Method for dyeing keratinous hair fibers, comprising applying a (poly)carbodiimide compound, a compound containing at least one carboxylic acid group, an aminosilicone, and a colorant

Abstract

The present invention relates to a method for dyeing keratinous hair fibers, comprising applying to the keratinous hair fibers at least one composition C containing a) at least one (poly)carbodiimide compound, b) at least one compound comprising at least one carboxylic acid group, c) at least one aminosilicone of formula (XIII), and d) at least one colorant chosen from pigments, direct dyes, and mixtures thereof.

Description

[Technical Field]

[0001] The present invention relates to a method for dyeing keratinous hair fibers, comprising applying to the keratinous hair fibers at least one composition C containing at least one (poly)carbodiimide compound, at least one compound containing at least one carboxylic acid group, at least one aminosilicone of formula (XIII), and at least one colorant chosen from pigments, direct dyes, and mixtures thereof. [Background technology]

[0002] In the field of dyeing keratin hair fibers, particularly human keratin fibers, it is already known practice to dye keratin hair fibers through various techniques using direct dyes or pigments for non-permanent coloration, or dye precursors for permanent coloration.

[0003] There are three basic processes for dyeing keratin hair fibers: a) "Permanent" dyeing: its function is to significantly modify the original color, this is done using oxidative dyes that penetrate the keratin hair fiber and form dyes through an oxidative condensation process; b) Non-permanent, semi-permanent or direct dyeing: without using the oxidative condensation process, and resistant to 4-5 shampoo washes. This involves dyeing keratin fibers with a dye composition containing a direct dye; c) Temporary dyeing: modifying the natural color of the keratin hair fiber, remaining from one shampoo wash to the next, and serving to enhance or correct the shade already obtained. This is sometimes associated with the "make-up" process.

[0004] Another dyeing method consists in using pigments, specifically on the surface of the keratin fibers, which generally makes it possible to obtain a visible coloration on dark keratin hair fibers, since the surface pigments mask the original color of the fibers. Summary of the Invention [Problem to be solved by the invention]

[0005] However, the coloration obtained by this dyeing method has the drawback that it is not only less resistant to shampooing, but also to external agents such as sebum, sweat, brushing and / or friction.

[0006] Furthermore, temporary keratin hair fiber dye compositions can result in cosmetic properties, and more particularly keratin hair fiber conditioning properties, that are not entirely satisfactory, especially in terms of the softness and smooth feel of the keratin hair fiber.

[0007] Therefore, there remains a need for a method for dyeing keratin hair fibers that produces a uniform colored coating on the keratin hair fiber with improved keratin hair fiber conditioning properties, particularly in terms of the softness and smooth feel of the keratin hair fiber, while at the same time forming a coating that is resistant to shampooing and to the various stresses to which the keratin hair fiber may be subjected, such as brushing and / or rubbing.

[0008] It is therefore an object of the present invention to develop a method for dyeing keratin hair fibers which has the advantage of producing a uniform colored coating on the keratin hair fiber with improved keratin hair fiber conditioning properties, in particular in terms of the suppleness and smooth feel of the keratin hair fiber, while forming a coating which is resistant to shampooing and to the various stresses to which the keratin hair fiber may be subjected, such as brushing and / or rubbing. [Means for solving the problem]

[0009] Thus, one subject of the present invention is a) at least one (poly)carbodiimide compound; b) at least one compound containing at least one carboxylic acid group; and c) at least one aminosilicone of formula (XIII) described hereinafter, d) at least one colorant selected from pigments, direct dyes, and mixtures thereof; A method for dyeing keratinous hair fibers, comprising applying to the keratinous hair fibers at least one composition C containing

[0010] The method for dyeing keratinous hair fibers according to the invention results in a colored coating on the keratinous hair fibers, which makes it possible to obtain a visible coloration on all keratinous hair fiber types and to obtain excellent keratinous hair fiber conditioning properties, in particular in terms of the flexibility and smooth feel of the keratinous hair fibers.

[0011] The resulting colored coating is resistant to shampooing and to external stresses such as blow drying and sweating to which keratinous hair fibers may be subjected.

[0012] For the purposes of the present invention, the term "colour that is resistant to shampooing" means that the colour obtained persists after at least one shampooing, preferably after three shampooings, and more preferentially after five shampooings.

[0013] The term "keratinous hair fibers" refers in particular to keratinous hair fibers or hair. In other words, the expressions "keratinous hair fibers", "hair keratinous fibers" and "hair" are equivalent in the rest of the description.

[0014] For the purposes of the present invention, the term "keratinous hair fibers" refers to keratinous hair fibers of the head. This term does not correspond to body hair, eyebrows, or eyelashes.

[0015] The term "at least one" means one or more.

[0016] Unless otherwise specified, the boundaries of a range of values ​​are encompassed within that range, particularly expressions such as "between" and "ranging from."

[0017] The invention is not limited to the illustrated embodiments, and features of the various embodiments may in particular be combined in variations not illustrated.

[0018] For purposes of the present invention, unless otherwise specified: - "Alkyl" group refers to a straight or branched chain saturated group containing, for example, 1 to 20 carbon atoms; - an "aminoalkyl" group refers to an alkyl group as defined above, wherein said alkyl group contains an NH group; - a "hydroxyalkyl" group refers to an alkyl group as defined above, wherein said alkyl group contains an OH group; - an "alkylene" group refers to a linear or branched saturated C2-C4 hydrocarbon-based divalent group, such as methylene, ethylene, or propylene; - a "cycloalkyl" or "alicycloalkyl" group refers to a cyclic saturated monocyclic or bicyclic, 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, wherein the cycloalkyl group may be optionally substituted with one or more (C1-C4) alkyl groups, such as methyl, in which case it is understood that the cycloalkyl group 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 of the formula: - "aryl" group is a monocyclic, bicyclic or tricyclic, fused or unfused, unsaturated aromatic hydrocarbon-based ring group 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 phenyl may be substituted with one or more (C1-C4) alkyl groups such as methyl, preferably tolyl, xylyl or methylnaphthyl, preferably an aryl group representing phenyl; - "arylene" group is a divalent aryl group with "aryl" as defined above, preferably arylene represents phenylene; - a "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" group is a divalent heterocyclic group having the above-defined "heterocyclic" group; - an "aryloxy" group refers to an aryloxy group having an "aryl" as defined above; - an "alkoxy" group refers to an alkyl-oxy group 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.

[0019] Unless otherwise specified, when a compound is referred to in this patent application, this also includes its optical isomers, its geometric isomers, its tautomers, or its salts, either alone or in mixtures. DETAILED DESCRIPTION OF THE INVENTION

[0020] Polycarbodiimide Compounds The composition C used in connection with the method according to the invention comprises at least one (poly)carbodiimide compound.

[0021] The composition may comprise at least two different (poly)carbodiimide compounds present as a mixture in the composition.

[0022] 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.

[0023] The term "carbodiimide group" refers to a divalent, linear, three-atom moiety of the general formula -(N=C=N)-.

[0024] 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 group.

[0025] 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 different from the carbodiimide group, preferably one or more terminal groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide (e.g., propylepoxide or butylepoxide), and azacyclopropane group.

[0026] According to a particular embodiment, the (poly)carbodiimide compound is selected from the compounds of formula (I) below: [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, preferably alkyl, optionally interrupted by one or more heteroatoms; a 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 an azacyclopropane group; a hydrocarbon-based group, preferably an alkyl group, 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, alkylepoxides, such as propylepoxide or butylepoxide, and azacyclopropane groups; - n represents an integer ranging from 1 to 1000; A is one of the following compounds: [ka] is a monomer selected from

[0027] According to another embodiment, the (poly)carbodiimide compound is selected from the compounds of formula (I') below: [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, 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 the aliphatic or aromatic groups may be partially or fully fluorinated; in this variation, Z1 and Z2 contain a linking group CG connecting Z1 to Y1 and Z2 to Y2, the group CG being 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, branched or cyclic aliphatic, aromatic or alkylaromatic groups linked via repeating carbonate, ester, ether, amide, urethane or urea 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).

[0028] 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.

[0029] Such (poly)carbodiimide compounds are sold, for example, by Stahl BV under the names Permutex XR, RelcaLink 10 or Picassian XL, and by Nisshinbo under the names Carbodilite of 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.

[0030] Preferably, the (poly)carbodiimide compound is selected from the compounds of 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 represents an arylene group and a mixture thereof; - E independently -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).

[0031] The term "hydrocarbon-based group" means a saturated or unsaturated, linear 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 group is a saturated linear group.

[0032] The hydrocarbon-based group may contain one or more cyclic groups.

[0033] The hydrocarbon-based group may be interrupted by one or more heteroatoms selected from O, S or N, in particular, 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 a salt.

[0034] 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 group, this heteroatom is preferably selected from an oxygen O, sulfur S or nitrogen N atom.

[0035] Preferably, X1 and X2 independently represent an oxygen atom.

[0036] Preferably, R1 and R2 are independently selected from dialkylamino alcohols from which the hydroxyl groups have been removed, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof.

