatment agents, such as ITT surface treatment agents sold by Daito Chemical Industry Co., Ltd.; - acrylate copolymer treatment agents, such as the APD surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - Perfluoroalkylphosphate / isopropyl titanium triisostearate treatment agent, such as PF+ITT surface treatment agent sold by Daito Kasei Kogyo Co., Ltd. is selected from.

[0202] According to a particular embodiment of the invention, the dispersant is present in composition B together with the organic or mineral pigment in particulate form of submicron size.

[0203] The terms "submicron size" or "submicron" refer to pigments that have been micronized by a micronization process and have an average particle size of less than 1 micrometer (μm), particularly 0.1 to 0.9 μm, and preferably 0.2 to 0.6 μm.

[0204] According to one embodiment, the dispersant and the pigment are present in an amount (dispersant:pigment) of 1:4 to 4:1, in particular 1.5:3.5 to 3.5:1, or even better 1.75:3 to 3:1, by weight ratio.

[0205] Thus, the dispersant may have a silicone backbone, such as a silicone polyether, and may be an aminosilicone type dispersant. Suitable dispersants include: aminosilicones, i.e. silicones containing one or more amino groups, such as those sold by BYK under the name BYK LPX 21879, and GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1 sold by Genesee Polymers; silicone acrylates, such as Tego® RC 902, Tego® RC 922, Tego® RC 1041 and Tego® RC 1043 sold by Evonik; - polydimethylsiloxane (PDMS) silicones with carboxyl groups, such as X-22162 and X-22370 from Shin-Etsu Chemical Co., Ltd., epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682 and GP-695 from Genesee Polymers or Tego® RC 1401, Tego® RC 1403, Tego® RC 1412 from Evonik.

[0206] According to a particular embodiment, the dispersant is cationic.

[0207] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments or organic pigments.

[0208] In one variant of the invention, the pigment is an organic pigment, preferentially an organic pigment surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment is a mineral pigment.

[0209] Preferably, the pigment is selected from iron oxides, in particular red, brown or black iron oxides, such as those sold by SunChemical under the name SunPuro® Red Iron Oxide.

[0210] direct dye Composition C used in connection with the method according to the invention may comprise one or more direct dyes.

[0211] The term "direct dyes" refers to natural and / or synthetic dyes other than oxidation dyes. These are dyes that diffuse superficially onto the fiber.

[0212] These can be ionic or non-ionic, preferably cationic or non-ionic.

[0213] Examples of suitable direct dyes include azo direct dyes, either alone or in mixtures; (poly)methine dyes, such as cyanine, hemicyanine, and styryl; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes; and natural direct dyes.

[0214] The direct dyes are preferably cationic direct dyes, and mention may be made of hydrazonocationic dyes of the following formulae (XIII) and (XIV) and azocationic dyes of the following formulae (XV) and (XVI): Het + -N(Ra)-N=C(Rb)-Ar,Q-(XIII), Het + -C(Ra)=NN(Rb)-Ar,Q(XIV), Het + -N=N-AR,Q-(XV), AR + -N=N-AR'', Q-(XVI) (In formulas (XIII) to (XVI), - Het + represents a cationic heteroaryl radical, preferentially having an intracyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted, preferentially with at least one (C1-C8) alkyl group, such as methyl, - Ar +represents an aryl group such as phenyl or naphthyl bearing an exocyclic cationic charge, preferentially ammonium, in particular tri(C1-C8)alkylammonium such as trimethylammonium; - Ar preferentially represents one or more electron-donating groups, such as i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8)(alkyl)amino, in which the alkyl group is optionally substituted with a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) an aryl group, in particular phenyl, optionally substituted with an optionally substituted N—(C1-C8) alkyl-N-aryl(C1-C8) alkylamino, or alternatively, Ar represents a julolidine group; Ar" represents an optionally substituted (hetero)aryl group, for example phenyl or pyrazolyl, preferentially optionally substituted with one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups; Ra and Rb may be identical or different and represent a hydrogen atom or an optionally substituted (C1-C8) alkyl group, preferentially by a hydroxyl group; the substituents Ra and Het+ and / or the substituents Rb and Ar, together with the atoms carrying them, form a (hetero)cycloalkyl, in particular Ra and Rb represent a (C1-C4)alkyl group optionally substituted by a hydrogen atom or a hydroxyl group, - Q- represents an organic or inorganic anionic counterion such as a halide or alkyl sulfate.

[0215] Mention may be made in particular of the azo and hydrazono direct dyes with an endocyclic cationic charge of the formulae (XIII) to (XVI) defined above, more particularly the cationic direct dyes with an endocyclic cationic charge described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954, preferentially the following direct dyes: [ka] (In formulas (XVII) and (XVIII), -R 1 represents a (C1-C4) alkyl group such as methyl; -R 2 and R 3 may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl; -R 4 represents a hydrogen atom or an electron donating group, such as optionally substituted (C-C) alkyl, optionally substituted (C-C) alkoxy or (di)(C-C)(alkyl)amino, in which the alkyl group is optionally substituted with a hydroxyl group, in particular R 4 is a hydrogen atom, Z represents a CH group or a nitrogen atom, preferentially CH, Q- is an anionic counterion as defined above, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0216] In particular, the dyes of formula (XV) and (XVI) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof, and Q′ is an anionic counterion as defined above, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0217] The direct dye can be selected from anionic direct dyes. The anionic direct dye of the present invention is a dye generally referred to as an "acid" direct dye, due to its affinity for alkaline substances. The term "anionic direct dye" refers to a direct dye containing at least one COR or SOR substituent in its structure, where R represents a hydrogen atom or a cation or ammonium ion derived from a metal or amine. The anionic dye can be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethanoic acid dyes, indoamine acid dyes, anthraquinonic acid dyes, indigoid dyes, and natural acid dyes.

[0218] Acid dyes useful in the present invention include dyes of the following formulae (XIX), (XIX'), (XX), (XX'), (XXI), (XXI'), (XXII), (XXII'), (XXIII), (XXIV), (XXV) and (XXVI): a) diaryl anionic azo dyes of formula (XIX) or (XIX'): [ka] (In formulas (XIX) and (XIX'), - R7, R8, R9, R 10 , R'7, R'8, R'9 and R' 10 may be the same or different and are hydrogen atoms or the following: - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be identical or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); - R"-S(O)2-, where R" represents a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group, preferentially a phenylamino or phenyl group; - R'''-S(O)2-X'-, where R''' represents an optionally substituted alkyl or aryl group and X' is as defined above; - (di)(alkyl)amino; - i) nitro; ii) nitroso; iii) (O)2S(O - )-, M + and iv) optionally substituted with one or more groups selected from alkoxy; M + aryl(alkyl)amino, wherein: - optionally substituted heteroaryl; preferentially a benzothiazolyl group; - cycloalkyl; in particular cyclohexyl; - Ar-N=N- (wherein Ar is an optionally substituted aryl group; preferentially one or more alkyl, (O)S(O - )-,M + or phenyl optionally substituted by a phenylamino group; or - two adjacent groups R7 and R8 or R8 and R9 or R9 and R 10 together form a fused benzo group A'; R'7 and R'8 or R'8 and R'9 or R'9 and R' 10 together form a fused benzo group B'; A' and B' are i) nitro; ii) nitroso; iii) (O)S(O - )-,M +iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N-; and xi) optionally substituted aryl(alkyl)amino; + , R°, X, X′, X″ and Ar are as defined above; - W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent radical i) -NR-, in which R is as defined above, or ii) methylene -C(Ra)(Rb)-, in which Ra and Rb may be identical or different and represent a hydrogen atom or an aryl group, or Ra and Rb together with the carbon atom carrying them form a spirocycloalkyl; preferentially, W represents a sulfur atom, or Ra and Rb together form a cyclohexyl; Formulas (XIX) and (XIX') contain at least one sulfonate group (O)S(O) on one of the rings A, A', B, B' or C. - )-,M + or one carboxylate group (O)CO - -,M + ; it is understood that it preferentially comprises sodium sulfonate.