[0037] In a preferred embodiment, R1 and R2 are independently selected from the following groups (i) to (iv): (i) a compound of 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, and preferably R7 is methyl, and R8 is a hydrogen atom or methyl). (ii) a compound of 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) (iii) a compound of 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) (iv) a compound of 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).

[0038] Preferably, R1 and R2 independently represent a compound of formula (VI), R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; and q represents an integer in the range of 4-30.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), 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.

[0043] Preferably, n represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0044] Preferably, z represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0045] Preferably, w is equal to one.

[0046] Preferably, w is equal to 1 and n+z represents an integer ranging from 4 to 10.

[0047] Preferably, L1 is a divalent C1-C6 alkyl group such as methylene, ethylene, and propylene. 18Aliphatic hydrocarbon groups, C3-C such as cyclopentylene, cycloheptylene, and cyclohexylene 15 C3-C such as cycloalkylene groups, imidazolene, pyrrolene, and furanylene 12 C6-C such as heterocycloalkylene group or phenylene 14 The aryl group is selected from arylene groups as well as mixtures thereof.

[0048] For example, L1 may be selected from groups 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.

[0049] Preferably, L1 is C3 to C 15 Cycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, such as compounds of formula (VII): [ka] is selected from.

[0050] Preferably, L1 is represented by the following formula (VIII): [ka] The corresponding 4,4-dicyclohexylenemethane is

[0051] According to another embodiment, L1 is C6 to C 14 When L1 is an arylene group, it is represented by the following formula (IX): [ka] It is not an m-tetramethylxylylene group represented by the formula:

[0052] As mentioned earlier, E is independently -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.

[0053] 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 Independently selected from alkylene groups as well as mixtures thereof.

[0054] 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.

[0055] 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 ethylene 18 It is selected from alkylene groups as well as mixtures thereof.

[0056] 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 It is selected from alkylene groups as well as mixtures thereof.

[0057] Preferably, E represents a -O-R3-O- group, where R3 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 The alkylene groups are selected from alkylene groups and mixtures thereof.

[0058] More preferentially, E represents a -O-R3-O- group, where R3 is a linear or branched C1-C6 alkylene, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms. 18 Represents an alkylene group.

[0059] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (X): [ka] (In the formula, 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, n represents an integer ranging from 2 to 100. It is a copolymer derived from α-methylstyryl isocyanate.

[0060] In this embodiment, the term "alkyl group" is as defined above.

[0061] In this embodiment, the term "cycloalkyl group" is as defined above.

[0062] 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.

[0063] 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

[0064] The "alkyl group", "cycloalkyl group" and "aryl group" are as defined above.

[0065] According to a preferred embodiment, the (poly)carbodiimide compound is selected from compounds of formula (I) or formula (II), in which: 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, - when n and z are present, they 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-C12 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 independently represent a group selected from C6-C 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; - 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 The alkylene groups are selected from alkylene groups and mixtures thereof.

[0066] Preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein X1 and X2 independently represent an oxygen atom; R1 and R2 are independently selected from dialkylamino alcohols from which the hydroxyl groups have been removed, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof; n and z represent integers ranging from 1 to 20, 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 independently represent a group selected from C6-C 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; 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 The alkylene groups are selected from alkylene groups and mixtures thereof.

[0067] More preferentially, the (poly)carbodiimide compound is chosen from compounds of formula (II), in which X1 and X2 independently represent an oxygen atom; R1 and R2 are independently a monoalkyl ether of a (poly)alkylene glycol from which a hydroxyl group has been removed; n and z represent integers ranging from 1 to 20, n+z≧2, and w is equal to 1; - L1 is C3~C 15 is a cycloalkylene group, - E independently -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- wherein R3 and R4 independently represent a group selected from C6-C 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; 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 The alkylene groups are selected from alkylene groups and mixtures thereof.

[0068] Even more preferentially, the (poly)carbodiimide compound is chosen from compounds of formula (II), in which 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) represents a compound of 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; q represents an integer ranging from 4 to 30; n and z represent integers ranging from 1 to 20, n+z ranging 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 group, - 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 groups are selected from alkylene groups and mixtures thereof.

[0069] Even more preferentially, the (poly)carbodiimide compound is chosen from compounds of formula (II), in which 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) represents a compound of 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; q represents an integer ranging from 4 to 30; n and z represent integers ranging from 1 to 20, n+z ranging 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 a 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 Represents an alkylene group.

[0070] 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, n+z is in the range of 4 to 10, E represents an -O-R3-O- group, 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 represents an alkylene group, and r and s represent integers ranging from 4 to 30. is a compound of

[0071] 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.

[0072] Compounds containing at least one carboxylic acid group Composition C used in connection with the dyeing process according to the invention comprises (ii) at least one compound containing at least one carboxylic acid group.

[0073] Preferably, the compound containing at least one carboxylic acid group is selected from silicone compounds containing at least one carboxyl group, polyurethanes, acrylic polymers, and mixtures thereof.

[0074] Polyurethane and acrylic polymers: According to a preferred embodiment, composition C comprises at least one compound containing at least one carboxylic acid group chosen from polyurethanes, acrylic polymers, and mixtures thereof.

[0075] Preferably, the compound containing at least one carboxylic acid group is in the form of an aqueous dispersion of particles of a polymer selected from polyurethanes, acrylic polymers, and mixtures thereof.

[0076] Preferably, composition C comprises at least one compound containing at least one carboxylic acid group in the form of an aqueous dispersion of particles of polyurethanes, acrylic polymers, and mixtures thereof.

[0077] The dispersion may be a simple dispersion of the cosmetic composition in an aqueous medium. A particular example of a dispersion is a latex.

[0078] The aqueous dispersion of polymer particles may be selected from aqueous dispersions of polyurethane particles.

[0079] More specifically, the polyurethane present in the aqueous dispersion used in the present invention is - 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 the radical of a low molecular weight diol optionally substituted with one or more ionic groups, - n represents an integer ranging from 1 to 5; - m is greater than 1) 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. and at least one chain extender according to - the following formula (C): H2N-R5-NH2(C) wherein R5 represents an alkylene group substituted with one or more ionic or potentially ionic groups. with at least one chain extender.

[0080] 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 high molecular weight dihydroxylated compounds 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.

[0081] 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.

[0082] 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.

[0083] 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(isocyanatomethyl)cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)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 isomer diphenylmethane 2,4-diisocyanate with, optionally, diphenylmethane 2,2'-diisocyanate, naphthalene 1,5-diisocyanate, and mixtures thereof.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] The prepolymer is chain extended by using chain extenders belonging to two groups: The first group of chain extenders corresponds to compounds of general formula (B):

[0090] 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.

[0091] 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 may optionally contain two groups that react with isocyanate groups and one group that is ionic or capable of forming an ionic group.

[0092] 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. Conversion of at least a portion of the groups that can be converted into salts of tertiary or quaternary ammonium groups may be carried out before or during mixing with water.

[0093] 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.

[0094] The polyurethanes that can be used according to the invention can also optionally contain compounds (chain terminators) located at each chain end to terminate 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.

[0095] 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.

[0096] 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 still 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 still from 30% to 50% by weight, relative to the total weight of the dispersion.

[0097] Also preferably, the glass transition temperature (Tg) of the aqueous dispersion of polyurethane particles is lower than or equal to -25°C, preferably lower than -35°C and more preferentially lower than -40°C.

[0098] The average size of the polyurethane particles may be up to about 1000 nm, for example, in the range of about 50 nm to about 800 nm, and even better, about 100 nm to about 500 nm. These particle sizes can be measured using a laser particle size distribution analyzer (e.g., Brookhaven BI90).

[0099] 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).

[0100] 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).

[0101] 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.

[0102] Preferably, the compound containing at least one carboxylic acid group 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.

[0103] For the purposes of the present invention, the term "polymer" means a compound corresponding to the repetition of one or more units, which are derived from compounds known as monomers, which or these units are repeated at least twice, preferably at least three times.

[0104] The term "film-forming polymer" refers to a polymer that is capable of forming a macroscopically continuous film, preferably a coherent film, on a substrate, in particular on keratinous materials such as keratinous hair fibers, either alone or in the presence of an auxiliary film-forming agent.

[0105] 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.

[0106] 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.

[0107] 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 , and even better C1~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.

[0108] 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.

[0109] Among the hydroxyalkyl(meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0110] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0111] 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 and even more particularly C1 to C4 alkyl (meth)acrylates.

[0112] According to the present invention, the alkyl group of the ester may be fluorinated or even perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms.

[0113] 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.

[0114] The acrylic polymer according to the invention may be a homopolymer or a copolymer, advantageously a copolymer, even better a copolymer of (meth)acrylic acid and a (meth)acrylic acid ester.

[0115] 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 , and even better C1~C 10 , more particularly C1-C4 alkyl (meth)acrylates; It contains one or more units derived from

[0116] Preferably, the aqueous dispersion of acrylic polymer particles is surfactant-free.

[0117] The term "surfactant" refers to any agent that can modify the surface tension between two surfaces.

[0118] 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 acrylate polymer, such as the compound sold by Daito Chemical Industry Co., Ltd. under the trade name Daitosol 3000 SLPN-PE1 or Daitosol 3000SLPN-SD.