[0219] Examples of dyes of formula (XIX) are Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid 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; Examples of dyes of formula (XIX') include Acid Red 111, Acid Red 134, and Acid Yellow 38; b) Pyrazolone anionic azo dyes of formula (XX) and (XX'): [ka] (In formulas (XX) and (XX'), -R 11 , R 12 and R 13 may be the same or different and are hydrogen or a halogen atom, an alkyl group, or -(O)S(O - ), M + (In the formula, M +is as defined above); -R 14 represents a hydrogen atom, an alkyl group, or -C(O)O - ,M + group (in the formula, M + is as defined above); -R 15 represents a hydrogen atom; -R 16 represents an oxo group, in which case R' 16 does not exist, or instead, R 15 is R 16 together to form a double bond; -R 17 and R 18 may be the same or different and represent a hydrogen atom or one of the following: - (O)2S(O - )-,M + (In the formula, M + is as defined above); - Ar-OS(O)2-, where Ar represents an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups. represents a group selected from: -R 19 and R 20 together form either a double bond or an optionally substituted benzo group D'; - R' 16 , R' 19 and R' 20 may be the same or different and represent a hydrogen atom or an alkyl group or a hydroxyl group; -R 21 represents a hydrogen atom, an alkyl group, or an alkoxy group; Ra and Rb may be identical or different and are as defined above, and preferentially, Ra represents a hydrogen atom and Rb represents an aryl group; Y represents either a hydroxyl group or an oxo group; - [ka] represents a single bond when Y is an oxo group; represents a double bond when Y is a hydroxyl group; Formulas (XX) and (XX') contain at least one sulfonate group (O)S(O - )-,M + or one carboxylate group -C(O)O - ,M + ; it is understood that it preferentially comprises sodium sulfonate).

[0220] Examples of dyes of formula (XX) include Acid Red 195, Acid Yellow 23, Acid Yellow 27, and Acid Yellow 76; examples of dyes of formula (XX') include Acid Yellow 17; c) Anthraquinone dyes of formula (XXI) and (XXI'): [ka] (In formulas (XXI) and (XXI'): -R 22 , R 23 , R 24 , R 25 , R 26 and R 27 may be the same or different and represent a hydrogen or halogen atom, or one of the following: - alkyl; - hydroxyl, mercapto; - alkoxy, alkylthio; - Alkyl and (O)2S(O - ),M + optionally substituted aryloxy or arylthio, which are preferentially substituted by one or more groups selected from + is as defined above); - Alkyl and (O)2S(O - )-,M + (M +is as defined above); - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino; - (O)2S(O - )-,M + (In the formula, M + is as defined above) represents a group selected from: Z' is a hydrogen atom or a group NR 28 R 29 (wherein R 28 and R 29 may be the same or different and are hydrogen atoms or the following: - alkyl; - polyhydroxyalkyl, such as hydroxyethyl; one or more groups, in particular i) alkyl, such as methyl, n-dodecyl, n-butyl; ii) (O)S(O - )-, M + (In the formula, M + is as defined above; iii) aryl optionally substituted with R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above and preferentially R° represents an alkyl group); - cycloalkyl; in particular cyclohexyl; - Z is hydroxyl and NR' 28 R' 29 (wherein R' represents a group selected from 28 and R' 29 may be the same or different, and are R 28 and R 29 represents the same atom or group as Formulas (XXI) and (XXI') contain at least one sulfonate radical (O)S(O - )-,M + or one carboxylate radical -C(O)O - ,M + , and it is understood that it preferentially comprises sodium sulfonate.

[0221] Examples of dyes of formula (XXI) include Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2, and an example of a dye of formula (XXI') is Acid Black 48. d) Nitro dyes of formula (XXII) and (XXII'): [ka] (In formulas (XXII) and (XXII'), -R 30 , R 31 and R 32 may be the same or different and represent a hydrogen or halogen atom, or - alkyl; - alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups; - hydroxyl, mercapto; - Nitro, nitroso; - polyhaloalkyl; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X', and X'' are as defined above); - (O)2S(O - )-,M + (In the formula, M + is as defined above); - (O)CO - -,M + (In the formula, M + is as defined above); - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino; - represents a group selected from heterocycloalkyl, such as piperidino, piperazino or morpholino; in particular R 30 , R 31 and R 32 represents a hydrogen atom; Rc and Rd may be identical or different and represent a hydrogen atom or an alkyl group; - W is as defined above; W represents, in particular, an -NH- group; - ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group; - n is 1 or 2; - p represents an integer between 1 and 5 (inclusive); - q represents an integer between 1 and 4 (inclusive); - u is 0 or 1; when n is 1, J represents a nitro or nitroso group, in particular nitro; - when n is 2, J is an oxygen or sulfur atom or a divalent -S(O) m - radical, where m represents an integer 1 or 2, and preferentially J represents a -SO2- radical, M' represents a hydrogen atom or a cationic counterion; - [ka] may be present or absent and may be one or more groups R as defined above 30 represents a benzo group optionally substituted with Formulas (XXII) and (XXII') contain at least one sulfonate radical (O)S(O - )-,M + or one carboxylate radical -C(O)O - ,M + , and it is understood that it preferentially comprises sodium sulfonate.

[0222] Examples of dyes of formula (XXII) include Acid Brown 13 and Acid Orange 3; examples of dyes of formula (XXII') include Acid Yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4'-N,N-2''-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7; e) Triarylmethane dyes represented by formula (XXIII): [ka] (In formula (XXIII), -R 33 , R 34 , R 35 and R 36 may be identical or different and represent a hydrogen atom or a group selected from alkyl, optionally substituted aryl and optionally substituted arylalkyl; in particular alkyl groups and optionally (O) m S(O - )-, M + group (in the formula, M + and m represents a benzyl group substituted with (as defined above); -R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 may be the same or different and are hydrogen atoms or the following: - alkyl; - alkoxy, alkylthio; - (di)(alkyl)amino; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be identical or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); - two adjacent groups R 41 and R 42 or R 42 and R 43 or R 43 and R 44 together form a fused benzo group: I'; I' is i) nitro; ii) nitroso; iii) (O)S(O - )-,M + iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; and ix) R°-X'-C(X)-X''-, where M + , R°, X, X' and X'' are as defined above). optionally substituted with one or more groups selected from In particular, R 37 ~R 40 represents a hydrogen atom, and R 41 ~R 44 may be the same or different and are hydroxyl groups or (O)S(O - )-,M + represents;R 43 and R 44 together form a benzo group, this is preferentially (O)S(O - )-group; At least one of the rings G, H, I, or I′ contains at least one sulfonate group (O)S(O -)- or one carboxylate group C(O)O - -; it is understood to preferentially include sulfonates.

[0223] Examples of dyes of formula (XXIII) include Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid Green 3, Acid Green 5 and Acid Green 50. f) Xanthene dyes of formula (XXIV): [ka] (In formula (XXIV): -R 45 , R 46 , R 47 and R 48 may be the same or different and represent a hydrogen or halogen atom; -R 49 , R 50 , R 51 and R 52 may be the same or different and represent a hydrogen or halogen atom, or one of the following: - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); represents a group selected from In particular, R 49 , R 50 , R 51 and R 52 represents a hydrogen or halogen atom, G represents an oxygen or sulfur atom or an NRe group, where Re is as defined above, and in particular G represents an oxygen atom; - L is alkoxide O - , M + , thioalkoxide S - , M + or an NRf group (wherein Rf represents a hydrogen atom or an alkyl group, and M + is as defined above, and M + is in particular sodium or potassium), L' is an oxygen or sulfur atom or an ammonium group: N + RfRg (wherein Rf and Rg may be the same or different and represent a hydrogen atom or an optionally substituted alkyl or aryl group). L' represents, in particular, an oxygen atom or one or more alkyl or (O) m S(O - )-, M + Groups (wherein m and M + represents a phenylamino group optionally substituted with (as defined above); Q and Q', which may be identical or different, represent an oxygen or sulfur atom; in particular, Q and Q' represent an oxygen atom; -M + is as defined above).

[0224] Examples of dyes of formula (XXIV) include Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; and Acid Violet 9. g) Indole dyes of formula (XXV): [ka] (In formula (XXV): -R 53 , R 54 , R 55 , R 56 , R 57 , R 58, R 59 and R 60 may be the same or different and are a hydrogen atom or one of the following: - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be identical or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); represents a group selected from G represents an oxygen or sulfur atom or an NRe group, where Re is as defined above, and in particular G represents an oxygen atom; Ri and Rh may be identical or different and represent a hydrogen atom or an alkyl group; Formula (XXIV) contains at least one sulfonate group (O)S(O-)-,M + or one carboxylate group -C(O)O - ,M + ; it is understood that it preferentially comprises sodium sulfonate).