[0119] 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.

[0120] Additional monomers include, for example, styrene monomers, particularly styrene and α-methylstyrene, preferably styrene.

[0121] 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.

[0122] 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.

[0123] Among the acrylic polymers, mention may be made of styrene / (meth)acrylate copolymers sold under the names Joncryl 77 by BASF, Yodosol GH41F by Akzo Nobel and Syntran 5760 CG by Interpolymer.

[0124] Preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles.

[0125] More preferentially, composition C comprises the following monomers: a) (meth)acrylic acid; and b) C1~C 30 , and more preferentially C1~C 20 , and even better C1~C 10 , more particularly C1-C4 alkyl (meth)acrylates; The composition comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more units derived from:

[0126] Preferably, the acrylic polymer (or active substance or solids) content of the aqueous dispersion of acrylic polymer particles is from 20% to 60% by weight, more preferentially from 22% to 55% by weight, and even better from 25% to 50% by weight, based on the weight of the dispersion.

[0127] Silicone Acrylic Copolymer According to a particular embodiment, the silicone compound comprising at least one carboxyl group is chosen from silicone acrylic copolymers.

[0128] Thus, according to a particular embodiment, the compound comprising at least one carboxyl function is chosen from silicone acrylic copolymers.

[0129] Preferably, the silicone acrylic copolymer comprises: at least one acrylic or methacrylic or crotonic unit, - at least one polydimethylsiloxane (PDMS) unit, Includes:

[0130] For the purposes of the present invention, the term "polydimethylsiloxane" (also abbreviated as PDMS) means, according to the generally accepted definition, any organosilicon polymer or oligomer with a linear structure of variable molecular weight, obtained by polymerization and / or polycondensation of appropriately functionalized silanes, essentially consisting of repeating main units in which silicon atoms are linked together through oxygen atoms (siloxane bond Si-O-Si), and which contain methyl groups bonded directly to said silicon atoms through carbon atoms.

[0131] The PDMS chains that can be used to obtain the copolymers used in accordance with the present invention preferably contain at least one polymerizable radical group located at at least one of the chain ends, i.e., the PDMS can have, for example, a polymerizable radical group at each of the two chain ends, or one polymerizable radical group at one end of the chain and one trimethylsilyl end group at the other end of the chain.

[0132] 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.

[0133] Preferably, the polymerizable radical group comprises at least one vinyl group.

[0134] 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.

[0135] 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 carboxyl group.

[0136] The term "carboxyl group" means a COOH or COO-functional group, the counterion of which can be selected from alkali metals, alkaline earth metals, and quaternary ammonium.

[0137] Preferably, the silicone acrylic copolymer comprises: at least one acrylic or methacrylic or crotonic unit and at least one acrylic or methacrylic or vinyl ester unit; and - at least one polydimethylsiloxane (PDMS) unit; Includes:

[0138] More preferentially, the composition comprises: - at least one unit selected from at least one croton unit and an alkyl crotonate unit, wherein the alkyl group is a linear or branched saturated group containing 1 to 20 carbon atoms; a vinyl acetate unit; a vinyl alkyl ester unit, wherein the alkyl group is a linear or branched saturated group containing 2 to 20 carbon atoms; and mixtures thereof; and - at least one polydimethylsiloxane (PDMS) unit; The silicone-acrylic copolymer contains one or more silicone acrylic copolymers including:

[0139] The term "crotonic unit" means a unit derived from a crotonic acid monomer or a salt thereof.

[0140] 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.

[0141] 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.

[0142] The term "vinyl acetate units" means units derived from vinyl acetate monomers.

[0143] 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 group being a saturated, linear or branched group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms, and - at least one polydimethylsiloxane (PDMS) unit, Includes:

[0144] 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, the alkyl group being a linear or branched saturated group containing 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:

[0145] 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 group being a saturated, linear or branched group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms, and - at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable radical group containing at least one vinyl group, The silicone acrylic copolymer comprises one or more silicone acrylic copolymers including:

[0146] 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, the alkyl group being a saturated, linear or branched group 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, The silicone acrylic copolymer comprises one or more silicone acrylic copolymers including:

[0147] Among the silicone acrylic copolymers that may be used in the context of 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.

[0148] The total amount of compounds containing at least one carboxylic acid group is preferably in the range of 0.1% to 30% by weight, more preferentially 0.5% to 20% by weight, even better still 0.5% to 15% by weight, and even more preferentially 1% to 10% by weight, relative to the total weight of composition C.

[0149] The total amount of aqueous dispersion of polymer particles chosen from polyurethanes, acrylic polymers and mixtures thereof preferably ranges from 0.1% to 50% by weight, more preferentially from 0.5% to 40% by weight, even better from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of composition C.

[0150] According to a particular embodiment, the total amount of aqueous dispersion of acrylic polymer particles preferably ranges from 0.1% to 50% by weight, more preferentially from 0.5% to 40% by weight, even better from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of composition C.

[0151] Advantageously, the total amount of silicone acrylic copolymer 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 preferentially from 2% to 10% by weight relative to the total weight of composition C.

[0152] Aminosilicones of formula (XIII) The composition C used in connection with the dyeing process according to the invention contains at least one aminosilicone of formula (XIII) below: [ka] (In the formula, R1 independently represents a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms; R2 independently represents a group of formula -C q H 2q represents a monovalent group of L, where q is a number ranging from 2 to 8, and L is optionally selected from the group: -N(R3)2;-N+(R3)3A - ;-NR3-YN(R3)2, and -NR-Y-N+(R3)3A - is a quaternized amine group selected from In the formula, R3 may be the same or different and is a hydrogen atom, a phenyl group, a benzyl group, or a monovalent saturated hydrocarbon group, for example, a C1-C 20 represents an alkyl group; Y represents a group of formula C r H 2r represents a linear or branched group, and r is an integer ranging from 2 to 6, preferably from 2 to 4; - represents a cosmetically acceptable anion, especially a halide, such as fluoride, chloride, bromide, or iodide; X represents the following formula (XIV): [ka] represents a group corresponding to the formula: - A independently represents a linear or branched alkylene group containing 1 to 10 carbon atoms, optionally interrupted by at least one heteroatom selected from O, S, NH, or a carbonyl group (CO), preferably NH; Q represents an alkylene group containing 1 to 20 carbon atoms, said alkylene group being optionally substituted with at least one alkoxy group containing 1 to 10 carbon atoms, a hydroxyl group, or an aminoalkyl group containing 1 to 20 carbon atoms; - n represents an integer in the range of 0 to 500, m represents an integer in the range of 1 to 500, o represents an integer in the range of 0 to 500, and n+m+o is in the range of 250 to 500).

[0153] The term "aminosilicone" refers to any silicone that contains at least one primary, secondary, or tertiary amine or quaternary ammonium group.

[0154] The weight average molecular weight of these aminosilicones can be measured by gel permeation chromatography (GPC) at room temperature (25°C) in terms of polystyrene. The column used is a μ-styragel column. The eluent is THF, and the flow rate is 1 ml / min. 200 μl of a solution containing 0.5% by weight of silicone in THF is injected. Detection is performed by refractive index measurement and UV measurement.

[0155] According to a preferred embodiment, the aminosilicone of formula (XIII) is: R1 independently represents a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms; - R2 independently represents a group of formula -C q H 2q represents a monovalent group of L, where q is a number in the range of 2 to 8, and L is optionally a group: -N(R3)2; -N(R3)-CH2-CH2-N(R3)2; wherein R3 may be the same or different and is a hydrogen atom, a phenyl group, a benzyl group, or a monovalent saturated hydrocarbon group, such as a C1-C 20 represents an alkyl group; X is of the following formula (XIV): [ka] represents a group corresponding to the formula: - A independently represents a linear or branched alkylene group containing 1 to 6 carbon atoms, optionally interrupted by at least one heteroatom selected from O, S, NH, or a carbonyl group (CO), preferably NH; - Q represents an alkylene group containing 1 to 10 carbon atoms, said alkylene group being optionally substituted with at least one alkoxy group containing 1 to 10 carbon atoms, a hydroxyl group, or an aminoalkyl group containing 1 to 20 carbon atoms; - n represents an integer ranging from 0 to 500, m represents an integer ranging from 1 to 500, o represents an integer ranging from 0 to 500, and n+m+o is in the range from 250 to 500; It is something.

[0156] According to a more preferred embodiment, the aminosilicone of formula (XIII) is: R1 independently represents a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms; - R2 independently represents a group of formula -C q H 2q represents a monovalent group of L, where q is a number ranging from 2 to 8, and L is a group represented by the following formula: -N(R3)-CH2-CH2-N(R3)2; is an amine group having In the formula, R3 represents a hydrogen atom. X is of the following formula (XV): [ka] represents a group corresponding to the formula: - Q represents an alkylene group containing 1 to 10 carbon atoms, said alkylene group being optionally substituted with at least one alkoxy group containing 1 to 10 carbon atoms, a hydroxyl group, or an aminoalkyl group containing 1 to 20 carbon atoms; - n represents an integer ranging from 0 to 500, m represents an integer ranging from 1 to 500, o represents an integer ranging from 0 to 500, and n+m+o is in the range from 250 to 500; It is something.