[0225] An example of a dye of formula (XXV) is Acid Blue 74; h) Quinoline dyes of formula (XXVI): [ka] (In formula (XXVI): -R 61represents a hydrogen atom, a halogen atom, or an alkyl group; -R 62 , R 63 and R 64 may be the same or different and are a hydrogen atom or (O)S(O - )-, M + group (in the formula, M + represents a hydrogen atom or a cationic counterion; or Instead, R 61 and R 62 or R 61 and R 64 together form one or more (O)S(O - )-, M + group (in the formula, M + represents a hydrogen atom or a cationic counterion), forming a benzo group optionally substituted with Formula (XXVI) contains at least one sulfonate radical (O)S(O - )-,M + It is understood that it preferentially comprises sodium sulfonate.

[0226] Examples of dyes of formula (XXVI) include Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0227] Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or decoctions containing these natural dyes may also be used, in particular poultices or extracts based on henna dye.

[0228] Preferably, the direct dye is selected from anionic direct dyes.

[0229] The colorants may be present in a total amount ranging from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, relative to the total amount of composition C; preferably, the colorants are chosen from pigments.

[0230] The pigments may be present in a total amount of from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight, and even better still from 0.5% to 10% by weight relative to the total amount of composition C.

[0231] The direct dyes may be present in a total amount ranging from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight, relative to the total weight of composition C.

[0232] Non-carboxylate anionic thickener Composition C used in the context of the method according to the invention may also comprise at least one non-carboxylate anionic thickener.

[0233] For purposes of the present invention, the term "non-carboxylic acid agent" refers to an agent that does not contain a carboxylic acid functional group (-COOH) or a carboxylate functional group (-COO - ) means a drug that does not contain

[0234] For the purposes of the present invention, the term "thickener" means a thickener that, when present at a concentration of 0.05% by weight, thickens the composition into which it is incorporated at room temperature (25°C) and atmospheric pressure at a shear rate of 1 s -1 The term "viscosity" refers to a compound that increases the viscosity of a composition by at least 20 cps, preferably at least 50 cps (viscosity can be measured using a cone / plate viscometer such as a Haake R600 rheometer).

[0235] Preferably, the non-carboxylic acid anionic thickener is chosen from non-carboxylic acid anionic polymers, more preferentially from anionic polymers containing sulfonic groups.

[0236] For purposes of the present invention, the term "anionic polymer" means a polymer that contains one or more anionic groups or anionic groups and no cationic groups or cationic groups.

[0237] Advantageously, the non-carboxylic acid anionic thickener is chosen from anionic polymers comprising at least one ethylenically unsaturated monomer bearing a sulfonic group, in free form or in partially or completely neutralized form.

[0238] The polymer may be crosslinked or non-crosslinked, preferably crosslinked.

[0239] These polymers can be associative or non-associative, preferably non-associative.

[0240] Recall that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0241] Its chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0242] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon chain containing at least 8 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms, more preferentially 18 to 30 carbon atoms.

[0243] Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also refer to a hydrocarbon-based polymer, such as polybutadiene.

[0244] The ethylenically unsaturated monomer having a sulfonic acid group is, in particular, vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylamide (C1-C 22) Alkyl sulfonic acid, N-(C1-C 22 ) Alkyl (meth)acrylamide (C1-C 22 ) alkyl sulfonic acids (such as undecylacrylamido methane sulfonic acid) and also partially or fully neutralized forms thereof.

[0245] More preferentially, (meth)acrylamides (C1-C 22 ) Alkyl sulfonic acids such as acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, as well as partially or fully neutralized forms thereof may be used.

[0246] More specifically, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or fully neutralized forms are used.

[0247] Among the 2-acrylamido-2-methylpropanesulfonic acid copolymers, mention may be made of partially or completely neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide, and particular mention may be made of the products described in Example 1 of EP 503853, to which reference may be made with regard to these polymers.

[0248] Mention may also be made of copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts and hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT 10 by the company SEPPIC (INCI name: Hydroxyethyl acrylate / Sodium acryloyldimethyltaurate copolymer).

[0249] Associative AMPS polymers are particularly suitable for C6-C 22 They can be selected from statistical associative AMPS polymers modified by reaction with n-mono- or di-n-alkylamines, such as those described in patent application WO 00 / 31154, the content of which forms an integral part. These polymers can also contain other ethylenically unsaturated hydrophilic monomers, such as (meth)acrylic acid derivatives, for example their esters with monohydric alcohols, or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidones, or mixtures of these compounds.

[0250] Preferred polymers of this family are selected from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0251] These same copolymers may also contain one or more ethylenically unsaturated monomers not containing a fatty chain, such as (meth)acrylic acid derivatives, in particular their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.

[0252] These copolymers are described in particular in EP-A-750899, U.S. Pat. No. 5,089,578 and the following publications from Yotaro Morishima: - Self-assembling amphiphilic polyelectrolytes and their nanostructures,Chinese Journal of Polymer Science,Vol.18,No.40,(2000),323-336; - Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering-Macromolecules,Vol.33,No.10(2000),3694-3704; - Solution properties of micelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte::salt effects on rheological behavior-Langmuir,Vol.16,No.12,(2000)5324-5332; - Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers-Polym.Preprint, Div. Polym. Chem., 40(2), (1999), 220-221.

[0253] Among these polymers, mention may be made of: - 15% to 60% by mass of AMPS units and 40% to 85% by mass of (C8 to C9 16 ) alkyl (meth) acrylamide or (C8-C 16 ) alkyl (meth)acrylate units, crosslinked or non-crosslinked, neutralized or non-neutralized copolymers, such as those described in EP-A-750899; - 10 mol% to 90 mol% of acrylamide units, 0.1 mol% to 10 mol% of AMPS units, and 5 mol% to 80 mol% of n-(C6 to C 18) terpolymers containing alkylacrylamide units, such as those described in U.S. Pat. No. 5,089,578.

[0254] Mention may also be made of fully neutralized copolymers of AMPS and dodecyl methacrylate and also crosslinked and non-crosslinked copolymers of AMPS and n-dodecyl methacrylamide, such as those described in the Morishima paper mentioned above.

[0255] Preferably, the non-carboxylic anionic thickener is chosen from sodium 2-acrylamido-2-methylpropanesulfonate / hydroxyethyl acrylate copolymers sold by SEPPIC (INCI name Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer).

[0256] Advantageously, the total amount of non-carboxylate anionic thickeners ranges from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even better from 0.1% to 5% by weight and even better still from 0.1% to 3% by weight relative to the total weight of composition C.

[0257] Associative Polymers Composition C according to the present invention may also comprise at least one associative polymer containing at least one carboxylic acid functional group and different from the non-carboxylic acid anionic thickeners defined above.

[0258] Recall that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0259] Its chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0260] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon chain containing at least 10 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms, more preferentially 18 to 30 carbon atoms.

[0261] Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also refer to a hydrocarbon-based polymer, such as polybutadiene.

[0262] Associative polymers can be nonionic, anionic, cationic or amphoteric.

[0263] Preferably, the associative polymer is selected from anionic associative polymers.

[0264] Among the associative polymers of the anionic type, mention may be made of: (a) those comprising at least one hydrophilic unit and at least one fatty-chain allyl ether unit, more particularly those in which the hydrophilic unit is made from an anionic ethylenically unsaturated monomer, even more particularly those formed from a vinyl carboxylic acid, most particularly those formed from acrylic acid or methacrylic acid or a mixture thereof;

[0265] Among these anionic associative polymers, those particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and / or methacrylic acid, 5% to 60% by weight of lower alkyl (meth)acrylates, 2% to 50% by weight of fatty-chain allyl ethers and 0 to 1% by weight of a crosslinker (a well-known copolymerizable unsaturated polyethylenic monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylbisacrylamide).

[0266] Among the latter polymers, the most preferred are crosslinked terpolymers of methacrylic acid, ethyl acrylate and polyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), in particular the aqueous 30% emulsion of crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10 allyl ether (40 / 50 / 10) sold by Ciba under the names Salcare SC 80® and Salcare SC 90®. - (b) those comprising i) at least one hydrophilic unit of the unsaturated olefinic carboxylic acid type, and ii) at least one hydrophobic unit of the type (C10-C30) alkyl ester of an unsaturated carboxylic acid, etc. The unsaturated carboxylic acids useful in the present invention (C 10 ~C 30 ) Alkyl esters include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, and dodecyl acrylate, and the corresponding methacrylic acid esters, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

[0267] Anionic polymers of this type are described and prepared, for example, by US Pat. No. 3,915,921 and US Pat. No. 4,509,949.

[0268] Among this type of anionic associative polymer, 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C 10 ~C 30 alkyl acrylate (hydrophobic unit) and 0 to 6% by mass of a cross-linkable polymerizable monomer, or the above-mentioned, 98% to 96% by mass of acrylic acid (hydrophilic unit), 1% to 4% by mass of C 10 ~C 30 More particularly, one consisting of alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of a cross-linking polymerizable monomer will be used.

[0269] Among the above-mentioned polymers, those most particularly preferred according to the invention are Pemulen TR1®, Pemulen TR2®, Carbopol 1382®, and even more preferentially the product sold by Goodrich under the trade name Pemulen TR1® and the product sold by SEPPIC under the name Coatex SX®.

[0270] Mention may also be made of the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer sold under the name Acrylidone LM by the company ISP. - (c) Maleic anhydride / C 30 ~C 38 α-olefin / alkyl maleate terpolymers, such as those sold under the trade name Performa V 1608® by Newphase Technologies (maleic anhydride / C 30 ~C 38 α-olefin / isopropyl maleate copolymer); (d) Acrylic terpolymers, including: i) approximately 20% by mass to 70% by mass of an α,β-monoethylenically unsaturated carboxylic acid [A]; ii) approximately 20% to 80% by weight of an α,β-monoethylenically unsaturated non-surfactant monomer other than [A]; iii) a nonionic monourethane which is a reaction product of approximately 0.5% to 60% by weight of a surfactant having one hydroxyl group with a monoethylenically unsaturated monoisocyanate; For example, the terpolymer described in EP-A-0 173 109, more particularly in Example 3, namely an aqueous 25% dispersion of terpolymer of methacrylic acid / methyl acrylate / behenyl alcohol dimethyl-meta-isopropenyl benzyl isocyanate ethoxylate (40 EO). (e) copolymers comprising, among these monomers, α,β-monoethylenically unsaturated carboxylic acids and esters of α,β-monoethylenically unsaturated carboxylic acids with oxyalkylenated fatty alcohols.

[0271] Preferentially, these compounds further comprise, as monomers, esters of α,β-monoethylenically unsaturated carboxylic acids and of C1-C4 alcohols.

[0272] Examples of this type of compound include Aculyn 22®, sold by Roehm & Haas, which is a terpolymer of methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate, and Aculyn 88, also sold by Roehm & Haas.

[0273] Advantageously, the associative polymer different from the compound containing at least one carboxylic acid function and different from the aforementioned non-carboxylic acid anionic thickeners is chosen from acrylic associative polymers, more preferentially carboxylic acrylic associative polymers.

[0274] Particularly preferably, the associative polymer is different from compounds containing at least one carboxylic acid function, different from the aforementioned non-carboxylic acid anionic thickeners, and is chosen from copolymers which contain among their monomers α,β-monoethylenically unsaturated carboxylic acids and esters of α,β-monoethylenically unsaturated carboxylic acids with oxyalkylenated fatty alcohols.

[0275] Advantageously, the total amount of associative polymers different from the compounds containing at least one carboxylic acid function and different from the non-carboxylic acid anionic thickeners mentioned above 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.

[0276] organic solvents Composition C according to the invention may comprise one or more organic solvents.

[0277] Examples of organic solvents include C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monomethyl ether, as well as aromatic alcohols, in particular aromatic monoalcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0278] The organic solvents may be present in a total amount of from 0.01% to 60% by weight, preferably from 0.05% to 50% by weight and more preferentially from 0.1% to 45% by weight relative to the total weight of composition C.

[0279] Composition C used in the context of the method according to the invention may be aqueous. The water content may range from 1% to 90% by weight, preferably from 10% to 80% by weight, and more preferentially from 20% to 75% by weight, relative to the total weight of composition C.

[0280] additives Composition C used in the context of the method according to the invention may contain any adjuvant or additive normally used.

[0281] Among the additives that may be contained in the composition, mention may be made of reducing agents, emollients, antifoaming agents, moisturizing agents, UV screening agents, peptidating agents, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than those previously described, preservatives, silicones other than the compounds previously described, oils, waxes and mixtures thereof.

[0282] The composition C used in the context of the method of the invention may in particular be in the form of a suspension, a dispersion, a gel, an emulsion, in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion or a multiphase emulsion (W / O / W or polyol / O / W or O / W / O), a cream, a mousse, a stick, a vesicle, in particular a dispersion of ionic or non-ionic lipids or a two-phase or multiphase lotion.

[0283] A person skilled in the art will be able, based on his general knowledge, to select a suitable presentation form as well as a method for preparing it, taking into account first the properties of the components used, in particular their solubility in the carrier, and then the intended use of the composition.

[0284] Application of heat to keratin hair fibers According to step b) of the method according to the invention, heat is applied to the keratin hair fibres at a temperature above 30°C.

[0285] The heat application step of the method of the present invention can be carried out using a hood, a hair dryer, a straightener, or a climazone hood.

[0286] Preferably, the heat application step of the method of the present invention is carried out using a hair dryer and, optionally, a straightening iron.

[0287] During step b) of applying heat to the keratinous hair fibers, the tresses can be subjected to mechanical action such as combing, brushing or hand combing.

[0288] Preferably, the keratinous hair fibers are dried by applying heat and also by using an air current, which makes it possible to improve the strand separation of the coating.

[0289] During drying, the tresses may be subjected to mechanical action such as combing, brushing or hand combing.

[0290] Advantageously, the temperature during step b) ranges from 30 to 250°C, preferably from 50 to 220°C.

[0291] Advantageously, step b) comprises drying the keratinous hair fibres at a temperature ranging from 30 to 150°C, preferably from 30 to 110°C and more preferentially from 50 to 110°C.

[0292] Advantageously, step b) comprises straightening with a straightening iron at a temperature ranging from 100 to 250°C, preferably from 150 to 220°C, and more preferentially from 180 to 220°C.

[0293] If a hood or a hair dryer is used during step b) of applying heat to the keratin hair fibres, the temperature is preferably between 30 and 110°C, preferentially between 50 and 110°C.

[0294] If a straightening iron is used during step b) of applying heat to the keratin hair fibres, the temperature is preferably between 100 and 250°C, more preferably between 150 and 220°C.

[0295] In a particular variant, the process of the present invention comprises a step (b1) of applying heat using a hood dryer, hair dryer or crimson hood, preferably a hair dryer, and a step (b2) of applying heat using a straightening iron or curling iron, preferably a straightening iron.

[0296] Step (b1) may be carried out before step (b2). Preferably, step (b1) is carried out before step (b2).

[0297] During step (b1), the keratinous hair fibers can be dried, for example, using a hood or a hair dryer at a temperature of at least 30°C, preferably between 30 and 110°C, more preferentially between 50 and 110°C.

[0298] The temperature at which the straightening iron or curling iron, preferably the straightening iron, is slid during step (b2) may preferably be in the range of 100°C to 250°C, preferably 150°C to 220°C, more preferably 180°C to 220°C.

[0299] Composition G The dyeing process according to the invention comprises c) the application to the keratinous hair fibres of at least one composition G, which composition G comprises: at least one (poly)carbodiimide compound, - comprises at least one compound containing at least one carboxylic acid functional group.

[0300] The (poly)carbodiimide compound is as defined above and has the same preferences as those indicated for composition C.

[0301] The (poly)carbodiimide compound used in composition G may be the same as or different from that used in composition C, and is preferably the same.

[0302] Advantageously, the total amount of (poly)carbodiimide compounds in composition G 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 G.