[0157] According to a more preferred embodiment, the aminosilicone is of the following formula (XVI): [ka] (In the formula, R1 independently represents a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms; Q represents an alkylene group containing 1 to 10 carbon atoms, said alkylene group being optionally substituted with at least one alkoxy group containing 1 to 10 carbon atoms, a hydroxyl group, or an aminoalkyl group containing 1 to 20 carbon atoms; - n represents an integer in the range of 0 to 500, m represents an integer in the range of 1 to 500, o represents an integer in the range of 0 to 500, and n+m+o is in the range of 250 to 500).

[0158] According to a particular embodiment, the aminosilicone of formula (XIII) is present in an emulsion or microemulsion together with a surfactant, preferably a non-ionic surfactant such as Trideceth-10.

[0159] Among the aminosilicones of formula (XIII) that can be used in composition C, mention may be made of the aminosilicone with the INCI name Bis-hydroxy / methoxy / methylamodimethicone crosspolymer.

[0160] Mention may also be made of the commercial product Belsil® DADM 3240E sold by the company Wacker.

[0161] The aminosilicones of formula (XIII) may be present in a total amount ranging from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight and even more preferentially from 0.25% to 8% by weight relative to the total weight of composition C.

[0162] Block silicone copolymer: The composition C used in connection with the dyeing process according to the invention may contain one or more block silicone copolymers different from the silicone compounds mentioned above.

[0163] Preferably, the silicone copolymer used in the composition according to the present invention is a linear block copolymer, i.e., a non-crosslinked copolymer obtained by chain extension, not by crosslinking.The term "block copolymer" refers to a polymer that comprises at least two different blocks.Each block of this polymer is derived from one type of monomer or from several different types of monomers.This means that each block can be composed of a homopolymer or a copolymer; this copolymer can be composed of blocks that can be random or alternating.It should also be noted that when a copolymer is "linear", the polymer structure is not branched, not star-branched, and not grafted.

[0164] The block silicone copolymer is preferably linear and is advantageously in the form of particles dispersed in an aqueous medium.

[0165] Block copolymers are obtained by chain extension.

[0166] The aqueous dispersions of block silicone copolymer particles used according to the invention can be chosen in particular from those described in EP-A-874017.

[0167] According to said document, the silicone copolymers that make up these particles are in particular those which contain at least: (a) a polysiloxane (i) containing at least one reactive group per molecule, preferably one or two reactive groups; and - (b) an organosilicon compound (ii) that reacts with polysiloxane (i) by a chain extension reaction; It can be obtained by chain extension reaction from

[0168] In particular, the polysiloxane (i) has the formula (XVII): [ka] wherein R1 and R2 independently represent a hydrocarbon group such as methyl, ethyl, propyl, or butyl, or an aryl group such as phenyl, or a reactive group containing 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, provided that there are on average 1 to 2 reactive groups per polymer, and n is an integer greater than 1. The compound is selected from the group consisting of:

[0169] The term "reactive group" means any group that can react with the organosilicon compound (ii) to form a block copolymer.

[0170] The reactive groups may include hydrogen; aliphatic unsaturated groups, particularly vinyl, allyl, or hexanyl groups; hydroxyl groups; alkoxy groups, such as methoxy, ethoxy, or propoxy; alkoxyalkoxy groups; acetoxy groups; amine groups; and mixtures thereof. Preferably, more than 90%, and even better, more than 98%, of the reactive groups are present at the chain ends. That is, R groups typically account for more than 90%, or even 98%, of the reactive groups.

[0171] Preferably, n may be an integer in particular ranging from 2 to 100, preferably from 10 to 30, and better still from 15 to 25.

[0172] The polysiloxane of formula (XVII) is preferably a linear polymer, i.e., it contains little branching and typically less than 2 mol% of siloxane units. Furthermore, the groups R1 and R2 may be optionally substituted with amine groups, epoxy groups, or groups containing sulfur, silicon, or oxygen.

[0173] Preferably, at least 80% of the R1 groups are alkyl groups, and better still methyl groups.

[0174] Preferably, the reactive group R2 is an aliphatically unsaturated group, especially vinyl.

[0175] Polysiloxanes (i) include, in particular, dimethylvinylsiloxy-polydimethylsiloxanes, compounds of formula (XVII) in which the group R1 is a methyl group, at the end of the chain the group R2 is a vinyl group, and the other two groups R2 are methyl groups.

[0176] The organosilicon compound (ii) can be selected from polysiloxanes of formula (XVII) or compounds which act as chain extenders.

[0177] In the compound of formula (XVII), the polysiloxane (i) contains a first reactive group and the organosilicon compound (ii) contains a second reactive group that reacts with the first reactive group.

[0178] If it is a chain extender, it can be a silane, siloxane (disiloxane or trisiloxane), or silazane.

[0179] Preferably, the organosilicon compound (ii) is a liquid organohydrogenpolysiloxane of formula (XVIII): [ka] wherein n is an integer greater than 1, preferably greater than 10, for example in the range 2 to 100, preferably in the range 10 to 30, and better still in the range 15 to 25. According to a particular embodiment of the invention, n is 20.

[0180] The silicone block copolymers used according to the invention advantageously contain no oxyalkylene groups, in particular no oxyethylene and / or oxypropylene groups.

[0181] The catalyst used in the reaction of the polysiloxane with the organosilicon compound can be selected from metals, in particular platinum, rhodium, tin, titanium, copper and lead, and is preferably platinum or rhodium.

[0182] The block silicone copolymer used according to the present invention is usually in the form of an aqueous dispersion of particles, which can be obtained, for example, by mixing (a) water, (b) at least one emulsifier, (c) polysiloxane (i), (d) organosilicon compound (ii), and (e) catalyst. Preferably, one of components (c), (d), or (e) is added last to the mixture so that the chain extension reaction is initiated only in the dispersion.

[0183] Emulsifiers that can be used in the preparation method for obtaining the aqueous particle dispersion described above include nonionic or ionic (anionic, cationic, or amphoteric) emulsifiers. These emulsifiers are preferably nonionic emulsifiers selected from polyalkylene glycol fatty alcohol ethers containing 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms; polyoxyalkylenated, particularly polyoxyethylenated, sorbitan alkyl esters in which the alkyl group contains 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms; polyoxyalkylenated, particularly polyoxyethylenated, alkyl esters in which the alkyl group contains 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms; polyethylene glycol; polypropylene glycol; diethylene glycol; and mixtures thereof. The amount of emulsifier is usually 1% to 30% by weight based on the total weight of the reaction mixture.

[0184] The emulsifier used to obtain the aqueous dispersion of the particles is preferably selected from polyethylene glycol fatty alcohol ethers and mixtures thereof, in particular polyethylene glycol alcohol ethers containing 12 or 13 carbon atoms and 2 to 100 oxyethylene units, preferably 3 to 50 oxyethylene units, and mixtures thereof. 12 ~C 13 Palace-3, C 12 ~C 13 Pareth-23, and mixtures thereof.

[0185] According to a particular embodiment of the present invention, the block silicone copolymer is obtained from dimethylvinylsiloxypolydimethylsiloxane (or divinyldimethicone) as compound (i) and a compound of formula (XVIII) (preferably n=20) as compound (ii), preferably in the presence of a platinum-based catalyst, preferably C 1 as emulsifier. 12 ~C 13 Palace-3 and C 12 ~C 13 It is obtained in the form of a dispersion of particles in the presence of Pareth-23.

[0186] Block silicone copolymer particles, especially C 12 ~C 13 Palace-3 and C 12 ~C 13 A product sold by Dow Corning under the name HMW 2220 Nonionic Emulsion (CTFA name: Divinyldimethicone / Dimethicone Copolymer / C12-C13 Pareth-3 / C12-C13 Pareth-23), which is an aqueous dispersion of divinyldimethicone / dimethicone copolymer containing Pareth-23, can be used.

[0187] The block silicone copolymers may be present in a total amount ranging from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, more preferentially from 0.1% to 8% by weight and even more preferentially from 0.25% to 5% by weight relative to the total weight of composition C.

[0188] coloring agent Composition C used in connection with the method according to the invention comprises one or more colorants chosen from pigments, direct dyes and mixtures thereof.

[0189] Preferably, the composition C used in connection with the method according to the invention may comprise one or more pigments.

[0190] 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.

[0191] Pigments that can be used are chosen in particular from organic and / or inorganic pigments known in the art, in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and Ullmann's Encyclopedia of Industrial Chemistry.

[0192] These may be natural products of natural origin or non-natural products.

[0193] These pigments may be in the form of pigment powder or paste. They may be coated or uncoated.

[0194] The pigments may be selected, for example, from inorganic pigments, organic pigments, special effect pigments such as lakes, pearlescent agents or glitter flakes, and mixtures thereof.

[0195] The pigment may be an inorganic pigment. The term "inorganic pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann's encyclopedia. Among the inorganic pigments useful in the present invention, mention may be made of iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium oxide.

[0196] 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 encyclopedia.

[0197] 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.

[0198] 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.

[0199] Examples of pigment pastes with organic pigments include those sold by Hoechst under the following names: - Cosmenyl Yellow 10G: Yellow 3 pigment (CI11710); - 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).

[0200] 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.

[0201] 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.

[0202] The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

[0203] Among the dyes, mention may be made of carminic acid. Mention may also be made of products 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).

[0204] An example of a lake is a product known as: D&C Red 7 (CI 15 850:1).

[0205] The pigments may also be special effect pigments. The term "special effect pigments" refers to pigments that generally produce a colored appearance (characterized by a particular hue, a particular vividness, and a particular level of brightness) that is not uniform and that varies 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.

[0206] 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.

[0207] 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 also pearlescent pigments based on bismuth oxychloride. Pearlescent pigments that may be mentioned include Cellini (mica-TiO2-lake) sold by BASF, Prestige (mica-TiO2) sold by Eckart, Prestige Bronze (mica-Fe2O3) sold by Eckart, and Colorona (mica-TiO2-Fe2O3) sold by Merck.

[0208] 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 under the name Copper 340A (Timica) by BASF; red-tinted pearlescent agents, in particular those sold under the name Sienna fine (17386) (Colorona) by Merck; yellow-tinted pearlescent agents, in particular those sold under the name Yellow (4502) (Chromalite) by BASF; gold-tinted red pearlescent agents, in particular those sold under the name Sunstone G012 (Gemtone) by BASF; pink-tinted pearlescent agents, in particular those sold under the name Tan opale G005 (Gemtone) by BASF; gold-tinted black pearlescent agents, in particular Nu-Antique Bronze 240 by BASF. blue pearlescent agents, in particular those sold under the name AB (Timica); blue pearlescent agents, in particular those sold under the name Matte blue (17433) (Microna) by Merck; silvery white pearlescent agents, in particular those sold under the name Xirona Silver by Merck;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.

[0209] Further examples of pearlescent agents include particles comprising a borosilicate substrate coated with titanium oxide.

[0210] Particles comprising a glass substrate coated with titanium oxide are sold in particular under the name Metashine MC1080RY by the company Toyal.

[0211] Finally, as examples of pearlescent agents, mention may be made of 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.

[0212] 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. This reflection can, where appropriate, 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.

[0213] 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.

[0214] These particles may have various morphologies, in particular platelet or spherical morphology, in particular spherical morphology.

[0215] Regardless of their morphology, the reflective particles may or may not have a multi-layer structure, and if they do have a multi-layer structure, they may have at least one layer of a particularly reflective material, for example of uniform thickness.

[0216] 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.

[0217] 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 inorganic materials.

[0218] 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.

[0219] The reflective material may include a metal or a layer of metallic material.

[0220] Reflective particles are described, inter alia, in JP-A-09-188830, JP-A-10-158450, JP-A-10-158541, JP-A-07-258460 and JP-A-05-017710.

[0221] Further examples of reflective particles comprising an inorganic substrate coated with a metal layer may include particles comprising a borosilicate substrate coated with silver.

[0222] 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.

[0223] 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.

[0224] Examples include SiO2 coated aluminum, bronze or copper powders sold under the name Visionaire by the company Eckart.

[0225] 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.

[0226] The variety of pigments that can be used in the present invention makes it possible to obtain a wide range of colors, as well as specific optical effects such as metallic or interference effects.

[0227] 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.

[0228] The pigment may be dispersed in the composition with a dispersant.

[0229] Dispersants serve to prevent the aggregation or flocculation of dispersed particles. They may 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 become physically or chemically bound 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, or 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.

[0230] 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.

[0231] The pigment used in the composition may be surface-treated with an organic agent.

[0232] Thus, the 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, pages 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.

[0233] 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.

[0234] Surface-treated pigments useful in connection with the present invention may be prepared according to surface treatment techniques well known to those skilled in the art, or may be commercially available as is.

[0235] Preferably, the surface-treated pigment is coated with an organic layer.

[0236] The organic agent for treating the pigment may be deposited onto 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.

[0237] 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.

[0238] Organic agents that are covalently bonded to the pigment are preferably used.

[0239] 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.

[0240] 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 Kasei Kogyo Co., Ltd.; - acrylate / dimethicone copolymer and perfluoroalkylphosphate treatment agents, such as the FSA surface treatment agent sold by Daito Kasei Kogyo 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.

[0241] According to a particular embodiment of the present invention, the dispersant is present together with an organic or inorganic pigment in particulate form of submicron size.

[0242] The terms "submicron-sized" 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.

[0243] 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 better still 1.75:3 to 3:1, by weight ratio.

[0244] Thus, the dispersant may be an aminosilicone type dispersant other than those mentioned above, which has a silicone backbone, such as a silicone polyether. Suitable dispersants may include: aminosilicones, i.e. silicones containing one or more amino groups, such as those sold by BYK under the name and reference BYK LPX 21879 and by Genesee Polymers under the names and references GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1; 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® RC1401, Tego® RC1403, Tego® RC1412 from Evonik.

[0245] According to a particular embodiment, the dispersant is of the aminosilicone type other than the aminosilicones mentioned above and is cationic.

[0246] Preferably, the pigment is selected from inorganic pigments, mixed inorganic-organic pigments or organic pigments.

[0247] 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 an inorganic pigment.

[0248] Preferably, the pigment is selected from iron oxides, in particular red, brown or black iron oxides, pearlescent agents, in particular titanium or bismuth oxychloride coated mica, titanium and iron oxide coated mica, iron oxide coated mica, and mixtures thereof.

[0249] An example of iron oxide is the iron oxide sold by Sun Chemical Company under the name SunPuro® Red Iron Oxide.

[0250] An example of a pearlescent agent is iron oxide coated mica sold under the name Prestige Super Soft Bronze by Sudarshan Chemical Company.

[0251] direct dye Composition C used in connection with the method according to the invention may comprise one or more direct dyes.

[0252] The term "direct dyes" means natural and / or synthetic dyes other than oxidation dyes. These are dyes that will diffuse superficially onto the fiber.

[0253] These may be ionic or non-ionic, preferably cationic or non-ionic.

[0254] 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.

[0255] The direct dyes are preferably cationic direct dyes, and mention may be made of hydrazonocationic dyes of the following formulae (XIX) and (XX) and azocationic dyes of the following formulae (XXI) and (XXII): Het + -N(Ra)-N=C(Rb)-Ar,Q- (XIX) Het + -C(Ra)=NN(Rb)-Ar,Q (XX) Het + -N=N-Ar,Q- (XXI) Ar +-N=N-Ar'',Q- (XXII) (In formulas (XIX) to (XXII), - Het + represents a cationic heteroaryl group, preferentially having an intracyclic cationic charge, such as imidazolium, indolium or pyridinium, which may be 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 an aryl group, in particular phenyl, optionally substituted by 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 by a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) 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, such as preferentially phenyl or pyrazolyl, 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 the same or different and represent a hydrogen atom or a (C1-C8) alkyl group which may be optionally substituted (preferentially by a hydroxyl group); Or else, Het +the substituents Ra together with the substituents of Ar and / or Rb together with the atoms carrying them form a (hetero)cycloalkyl; in particular Ra and Rb represent a (C1-C4)alkyl group optionally substituted with a hydrogen atom or a hydroxyl group; - Q- represents an organic or inorganic anionic counterion such as a halide or alkyl sulfate).

[0256] Mention may be made in particular of azo and hydrazono direct dyes having a cationic charge in the ring of the formulae (XIX) to (XXII) defined above, more particularly the cationic direct dyes having a cationic charge in the ring described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954, preferentially the following direct dyes: [ka] (In formulas (XXIII) and (XXIV), -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 (C1-C8) alkyl, optionally substituted (C1-C8) alkoxy, or (di)(C1-C8)(alkyl)amino, wherein 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).

[0257] In particular, the dyes of formula (XXIII) and (XXIV) 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.

[0258] The direct dye may be selected from anionic direct dyes. The anionic direct dyes of the present invention are dyes commonly referred to as "acid" direct dyes due to their 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 (wherein R represents a hydrogen atom or a cation or ammonium ion derived from a metal or amine). The anionic dye may be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes, and natural acid dyes.

[0259] Acid dyes useful in the present invention include dyes of the following formulae (XXV), (XXV'), (XXVI), (XXVI'), (XXVII), (XXVII'), (XXVIII), (XXVIII'), (XXIX), (XXX), (XXXI), and (XXXII).

[0260] a) diaryl anionic azo dyes of formula (XXV) or (XXV'): [ka] (In formulas (XXV) and (XXV'), - R7, R8, R9, R 10 , R'7, R'8, R'9 and R' 10 may be the same or different and represent a hydrogen atom, or - 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 the same 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- (wherein 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 represents a group selected from - 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, wherein M + , R°, X, X′, X″ and Ar are as defined above; - W represents a sigma bond σ, an oxygen atom or a sulfur atom or a divalent radical: i) -NR-, where R is as defined above, or ii) methylene-C(Ra)(Rb)-, where Ra and Rb, which may be the same or different, represent a hydrogen atom or an aryl group, or alternatively Ra and Rb, together with the carbon atom to which they are attached, form a spirocycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl; Formulas (XXV) and (XXV') 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).