[0303] The compound containing at least one carboxylic acid functional group is as defined above with the same priority as indicated for composition C.

[0304] The compound containing at least one carboxylic acid functional group used in composition G may be the same as or different from that used in composition C, preferably the same.

[0305] Advantageously, the total amount of compounds comprising at least one carboxylic acid function ranges from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferentially from 1% to 15% by weight and even better from 2% to 10% by weight relative to the total weight of composition D.

[0306] Composition G may also contain at least one colorant selected from the pigments, direct dyes and mixtures thereof described above.

[0307] Preferably, composition G does not contain any coloring agent selected from pigments, direct dyes and mixtures thereof.

[0308] Composition G may also include a non-carboxylate anionic thickener and / or an associative polymer as defined above.

[0309] According to a particularly preferred embodiment, composition G comprises the same (poly)carbodiimide compound as composition C and the same compound comprising at least one carboxylic acid functional group as composition C, preferably composition G does not comprise a colorant.

[0310] Application of heat to keratin hair fibers According to step d) of the method according to the invention, heat can be applied to the keratinous hair fibres at a temperature of at least 30° C. If carried out, this step can be carried out in the same way as envisaged in step b) described below.

[0311] Advantageously, the temperature during step d) ranges from 30 to 250°C, preferably from 50 to 220°C.

[0312] protocol The composition C described above can be used on wet or dry keratinous hair fibers and on all types of keratinous hair fibers, whether light or dark, natural or dyed, permanently waved, bleached or straightened.

[0313] According to a particular embodiment of the invention, the keratinous hair fibers are washed before applying composition C.

[0314] After applying composition C to the keratinous hair fibres, a washing, rinsing or draining step may be carried out before step b) of applying heat.

[0315] Application to keratinous hair fibers can be carried out by any conventional means, in particular with a comb, a fine-toothed brush, a wide-toothed brush, a sponge or the fingers.

[0316] The application of composition C to keratinous hair fibers is generally carried out at room temperature (15 to 25° C.).

[0317] After application of composition C to the keratinous hair fibers, it is possible to wait from 1 minute to 6 hours, in particular from 1 minute to 2 hours, more particularly from 1 minute to 1 hour and more preferentially from 1 minute to 30 minutes, for example before the washing, rinsing or draining step and / or before step b).

[0318] After application of composition C, heat is applied to the keratin hair fibres according to step b) at a temperature of at least 30°C.

[0319] The method according to the invention therefore comprises a step b) of applying heat to the keratinous hair fibres using a heating tool, as described above.

[0320] Next, the above composition G is applied to the keratin hair fibers, and then, if necessary, heat is applied to the keratin hair fibers at a temperature of 30° C. or higher according to step d).

[0321] Preferably, the present invention relates to a method for dyeing keratinous hair fibers, comprising: i) at least one (poly)carbodiimide compound as defined above, - at least one compound containing at least one carboxylic acid functional group, as described above; and - applying to the keratinous hair fibres at least one composition C comprising at least one colouring agent chosen from the aforementioned pigments, direct dyes and mixtures thereof; then ii) optionally leaving said composition C on the keratin hair fibres for a period of 1 minute to 30 minutes, preferably 1 to 20 minutes; then iii) optionally washing, rinsing, dewatering or drying the fibers, then iv) subjecting the keratin hair fibers to heat at a temperature of 30°C or higher; and then v) - at least one (poly)carbodiimide compound as described above, - applying to the keratinous hair fibres at least one composition G comprising at least one compound containing at least one carboxylic acid functional group, as previously described; and vi) optionally leaving the composition G on the keratin hair fibres for 1 minute to 30 minutes, preferably 1 to 20 minutes; then vi) optionally washing, rinsing, draining or drying the keratinous hair fibers; Next, viii) optionally applying heat to the keratin hair fibre at a temperature of 30°C or higher.

[0322] Preferably, the heat application step b) comprises a keratinous hair fibre drying step as described above, optionally followed by a straightening step with a straightening iron as described above.

[0323] Preferably, Composition C also contains at least one non-carboxylate anionic thickener as described above.

[0324] Preferably, composition C also comprises at least one associative polymer as described above, different from the compound containing at least one carboxylic acid functional group and different from the non-carboxylic acid anionic thickener defined above.

[0325] Advantageously, the step of applying composition C to the keratinous hair fibres is repeated several times.

[0326] Preferably, composition G does not contain any coloring agents selected from pigments, direct dyes and mixtures thereof, as defined above.

[0327] Composition G may also include at least one non-carboxylate anionic thickener as described above.

[0328] Preferably, composition G also comprises at least one associative polymer as described above, different from the compound containing at least one carboxylic acid functional group and different from the non-carboxylic acid anionic thickeners defined above.

[0329] The step of applying composition G to the keratinous fibers may be repeated several times.

[0330] Advantageously, in the dyeing method according to the invention, step a) consists, at the time of use, in extemporaneously mixing at least two compositions A and B to obtain a composition C, and applying composition C to the keratinous hair fibres: composition A comprises at least one (poly)carbodiimide compound as defined above, composition B comprises at least one compound containing at least one carboxylic acid functional group as defined above, Composition A and / or Composition B comprise at least one colorant selected from pigments, direct dyes and mixtures thereof as defined above.

[0331] Advantageously, in the dyeing method according to the invention, step c) consists, at the time of use, in extemporaneous mixing of at least two compositions E and F to obtain composition G, and applying composition G to keratinous hair fibres: composition E comprises at least one (poly)carbodiimide compound as defined above; Composition F comprises at least one compound containing at least one carboxylic acid function as defined above.

[0332] According to a preferred embodiment, the dyeing method according to the invention is a method for dyeing keratinous hair fibers, comprising: a) at the time of use, extemporaneously mixing at least two compositions A and B to obtain composition C, and applying composition C to keratinous hair fibers, composition A comprises at least one (poly)carbodiimide compound as defined above, composition B comprises at least one compound containing at least one carboxylic acid function as defined above, Composition A and / or composition B contain at least one colorant selected from pigments, direct dyes and mixtures thereof as defined above; then b) subjecting the keratin hair fibers to heat at a temperature of 30°C or higher; and then c) at the time of use, extemporaneously mixing at least two compositions E and F to obtain composition G, and applying composition G to keratinous hair fibers, composition E comprises at least one (poly)carbodiimide compound as defined above; - composition F comprises at least one compound containing at least one carboxylic acid functional group as defined above; then d) optionally applying heat to the keratin hair fibres at a temperature of 30°C or higher.

[0333] Composition A and / or Composition B may optionally comprise at least one non-carboxylate anionic thickener as described above and / or at least one associative polymer as described above, which is different from the compound containing at least one carboxylic acid functional group and different from the non-carboxylate anionic thickener as defined above.

[0334] Preferably, composition B comprises at least one colorant selected from the previously mentioned pigments, direct dyes and mixtures thereof.

[0335] Preferably, composition A does not contain at least one colorant selected from the previously mentioned pigments, direct dyes and mixtures thereof.

[0336] According to this embodiment, the mixing of compositions A and B is preferably carried out less than 15 minutes before application to the keratinous hair fibres, more preferentially less than 10 minutes and even better still less than 5 minutes before application.

[0337] The weight ratio of composition A to composition B is preferably in the range of 0.1 to 10, preferentially 0.2 to 5, better still 0.5 to 2, or even 0.6 to 1.5. In a particular embodiment, the weight ratio of composition A to composition B is equal to 1.

[0338] Composition E and / or Composition F may optionally comprise at least one non-carboxylic acid anionic thickener as described above and / or at least one associative polymer as described above, which is different from the compound containing at least one carboxylic acid functional group and different from the non-carboxylic acid anionic thickener as defined above.

[0339] Preferably, compositions E and F do not contain any coloring agent selected from the pigments, direct dyes and mixtures thereof as defined above in an amount sufficient to dye keratinous hair fibers. According to a preferred method, compositions E and F do not contain any coloring agent.

[0340] According to this embodiment, the mixing of compositions E and F is preferably carried out less than 15 minutes before application to the keratinous hair fibres, more preferentially less than 10 minutes and even better still less than 5 minutes before application.