[0261] Examples of dyes of formula (XXV) 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 the dye of formula (XXV') include Acid Red 111, Acid Red 134, and Acid Yellow 38.

[0262] b) Pyrazolone anionic azo dyes of formula (XXVI) and (XXVI'): [ka] (In formulas (XXVI) and (XXVI'), -R 11 , R 12 and R 13 may be the same or different and are a hydrogen atom 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 with and form a double bond; -R 17 and R 18 may be the same or different and represent a hydrogen atom, or - (O)2S(O - )-,M + (In the formula, M + is as defined above); - Ar-OS(O)2-, where Ar represents an optionally substituted aryl group, and preferentially a phenyl group, 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, an alkyl group, or a hydroxyl group; -R 21 represents a hydrogen atom, an alkyl group, or an alkoxy group; Ra and Rb, which may be the same or different, 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 (XXVI) and (XXVI') 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).

[0263] Examples of the dye of formula (XXVI) include Acid Red 195, Acid Yellow 23, Acid Yellow 27, and Acid Yellow 76, and an example of the dye of formula (XXVI') is Acid Yellow 17.

[0264] c) Anthraquinone dyes of formulae (XXVII) and (XXVII'): [ka] (In formulas (XXVII) and (XXVII'), -R 22 , R 23 , R 24 , R 25 , R 26 and R 27 may be the same or different and represent a hydrogen atom or a halogen atom, or - 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 represents R 28 and R 29 may be the same or different and represent a hydrogen atom, or - 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; especially cyclohexyl represents a group selected from: - Z is hydroxyl and NR' 28 R' 29 R' represents a group selected from 28 and R' 29 may be the same or different, and R 28 and R 29 represents the same atom or group as Formulas (XXVII) and (XXVII') 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).

[0265] Examples of dyes of formula (XXII) 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 dyes of formula (XXVII') is Acid Black 48.

[0266] d) Nitro dyes of formula (XXVIII) and (XXVIII'): [ka] (In formulas (XXVIII) and (XXVIII'), -R 30 , R 31 and R 32 may be the same or different and represent a hydrogen atom or a 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; 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 the same 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 - group, where m represents an integer of 1 or 2, and preferentially, J represents a -SO2- group; 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 by Formulas (XXVIII) and (XXVIII') 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).

[0267] Examples of dyes of formula (XXVIII) include Acid Brown 13 and Acid Orange 3, and examples of dyes of formula (XXVIII') 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.

[0268] e) Triarylmethane dyes of formula (XXIX): [ka] (In formula (XXIX), -R 33 , R 34 , R 35 and R 36 are the same 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 is as defined above) represents a benzyl group optionally substituted; -R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 may be the same or different and represent a hydrogen atom, or - 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 the same 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) or represents a group selected from - 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)-; ix) R°-X'-C(X)-X''-; M + , R°, X, X', and X'' are as defined above, in particular R 37 ~R 40 represents a hydrogen atom, and R 41 ~R 44 may be the same or different and are hydroxyl or (O)S(O-),M + represents a group, and R 43 R 44together to form a benzo group, it is preferentially substituted with an (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 that it preferentially comprises sulfonates).

[0269] Examples of dyes of formula (XXIX) 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.

[0270] f) Xanthene dyes of formula (XXX): [ka] (In formula (XXX), -R 45 , R 46 , R 47 and R 48 may be the same or different and represent a hydrogen atom or a halogen atom; -R 49 , R 50 , R 51 and R 52 may be the same or different and represent a hydrogen atom or a halogen atom, or - 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 atom or a halogen atom; G represents an oxygen or sulfur atom or an NRe group, where Re is as defined above, 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; M + is in particular sodium or potassium); L' is an oxygen or sulfur atom or an ammonium group: N + RfRg, where 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 the same or different, represent an oxygen or sulfur atom; in particular, Q and Q' represent an oxygen atom; -M + is as defined above).

[0271] Examples of dyes of formula (XXX) include Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; and Acid Violet 9.

[0272] g) Indole dyes of formula (XXXI): [ka] (In formula (XXXI), -R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 may be the same or different and represent a hydrogen atom, or - 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 the same 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 the same or different and represent a hydrogen atom or an alkyl group; Formula (XXXI) 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).

[0273] An example of a dye of formula (XXXI) is Acid Blue 74.

[0274] h) Quinoline dyes of formula (XXXII): [ka] (In formula (XXXII), -R 61 represents 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 (XXXII) contains at least one sulfonate group (O)S(O - )-,M + , which is understood to preferentially include sodium sulfonates).

[0275] Examples of dyes of formula (XXXII) include Acid Yellow 2, Acid Yellow 3, and Acid Yellow 5.

[0276] 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.

[0277] Preferably, the direct dye is selected from anionic direct dyes.

[0278] 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 weight of composition C; preferably, the colorants are chosen from pigments.

[0279] 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 weight of composition C.

[0280] The direct dye may be present in an amount ranging from 0.001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of composition C.

[0281] organic solvents Composition C used in connection with the method according to the invention may comprise one or more organic solvents.

[0282] Preferably, the composition contains ethanol.

[0283] The organic solvents may be present in a total amount ranging from 1% to 30% by weight, preferably from 3% to 20% by weight, preferably from 5% to 15% by weight, relative to the total weight of composition C.

[0284] The composition C used in connection with 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 the composition C.

[0285] additives Composition C used in connection with the method according to the invention may contain any adjuvant or additive normally used.

[0286] Among the additives that may be included in the composition are reducing agents, emollients, antifoaming agents, moisturizing agents, UV filters, deflocculants, solubilizing agents, thickeners, fragrances, proteins, vitamins, preservatives, oils, waxes, and mixtures thereof.

[0287] The composition C used in connection with the method according to 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), in the form of a cream, a mousse, a stick, a dispersion of vesicles, in particular of ionic or non-ionic lipids, or in the form of a two-phase or multiphase lotion.

[0288] 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 nature of the components used, in particular their solubility in the carrier, and then the intended use of the composition.

[0289] Application of Composition D The method for dyeing keratinous hair fibers according to the invention may also comprise applying to the keratinous hair fibers a composition D comprising at least one silicone compound containing at least one carboxyl group.

[0290] Preferably, the silicone compound containing at least one carboxyl group is a compound other than b) compounds containing at least one carboxylic acid group and c) compounds other than the aminosilicones and block silicone copolymers of formula (XIII).

[0291] 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.

[0292] The silicones that can be used may be soluble or insoluble in composition D and they may be in the form of oils, waxes, resins or gums, with silicone oils and gums being preferred.

[0293] Silicones are particularly well-described in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press.

[0294] Preferably, the silicone compound containing at least one carboxyl group has the following formula (XXXIII): [ka] (In the formula, R1 independently represents an alkyl group containing 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; a hydroxyl group; an alkoxy group containing 1 to 20 carbon atoms or an aryl group containing 6 to 12 carbon atoms; - R2 independently represent a group R4-COOM (R4 represents a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur, nitrogen, oxygen, and mixtures thereof, and M represents a hydrogen atom); an alkali metal or alkaline earth metal or quaternary ammonium NR'3 (R' may be the same or different and represent H or an alkyl group containing 1 to 4 carbon atoms); a carboxyl group COOH or a pyrrolidone group containing a group Ra-(ORb)x-COOM (where Ra represents a linear or branched alkylene group containing 1 to 4 carbon atoms, Rb represents an alkyl group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; M represents a hydrogen atom, an alkali metal or alkaline earth metal or quaternary ammonium NR'3, and R' may be the same or different and represent H or an alkyl group containing 1 to 4 carbon atoms); - R3 independently represents an alkyl group containing 1 to 20 carbon atoms; a hydroxyl group; an R4-COOM group (R4 represents a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms, and mixtures thereof, and M represents a hydrogen atom); an alkali metal or alkaline earth metal or quaternary ammonium NR'3 (R' may be the same or different and represents H or an alkyl group containing 1 to 4 carbon atoms); an alkoxy group containing 1 to 20 carbon atoms; an aryl group containing 6 to 12 carbon atoms or R a -(OR b ) x -COOM group (in the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, and R b represents an alkyl group having 1 to 4 carbon atoms, x is an integer ranging from 1 to 200; M represents a hydrogen atom, an alkali metal or alkaline earth metal, or a quaternary ammonium NR'3 (wherein R' may be the same or different and represents H or an alkyl group having 1 to 4 carbon atoms); - n represents an integer ranging from 1 to 1000; - p represents an integer ranging from 0 to 1000; It is understood that at least one of the R2 and / or R3 groups comprises a carboxyl group COOH or COOM, where M represents an alkali metal or alkaline earth metal or a quaternary ammonium NR'3, where R' may be the same or different and represents H or alkyl containing 1 to 4 carbon atoms. The organosiloxanes are selected from the following:

[0295] In particular, the silicone compound containing at least one carboxyl group is an organosiloxane of formula (XXXIV): [ka] (In the formula, R1 independently represent a linear or branched alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and even better from 1 to 6 carbon atoms, preferentially methyl; R4 independently represents a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms, and mixtures thereof; or a divalent group R a -(OR b ) x -(In the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, and R b represents an alkylene group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; M independently represents a hydrogen atom, an alkali metal or alkaline earth metal, or a quaternary ammonium NR'3, where R', which may be the same or different, represents H or alkyl containing 1 to 4 carbon atoms; - n represents an integer ranging from 1 to 1000); organosiloxanes of formula (XXXV): [ka] (In the formula, R1 independently represent an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferentially methyl; R4 is a linear or branched, saturated or unsaturated alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms, and mixtures thereof; or a divalent group R a -(OR b ) x -(In the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, and R b represents an alkylene group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; M represents a hydrogen atom, an alkali metal or alkaline earth metal or a quaternary ammonium NR'3, where R', which may be the same or different, represents H or alkyl containing 1 to 4 carbon atoms; - p represents an integer ranging from 1 to 1000; - n represents an integer ranging from 1 to 1000); organosiloxanes of formula (XXXVI): [ka] (In the formula, R1 independently represent an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and even better from 1 to 6 carbon atoms, preferentially methyl; R4 is a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms, and mixtures thereof; or a divalent group R a -(OR b ) x -(In the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, and Rb represents an alkylene group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; R3 represents an alkyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms, or an aryl group containing 6 to 12 carbon atoms; M independently represents a hydrogen atom, an alkali metal or alkaline earth metal, or a quaternary ammonium NR'3, where R'' may be the same or different and represents H or alkyl containing 1 to 4 carbon atoms; - n represents an integer ranging from 1 to 1000); organosiloxanes of formula (XXXVII): [ka] (In the formula, R8 represents an alkyl group containing 1 to 6 carbon atoms, preferably methyl; - m represents an integer ranging from 1 to 1000; - n represents an integer ranging from 1 to 1000); - and mixtures thereof may be selected from:

[0296] Among the organosiloxanes of formula (XXXIV), mention may be made of polydimethylsiloxanes (PDMS) having carboxyl end groups, such as the compound sold by the company Momentive under the trade name Silform INX (INCI name: Biscarboxydecyldimethicone).

[0297] Among the organosiloxanes of formula (XXXV) there may be mentioned polydimethylsiloxanes (PDMS) having pendant carboxyl groups, such as the compound sold by Shin-Etsu Chemical Co., Ltd. under the trade name X-22-3701E.

[0298] Among the organosiloxanes of formula (XXXVI), mention may be made of polydimethylsiloxanes (PDMS) having carboxyl end groups, such as the compound sold by Shin-Etsu Chemical Co., Ltd. under the trade name X-22-3710.

[0299] Among the organosiloxanes of formula (XXXVII), mention may be made of the compound sold by Grant Industries under the trade name Grandsil SiW-PCA-10 (INCI name: dimethicone and PCA dimethicone and butylene glycol and decyl glucoside).

[0300] The silicone compounds containing carboxyl groups can correspond, for example, to the compounds described in European Patent No. 186507 in the name of Chisso Corporation, which is incorporated herein by reference.

[0301] Preferably, the silicone compound containing at least one carboxyl group is selected from organopolysiloxanes of formula (XXXIV), organopolysiloxanes of formula (XXXV), and mixtures thereof.

[0302] More preferentially, the silicone compound containing at least one carboxyl group has the following formula (XXXIV): [ka] (In the formula, R1 independently represent a linear or branched alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and even better from 1 to 6 carbon atoms, preferentially methyl; R4 independently represents a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms, and mixtures thereof; or a divalent group R a -(OR b ) x -(In the formula, Ra represents a linear or branched alkylene group containing 1 to 4 carbon atoms, and R b represents an alkylene group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; M independently represents a hydrogen atom, an alkali metal or alkaline earth metal, or a quaternary ammonium NR'3, where R', which may be the same or different, represents H or alkyl containing 1 to 4 carbon atoms; - n represents an integer ranging from 1 to 1000 The organopolysiloxane is selected from the following:

[0303] Advantageously, the total amount of silicone compounds comprising at least one carboxylic acid group ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferentially from 0.5% to 10% by weight and even better from 1% to 5% by weight relative to the total weight of composition D.

[0304] oil Composition D may also include one or more oils.

[0305] Preferably, composition D comprises one or more oils. More preferentially, composition D comprises one or more oils chosen from alkanes.

[0306] The term "oil" refers to oil at room temperature (25°C) and atmospheric pressure (760 mmHg, i.e., 1.013 x 10 5 "Liquid" refers to a fatty substance that is liquid at temperatures below 100°C (Pa).

[0307] The oil may be volatile or non-volatile.

[0308] The term "volatile oil" refers to an oil that can evaporate in less than one hour upon contact with the skin at room temperature and atmospheric pressure. Volatile oils are cosmetic volatile oils that are liquid at room temperature. More specifically, the evaporation rate of volatile oils is between 0.01 and 200 mg / cm. 2 / min inclusive (see evaporation rate measurement procedure later in the text).

[0309] The term "non-volatile oil" refers to oil that remains on the skin or keratin fibers at room temperature and atmospheric pressure. More specifically, the evaporation rate of non-volatile oil is exactly 0.01 mg / cm 2 / min (see the evaporation rate measurement procedure later in the text).

[0310] Preferably, the composition contains C6 to C 16 It comprises one or more oils selected from alkanes and / or mixtures thereof.

[0311] C6~C 16 With respect to alkanes, these may be straight-chain or branched, and optionally cyclic.

[0312] In particular, branches C8 to C 16 Alkanes, e.g., C8-C 16 Mention may be made of isoalkanes (also known as isoparaffins), isododecane, isodecane or isohexadecane, for example the oils sold under the trade names Isopar or Permethyl, and mixtures thereof.

[0313] Mention may also be made of linear alkanes, preferably of plant origin, containing 7 to 15 carbon atoms, in particular 9 to 14 carbon atoms, more particularly 11 to 13 carbon atoms.

[0314] Examples of linear alkanes suitable for use in the present invention include n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14) and n-pentadecane (C15) and mixtures thereof, in particular the mixture of n-undecane (C11) and n-tridecane (C13) described in Example 1 of Cognis patent application WO 2008 / 155059.

[0315] Mention may also be made of n-dodecane (C12) and n-tetradecane (C14), sold under the trade designations Parafol 12-97 and Parafol 14-97, respectively, by Sasol, as well as mixtures thereof.

[0316] Examples of alkanes suitable for use in the present invention include those described in patent applications WO 2007 / 068371 and WO 2008 / 155059. These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut kernel oil or palm oil.

[0317] According to a particular embodiment, the composition comprises isododecane. A compound of this type is, for example, isododecane sold by Ineos under the trade designation Isododecane.

[0318] Preferably, composition D is C8 to C 16 It comprises one or more oils chosen from alkanes, more preferentially from isododecane, isohexadecane, tetradecane and / or mixtures thereof.

[0319] More preferentially, composition D comprises isododecane.

[0320] Composition D may comprise one or more oils present in a total amount of from 30% to 99% by weight, preferably from 50% to 99% by weight and even better still from 70% to 99% by weight relative to the total weight of the composition.

[0321] Composition D may contain at least one colorant selected from the pigments, direct dyes and mixtures thereof previously described.

[0322] protocol Composition C and optional composition D described above can be used on wet or dry keratinous hair fibers, and on any type of light or dark, natural or dyed, permed, bleached or straightened fibers.

[0323] According to a preferred embodiment, composition C and composition D are applied simultaneously to the keratinous fibers.

[0324] According to another preferred embodiment, composition D is applied to the keratinous hair fibres after application of composition C to the keratinous hair fibres.

[0325] According to another preferred embodiment, composition D is applied to the keratinous hair fibers before applying composition C to the keratinous hair fibers.

[0326] More preferentially, composition D is applied to the keratin hair fibres after composition C has been applied to the keratin hair fibres.

[0327] According to a particular embodiment of the invention, the keratinous hair fibers are washed before applying composition C and / or composition D.

[0328] Preferably, a washing, rinsing, dewatering or drying step is carried out after applying composition C to the keratinous hair fibers and before applying composition D to the keratinous hair fibers.

[0329] More preferentially, a drying step is carried out after applying composition C to the keratinous hair fibres and optionally before applying composition D to the keratinous hair fibres.

[0330] Application to keratinous hair fibers can be carried out via any standard means, in particular with a comb, a fine-toothed brush, a wide-toothed brush, a sponge, or the fingers.

[0331] The application of composition C to keratinous hair fibers and / or the application of composition C followed by composition D is usually carried out at room temperature (15 to 25°C).

[0332] After composition C has been applied to the keratinous hair fibres, it can be left for 1 minute to 6 hours, in particular 1 minute to 2 hours, more particularly 1 minute to 1 hour, and more preferentially 1 minute to 30 minutes, for example before applying composition D to the keratinous hair fibres or before a washing, rinsing, dewatering or drying step, for example.