[0341] The weight ratio of composition E to composition F is preferably in the range of 0.1 to 10, preferentially 0.2 to 5, better still 0.5 to 2, and even more preferably 0.6 to 1.5. In a particular embodiment, the weight ratio of composition E to composition F is equal to 1.

[0342] The total amount of the (poly)carbodiimide compounds is preferably in the range of 0.01% by mass to 40% by mass, more preferentially 0.1% by mass to 30% by mass, even better 0.5% by mass to 20% by mass, and even more preferentially 1% by mass to 12% by mass, relative to the total mass of composition A.

[0343] The total amount of compounds containing at least one carboxylic acid functional group is preferably in the range of 0.2% to 60% by weight, more preferentially 1% to 40% by weight, even more preferably 1% to 30% by weight, and even more preferentially 2% to 20% by weight, relative to the total weight of composition B.

[0344] The total amount of aqueous dispersion of particles of polymers chosen from polyurethanes, acrylic polymers, and mixtures thereof preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 50% by weight, even more preferably from 1% to 40% by weight, and even more preferentially from 2% to 30% by weight, relative to the total weight of composition B.

[0345] According to a particular embodiment, the total amount of the aqueous dispersion of acrylic polymer particles preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 50% by weight, even better from 1% to 40% by weight and even more preferentially from 2% to 30% by weight relative to the total weight of composition B.

[0346] The total amount of (poly)carbodiimide compounds is preferably in the range of 0.01% by mass to 40% by mass, more preferentially 0.1% by mass to 30% by mass, even better 0.5% by mass to 20% by mass, and even more preferentially 1% by mass to 12% by mass, relative to the total mass of composition E.

[0347] The total amount of compounds containing at least one carboxylic acid functional group is preferably in the range of 0.2% to 60% by weight, more preferentially 1% to 40% by weight, even more preferably 1% to 30% by weight, and even more preferentially 2% to 20% by weight, relative to the total weight of composition F.

[0348] The total amount of aqueous dispersion of particles of polymers chosen from polyurethanes, acrylic polymers, and mixtures thereof preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 50% by weight, even more preferably from 1% to 40% by weight, and even more preferentially from 2% to 30% by weight, relative to the total weight of composition F.

[0349] According to a particular embodiment, the total amount of aqueous dispersion of acrylic polymer particles preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 50% by weight, even better from 1% to 40% by weight and even more preferentially from 2% to 30% by weight relative to the total weight of composition F.

[0350] Multi-compartment devices (kits) The present invention also relates to a device for dyeing keratinous hair fibers, comprising: In a first compartment, composition A comprising: (1) a composition comprising at least one (poly)carbodiimide compound as described above; In a second compartment, composition B comprising: (2) a composition comprising at least one compound containing at least one carboxylic acid functional group, as described above; and Composition A and / or Composition B comprise at least one colorant selected from pigments, direct dyes and mixtures thereof as defined above; In a third compartment, composition E comprising: (3) a composition comprising at least one (poly)carbodiimide compound as described above; In a fourth compartment, composition F comprising: (4) As previously described, it includes several compartments that contain a composition that includes at least one compound that contains at least one carboxylic acid functional group.

[0351] The present invention also provides a system for dyeing keratinous hair fibers, comprising a first device and a second device, - The first device is In a first compartment, composition A comprising: (1) a composition comprising at least one (poly)carbodiimide compound as described above; In a second compartment, composition B comprising: (2) a composition comprising at least one compound containing at least one carboxylic acid functional group, as described above; and Composition A and / or Composition B comprise at least one colorant selected from pigments, direct dyes and mixtures thereof as defined above; - The second device In a first compartment, composition E comprising: (3) a composition comprising at least one (poly)carbodiimide compound as described above; In a second compartment, composition B comprising: (4) A system, as described above, comprising a composition comprising at least one compound containing at least one carboxylic acid functional group.

[0352] The present invention will now be explained in more detail by means of examples, which in no way limit the scope of the invention, but which make it possible to support certain features, variants and preferred embodiments of the invention. [Example]

[0353] The (poly)carbodiimides of the present invention can be obtained via synthetic methods known to those skilled in the art, starting from commercially available products or reagents that can be synthesized according to chemical reactions known to those skilled in the art, for example, in the book Sciences of Synthesis - Houben-Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag KG, Rüdigerstrasse 14, D-70469 Stuttgart, or in U.S. Pat. No. 4,284,730 or Canadian Patent Application No. 2,509,861.

[0354] More specifically, the process for preparing the (poly)carbodiimide of the present invention comprises, in a first step, reacting a diisocyanate reagent (1): O=C=N-L1-N=C=O(1), (wherein L1 is as defined above) in the presence of a carbodiimidization catalyst (2) such as those described in U.S. Pat. No. 4,284,730, particularly a phosphorus-based catalyst, particularly one selected from phospholene oxides and phospholene sulfoxides, diaza- and oxaza-phosphoranes, preferably in an inert atmosphere (nitrogen or argon), particularly preferably in an aprotic polar solvent such as THF, glyme, diglyme, 1,4-dioxane or DMF, at a temperature between room temperature and the reflux temperature of the solvent, preferably about 140° C., to produce a carbodiimide diisocyanate compound (3): O=C=N-L1-(N=C=N-L1) n -N=C=O(3), (3) wherein L1 and n are as defined above. A benzoyl halide such as benzoyl chloride may be added to deactivate the catalyst.

[0355] In the second step of this preparation process, to obtain a "symmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 eq.) of the nucleophilic reagent R1-X1-H, followed by 0.5 eq. of the reagent HEH (wherein R1, X1 and E are as defined above), to give the "symmetric" compound (4) according to the invention: [R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)]2-E(4), (In formula (4), R1, X1, L1, n, and E are as defined above.) According to one variant to obtain compound (4) from (3), it is possible to first add 0.5 eq. of the reagent HEH, followed by 1 eq. of the reagent R1-X1-H.

[0356] In the second step of this preparation process, to obtain an "unsymmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 eq.) of the nucleophilic reagent R1-X1-H, and then with 1 eq. of the reagent HEH (wherein R1, X1 and E are as defined above), to give compound (5): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EH(5), (In formula (5), R1, X1, L1, n, and E are as defined above.) get.

[0357] According to one variant to obtain compound (5) from (3), it is possible to first add 1 eq. of reagent R1-X1-H, followed by 0.5 eq. of reagent HEH. In the third step, compound (5) is reacted with 1 equivalent of compound (6): R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O (6) (the compound (6) is a compound (3'): O=C=N-L1-(N=C=N-L1) z -N=C=O(3'), (wherein L1 and z are as defined above) with 1 eq. of a nucleophilic reagent R2-X2-H (wherein L1, R2, X2 and z are as defined above) to give the asymmetric compound (7): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EC(O)-NH-L1-(N=C=N-L1) z -NH-C(O)-X2-R2(7), (wherein R1, X1, L1, R2, X2, n, z and E are as defined above) is obtained.

[0358] 1 molar equivalent of the compound O=C=N-L1-(N=C=N-L1) z-N=C=O (3') is reacted with 1 / w molar equivalent of HEH, followed by reaction with 1 eq. of nucleophile R2-X2-H to give compound (8): H-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NH-C(O)-X2-R2(8), (wherein L1, R2, X2, z and E are as defined above, and w is an integer of 1 to 3; more preferentially, w=1) can also be obtained.

[0359] The final compound (8) is then reacted with 1 eq. of compound (4'): R1-X1~C(O)-NH-L1-(N=C=N-L1) n -N=C=O(4') (The compound (4') can be synthesized by reacting 0.5 eq. of a nucleophilic reagent R1-X1-H with 1 eq. of the compound (3)) to obtain the (poly)carbodiimide (9) of the present invention: R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NH C(O)-X2-R2(9), (In formula (9), L1, R1, X1, R2, X2, n, z, w and E are as defined above.)

[0360] The (poly)carbodiimide compounds and all reaction intermediates and reagents as well can be purified by conventional methods known to those skilled in the art, such as extraction with water and water-immiscible organic solvents, precipitation, centrifugation, filtration and / or chromatography.

[0361] Example 1: Method for synthesizing (poly)carbodiimide compounds A 500 mL three-necked round-bottom flask equipped with a thermometer, a stirrer, and a reflux condenser is charged with 50 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphole 1-oxide with stirring.

[0362] 2200-2300 cm by infrared spectroscopy -1 The reaction medium is heated under nitrogen at 140°C for 4 hours, and then cooled to 120°C, while the reaction is monitored by the absorption of isocyanate groups.

[0363] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol is introduced into the reaction medium with stirring. -1 The temperature is monitored and maintained at 120°C until the isocyanate groups have completely disappeared, and then cooled to room temperature.

[0364] After cooling to room temperature, the reaction medium is added dropwise, with vigorous stirring, to a 500 mL glass beaker containing 85 g of distilled water, to obtain the desired product in the form of a translucent yellow liquid.

[0365] Example 2 Compositions A and B described in Tables 1 and 2 below were prepared: amounts are expressed as g / 100g of starting material obtained unless otherwise stated.

[0366] [Table 1]

[0367] (1) Synthesized according to the synthesis process described in Example 1 (containing 40% active substance in water); (2) SEPPIC sells it under the name Sepinov EMT10 (containing 90% of the active material), (3) Sold by Wacker under the name Belsil ADM LOG 1 (containing 15% active material).

[0368] [Table 2]

[0369] (4) Daito Kasei Kogyo Co., Ltd. (Daito Kasei Kogyo) sells it under the trade name Daitosol 3000SLPN-PE1 (aqueous dispersion containing 30% active substance). (5) Sold by Roehm & Haas under the trade name Aculyn 22® (oxyalkylenated methacrylic acid / ethyl acrylate / stearyl methacrylate terpolymer containing 30% active material)

[0370] Composition A was then mixed with composition B in a 50 / 50 weight ratio to obtain composition C according to the present invention.

[0371] Compositions E and F were prepared as set out in Tables 3 and 4 below: amounts are expressed as g / 100g of starting material obtained unless otherwise stated.

[0372] [Table 3]

[0373] [Table 4]

[0374] Composition E was then mixed with composition F in a 50 / 50 weight ratio to obtain composition G according to the present invention.

[0375] protocol Three application processes were used.

[0376] According to a first method, known as Method P1, Composition C was manually applied to tresses of dry natural keratin hair fibers containing 90% white keratin hair fiber strands using a brush at a rate of 0.8 g of composition per gram of tress. The keratin hair fiber tresses were then detangled, dried with a hair dryer, and then combed. Drying with a hair dryer was carried out at a temperature of 100°C.

[0377] This is therefore a comparative process.

[0378] According to a second method, known as Method P2, Composition C was applied manually using a brush to a mass of dry natural keratin hair fibers containing 90% white keratin hair fiber strands, at a rate of 0.8 g of composition per gram of mass. The keratin hair fiber strands were then detangled, dried with a hair dryer, and then combed. Drying with a hair dryer was carried out at a temperature of 100°C.

[0379] Next, Composition G was manually applied to a tress of dry natural keratin hair fibers containing 90% white keratin hair fiber strands using a brush, at a rate of 0.8 g of composition per gram of tress.The tress of keratin hair fibers was then detangled, dried with a hair dryer, and then combed.Drying with a hair dryer was carried out at a temperature of 100°C.

[0380] This is therefore the method according to the invention.

[0381] The process applied is summarized in Table 5 below.

[0382] [Table 5]

[0383] The keratin hair fibre tresses treated by steps P1 and P2 were then subjected to a test consisting of several repeated shampoo washes to assess the resistance (durability) of the colouring agent obtained to shampoo washes, according to the shampoo wash protocol described below.

[0384] Shampoo Wash Protocol: The keratin hair fiber tresses are combed, moistened with water at 35°C, and then passed through the fingers 5 times for 5 seconds. The keratin hair fiber tresses are then squeezed between two fingers and dried.

[0385] A standard shampoo (Garnier Ultra Doux) is applied evenly to the dyed tresses at a rate of 0.4 g of standard shampoo per gram of tress and the keratin hair fiber tresses are gently massaged from root to end along their length (6 passes) for 15 seconds.

[0386] The keratin hair fiber tress is then placed on a watch glass and allowed to stand for 1 minute.

[0387] The keratin hair fiber tresses are then rinsed with water while passing them through the fingers (15 passes).The keratin hair fiber tresses are then squeezed dry between two fingers before the next shampoo wash.

[0388] After several shampoo washes have been tested, the keratin hair fibre tresses are combed and dried with a hair dryer.

[0389] result The color persistence of the tresses was evaluated using the CIE L*a*b* system using a Minolta CM3610A spectrophotometer (illuminant D65, angle 10°, including specular component).

[0390] In this L*a*b* system, L* represents the intensity of the color, a* indicates the green / red axis, and b* indicates the blue / yellow axis.

[0391] The persistence of the colour is assessed by the colour difference ΔE between measurements taken on a dyed tress before shampooing and then after five shampooings according to the protocol described above. The lower the ΔE value, the better the persistence of the colour to shampooing.

[0392] The ΔE value is calculated according to the following formula:

number

[0393] where L*, a*, b* represent measurements taken on keratin hair fibers after dyeing and after shampooing, and L0*, a0*, b0* represent measurements taken on keratin hair fibers after dyeing and before shampooing.

[0394] [Table 6]

[0395] A tress of keratinous hair fibres treated by the method P2 according to the invention and washed with 5 shampoo washes has a significantly lower colour difference than a tress of keratinous hair fibres treated by the comparative method P1.

[0396] The pigmented coatings obtained by the process according to the invention therefore exhibit improved resistance to shampoo washing.

Claims

1. 1. A method for dyeing keratinous hair fibers, comprising: a) at least one (poly)carbodiimide compound, at least one compound containing at least one carboxylic acid function; and applying at least one composition C to said keratinous hair fibres, comprising at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; then b) subjecting said keratin hair fibers to heat at a temperature of 30°C or higher; then c) at least one (poly)carbodiimide compound, - applying to said keratinous hair fibres at least one composition G comprising at least one compound containing at least one carboxylic acid functional group; and d) optionally applying heat to said keratinous hair fibers at a temperature of 30°C or higher. A method comprising:

2. The (poly)carbodiimide compound is a compound of the following formula (I): 【Chemistry 1】 (In the formula, -X １ and X ２ independently represent an oxygen atom O, a sulfur atom S, or an NH group; -R １ and R ２ are independently selected from hydrocarbon-based groups, preferably alkyl, optionally interrupted by one or more heteroatoms; alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxides, such as propylepoxide or butylepoxide, and azacyclopropane groups; and one or more represents a hydrocarbon-based group, preferably a group selected from alkyl, optionally interrupted by one or more groups selected from the above heteroatoms and alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, for example propylepoxide or butylepoxide, and azacyclopropane groups; n represents an integer ranging from 1 to 1000; and A is the following compound: 【Chemistry 2】 is a monomer selected from The method of claim 1, wherein the compound is selected from the group consisting of:

3. The (poly)carbodiimide compound is a compound of the following formula (II): 【Transformation 3】 (In the formula, -X １ and X ２ independently represent an oxygen atom O, a sulfur atom S, or an NH group; -R １ and R ２ independently represent a hydrocarbon-based group optionally interrupted by one or more heteroatoms; n and z represent integers ranging from 1 to 20, where n+z≧2, and w represents an integer ranging from 1 to 3; - L １ are independently divalent C １ ~C １８ Aliphatic hydrocarbon group, C ３ ~C １５ Cycloalkylene group, C ３ ~C １２ Heterocycloalkylene group or C ６ ~C １４ represents arylene groups and mixtures thereof; - E independently -O-R ３ -O-;-S-R ４ -S-;-R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ -; (where R ３ and R ４ independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; -R ５ independently represent a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; -R ６ independently represent a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms. represents a group selected from The method of claim 1, wherein the compound is selected from the group consisting of:

4. The (poly)carbodiimide compound is selected from compounds of formula (II): -X １ and X ２ independently represent an oxygen atom; -R １ and R ２ are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, from which the hydroxyl groups have been removed, and mixtures thereof; n and z represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L1 is C １ ~C １８ a divalent aliphatic hydrocarbon group represented by C ３ ~C １５ Cycloalkylene group, C ３ ~C １２ Heterocycloalkylene group or C ６ ~C １４ arylene groups and mixtures thereof; - E independently -O-R ３ -O-;-S-R ４ -S-;-R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ -; wherein R and R independently represent a C group optionally interrupted by one or more heteroatoms. ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups and mixtures thereof; -R ５ is not a covalent bond, R ５ is optionally interrupted by one or more heteroatoms, ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups and mixtures thereof; and -R ６ optionally interrupted by one or more heteroatoms, C ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ 4. The method of claim 3, wherein the aryl group represents a group selected from the group consisting of alkylene groups and mixtures thereof.

5. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ independently represent an oxygen atom; -R １ and R ２ are independently monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed; n and z represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L １ But C ３ ~C １５ is a cycloalkylene group; - E independently -O-R ３ -O-;-S-R ４ -S-;-R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - (In the formula, R ３ and R ４ are independently C optionally interrupted by one or more heteroatoms ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups and mixtures thereof; -R ５ is not a covalent bond, R ５ is optionally interrupted by one or more heteroatoms, ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups and mixtures thereof; and -R ６ is optionally interrupted by one or more heteroatoms, ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ 5. The method of claim 3 or 4, wherein R represents a group selected from the group consisting of alkylene groups and mixtures thereof.

6. The (poly)carbodiimide compound is selected from compounds of formula (II): -X １ and X ２ independently represent an oxygen atom; -R １ and R ２ are independently represented by the following formula (VI): R １３ -[O-H ２ -C(H)(R １４ )] ｑ - (VI) (In the formula, R １３ is C １ ~C ４ alkyl group or phenyl, preferably C １ ~C ４ represents an alkyl group, more preferably methyl, R １４ is a hydrogen atom or C １ ~C ４ represents an alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30. represents a compound of formula (I); n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10 and w is equal to 1; - L １ However, C cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane ３ ~C １５ is a cycloalkylene group; and - E is -O-R ３ -O- group (in the formula, R ３ is optionally interrupted by one or more heteroatoms, ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ 6. The method according to claim 3, wherein the aryl group is selected from alkylene groups and mixtures thereof.

7. The (poly)carbodiimide compound is selected from compounds of formula (II): -X １ and X ２ independently represent an oxygen atom; -R １ and R ２ are independently represented by the following formula (VI): R １３ -[O-H ２ -C(H)(R １４ )] ｑ - (VI) (In the formula, R １３ is C １ ~C ４ alkyl group or phenyl, preferably C １ ~C ４ represents an alkyl group, more preferably methyl, R １４ is a hydrogen atom or C １ ~C ４ represents an alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30. represents a compound of formula (I); n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10 and w is equal to 1; - L １ C cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane ３ ~C １５ a cycloalkylene group, preferably 4,4-dicyclohexylenemethane; - E is -O-R ３ -O- group (in the formula, R ３ is a straight or branched C alkyl group such as methylene, propylene, butylene, or ethylene, optionally interrupted by one or more heteroatoms; １ ~C １８ The method according to any one of claims 3 to 6, wherein R represents an alkylene group.

8. The (poly)carbodiimide compound is a compound of the following formula (XII): 【Chemistry 4】 (In the formula, L １ is 4,4-dicyclohexylenemethane, n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10, and E is -O-R ３ -O- group (in the formula, R ３ is a straight or branched C alkyl group such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms; １ ~C １８ an alkylene group), and r and s represent integers ranging from 4 to 30. The method according to any one of claims 3 to 7, wherein the compound is selected from the group consisting of:

9. 9. The method according to any one of claims 1 to 8, wherein the total amount of (poly)carbodiimide compounds 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 even more preferentially from 1% to 6% by weight, relative to the total weight of composition C.

10. 10. The method according to any one of claims 1 to 9, wherein the total amount of (poly)carbodiimide compounds 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 even more preferentially from 1% to 6% by weight, relative to the total weight of composition C.

11. 11. The method according to any one of claims 1 to 10, wherein the compound comprising at least one carboxylic acid functional group is selected from silicone compounds comprising at least one carboxyl group, polyurethanes, acrylic polymers and mixtures thereof.

12. 12. The method according to any one of claims 1 to 11, wherein said compound containing at least one carboxylic acid function is in the form of an aqueous dispersion of particles of a polymer chosen from polyurethanes, acrylic polymers and mixtures thereof, preferably in the form of an aqueous dispersion of acrylic polymer particles, more preferentially in the form of an aqueous dispersion of film-forming acrylic polymer particles.

13. The acrylic polymer may comprise the following monomers: a) (meth)acrylic acid; and b) C １ ~C ３０ , more preferentially C １ ~C ２０ , or better C １ ~C １０ , more specifically C １ ~C ４ One or more units derived from alkyl (meth)acrylate 13. The method of claim 12, comprising:

14. 14. The method according to any one of the preceding claims, wherein the total amount of said compounds comprising at least one carboxylic acid function ranges from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferentially from 1% to 15% by weight, and even more preferably from 2% to 10% by weight relative to the total weight of composition C.

15. 15. The method according to any one of the preceding claims, wherein the total amount of said compounds comprising at least one carboxylic acid function ranges from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferentially from 1% to 15% by weight, and even more preferably from 2% to 10% by weight relative to the total weight of composition C.

16. 14. The method according to claim 12 or 13, wherein the total amount of said aqueous dispersion of particles of polymer chosen from polyurethanes, acrylic polymers and mixtures thereof preferably ranges from 0.1% to 40% by weight, more preferentially from 0.5% to 30% by weight, even more preferentially from 1% to 25% by weight and even more preferentially from 2% to 20% by weight relative to the total weight of composition C.

17. 17. The method according to any one of claims 12, 13 and 16, wherein the total amount of said aqueous dispersion of particles of polymer chosen from polyurethanes, acrylic polymers and mixtures thereof ranges from 0.1% to 40% by weight, more preferentially from 0.5% to 30% by weight, even more preferentially from 1% to 25% by weight and even more preferentially from 2% to 20% by weight relative to the total weight of composition G.

18. 18. The method according to any one of the preceding claims, wherein the total amount of said colorants chosen from pigments, direct dyes and mixtures thereof ranges from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, relative to the total weight of composition C.

19. 19. The method according to any one of the preceding claims, wherein step b) comprises drying the keratinous hair fibres at a temperature ranging from 30 to 150°C, preferably from 30 to 110°C, more preferentially from 50 to 110°C.

20. 20. The method according to any one of the preceding claims, wherein step b) comprises straightening with a straightening iron at a temperature ranging from 100 to 250°C, preferably from 150 to 220°C, more preferentially from 180 to 220°C.

21. The method according to any one of claims 1 to 20, wherein said composition G does not contain a colorant selected from pigments, direct dyes and mixtures thereof.

22. The process according to any one of the preceding claims, wherein the temperature during step d) is in the range of from 30 to 250°C, preferably from 50 to 220°C.

23. step a) consists, at the time of use, in extemporaneously mixing at least two compositions A and B to obtain composition C, and applying composition C to said keratinous hair fibres, composition A comprises at least one (poly)carbodiimide compound according to any one of claims 1 to 8; composition B comprises at least one compound containing at least one carboxylic acid function according to any one of claims 1 and 11 to 13, 23. The method according to any one of claims 1 to 22, wherein composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof as defined in claim 1.

24. step c) consists, in use, in extemporaneously mixing at least two compositions E and F to obtain composition G, and applying composition G to said keratinous hair fibres, composition E comprises at least one (poly)carbodiimide compound according to any one of claims 1 to 8; - A method according to any one of claims 1 to 23, in which composition F comprises at least one compound containing at least one carboxylic acid function according to any one of claims 1 and 11 to 13.

25. 1. A device for dyeing keratinous hair fibers, comprising: * In the first compartment, composition A comprising: (1) A composition comprising at least one (poly)carbodiimide compound according to any one of claims 1 to 8; * In a second compartment, composition B comprising: (2) A composition comprising at least one compound containing at least one carboxylic acid functional group according to any one of claims 1 and 11 to 13; Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof as defined in claim 1; * In a third compartment, composition E comprising: (3) A composition comprising at least one (poly)carbodiimide compound according to any one of claims 1 to 8; * In a fourth compartment, composition F comprising: (4) A device comprising several compartments containing a composition comprising at least one compound containing at least one carboxylic acid functional group according to any one of claims 1 and 11 to 13.

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