[0333] Preferably, no standing time is allowed after application of composition C to the keratinous hair fibres and before application of composition D to the keratinous hair fibres.

[0334] After applying composition C and / or composition C followed by composition D, the keratinous hair fibres may be allowed to dry naturally or may be dried at a temperature of, for example, 30°C or higher.

[0335] Thus, the method according to the invention may comprise the step of applying heat to the keratinous fibres using a heating tool.

[0336] The heat application step of the method of the present invention can be carried out using a hood dryer, a hair dryer, a straightener, a curling iron, a Climazon hood, or the like.

[0337] Preferably, the step of applying heat of the method of the present invention is carried out using a hair dryer.

[0338] When the method of the present invention includes the step of applying heat to the keratinous hair fibers, the step of applying heat to the keratinous hair fibers is carried out after applying composition C and optional composition D to the keratinous hair fibers.

[0339] During the process of applying heat to the keratinous hair fibers, the hair strands may be subjected to mechanical action such as combing, brushing or hand combing.

[0340] If the step of applying heat to the keratinous hair fibres is carried out using a hood dryer or a hair dryer, the temperature is preferably between 30°C and 110°C, preferentially between 50°C and 90°C.

[0341] If the step of applying heat to the keratin hair fibres is carried out using a straightening iron, the temperature is preferably between 110°C and 220°C, preferably between 140°C and 200°C.

[0342] In a particular variant, the method of the invention comprises a step (c1) of applying heat using a hood dryer, a hair dryer or a crimson hood, preferably a hair dryer, and a step (c2) of applying heat using a straightening iron or curling iron, preferably a straightening iron.

[0343] Step (c1) may be carried out before step (c2).

[0344] During the implementation of step (c1), also referred to as the drying step, the keratinous hair fibers can be dried, for example, at a temperature of at least 30° C. According to a particular embodiment, this temperature is greater than 40° C. According to a particular embodiment, this temperature is greater than 45° C. and less than 110° C.

[0345] Preferably, when drying the keratinous hair fibers, in addition to the supply of heat, the drying is carried out by using an air current, which thus makes it possible to improve the separation of the coating of the hair strands.

[0346] During drying, the hair strands can be subjected to mechanical action such as combing, brushing or hand combing.

[0347] The temperature at which the straightening iron or curling iron is slid in the drying step (c2) may preferably be in the range of 110°C to 220°C, more preferably 140°C to 200°C.

[0348] After the heating step, a shaping step may be carried out using, for example, a straightening iron, and the temperature in the shaping step is between 110°C and 220°C, preferably between 140°C and 200°C.

[0349] Preferably, the present invention relates to a method for dyeing keratinous hair fibers, comprising: i) a) at least one (poly)carbodiimide compound as described above; b) at least one compound containing at least one carboxylic acid group as described above; and c) at least one aminosilicone of formula (XIII) above; d) at least one colorant selected from pigments, direct dyes, and mixtures thereof; applying to the keratinous hair fibres at least one composition C containing ii) optionally leaving said composition C on the keratin hair fibres for 1 minute to 30 minutes, preferably 1 to 20 minutes; then iii) optionally washing, rinsing, dewatering or drying the keratinous hair fibers; and iv) optionally applying to the keratinous hair fibres at least one composition D comprising at least one silicone compound containing at least one carboxyl group as described above; then v) optionally leaving said composition D on the keratin hair fibres for 1 minute to 30 minutes, preferably 1 to 20 minutes; then vi) optionally washing, rinsing, dehydrating or drying the keratinous hair fibers; The method includes:

[0350] Preferably, the step of applying composition C to the keratinous hair fibres is repeated several times.

[0351] Advantageously, the dyeing process comprises a step iv) of applying to the keratinous hair fibres a composition D comprising at least one silicone compound containing at least one carboxyl group as defined above.

[0352] According to a preferred embodiment, the dyeing method according to the invention is a method for coloring keratinous hair fibers, which method comprises extemporaneously mixing at least two compositions A and B at the time of use to obtain a composition C, and applying composition C to the keratinous 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 group as defined above, Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof; Composition A and / or Composition B comprise at least one aminosilicone of formula (XIII) described above.

[0353] Advantageously, the dyeing method also comprises applying to the keratin hair fibres at least one composition D comprising at least one silicone compound containing at least one carboxyl group as defined above, said composition D being applied to the keratin hair fibres before and / or after applying to the keratin hair fibres composition C.

[0354] Preferably, composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof.

[0355] Preferably, composition A does not contain at least one colorant selected from pigments, direct dyes and mixtures thereof.

[0356] According to this embodiment, compositions A and B are preferably mixed within 15 minutes before application to keratin hair fibers, more preferentially within 10 minutes before application to keratin hair fibers, and even better still within 5 minutes before application to keratin hair fibers.

[0357] The mass 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, and even better still 0.6 to 1.5.

[0358] In certain embodiments, the weight ratio of composition A and composition B is equal to 1.

[0359] According to a preferred embodiment, the dyeing method according to the invention is a method for dyeing keratinous hair fibers, which method comprises extemporaneously mixing at least two compositions A and B at the time of use to obtain a composition C, and applying composition C to the 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 group as defined above and at least one colorant chosen from pigments, direct dyes and mixtures thereof; Composition A and / or Composition B comprises at least one aminosilicone of formula (XIII) as defined above, - optionally applying to the keratinous hair fibres at least one composition D comprising at least one silicone compound comprising at least one carboxyl group as defined above, said composition D being applied to the keratinous hair fibres before and / or after applying composition C to the keratinous hair fibres.

[0360] According to a preferred embodiment, the dyeing method according to the invention is a method for dyeing keratinous hair fibers, which method comprises extemporaneously mixing at least two compositions A and B at the time of use to obtain a composition C, and applying composition C to the 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 group as defined above, at least one colorant chosen from pigments, direct dyes and mixtures thereof, and at least one aminosilicone of formula (XIII) as defined above, - optionally applying to the keratinous hair fibres at least one composition D comprising at least one silicone compound comprising at least one carboxyl group as defined above, said composition D being applied to the keratinous hair fibres before and / or after applying composition C to the keratinous hair fibres.

[0361] 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.

[0362] The total amount of compounds having at least one carboxylic acid group is preferably in the range of 2% by weight to 40% by weight, more preferentially 5% by weight to 30% by weight, and even better still 5% by weight to 20% by weight, relative to the total weight of composition B.

[0363] The aminosilicone of formula (XIII) described above may be present in a total amount ranging from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight, and even more preferentially from 0.5% to 5% by weight, relative to the total weight of composition B.

[0364] Multi-compartment devices (kits) The present invention relates to a device for dyeing keratinous hair fibers, comprising one or more compartments, - In the first compartment, a) at least one (poly)carbodiimide compound as described above; b) at least one compound containing at least one carboxylic acid group as described above; and c) at least one aminosilicone of formula (XIII) above; d) at least one colorant selected from pigments, direct dyes, and mixtures thereof; Composition C comprising: - optionally, in a second compartment, a composition D comprising at least one silicone compound comprising at least one carboxyl group as described above; It also relates to devices.

[0365] The present invention relates to a device for dyeing keratinous hair fibers, comprising a plurality of compartments, - In the first compartment, a) a composition A containing at least one (poly)carbodiimide compound as described above; - In the second compartment, b) composition B comprising at least one compound containing at least one carboxylic acid group as described above; Composition A and / or Composition B comprises c) at least one aminosilicone of formula (XIII) above; Composition A and / or Composition B comprises d) at least one colorant selected from pigments, direct dyes, and mixtures thereof; - optionally, in a third compartment, a composition D comprising at least one silicone compound comprising at least one carboxyl group as described above; It also relates to devices.

[0366] According to a preferred embodiment, the device according to the invention is a device for dyeing keratinous hair fibres, comprising several compartments, - In the first compartment, a) a composition A containing at least one (poly)carbodiimide compound as described above; - In the second compartment, b) at least one compound containing at least one carboxylic acid group as described above; and d) at least one colorant selected from pigments, direct dyes, and mixtures thereof; Composition A and / or Composition B comprises c) at least one aminosilicone of formula (XIII) above; - optionally, in a third compartment, a composition D comprising at least one silicone compound comprising at least one carboxyl group as described above; It is a device.

[0367] According to a preferred embodiment, the device according to the invention is a device for dyeing keratinous hair fibres, comprising several compartments, - In the first compartment, a) a composition A containing at least one (poly)carbodiimide compound as described above; - In the second compartment, b) at least one compound containing at least one carboxylic acid group as described above; c) at least one aminosilicone of formula (XIII) as described above; and d) at least one colorant selected from pigments, direct dyes, and mixtures thereof; - optionally, in a third compartment, a composition D comprising at least one silicone compound comprising at least one carboxyl group as described above; It is a device.

[0368] The present invention will now be explained in more detail using examples, which in no way limit the scope of the present invention, but which make it possible to support certain features, variants and preferred embodiments of the present invention. [Example]

[0369] 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.

[0370] More specifically, the method for preparing a (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) (wherein L1 and n are as defined above) To deactivate the catalyst, a benzoyl halide such as benzoyl chloride may be added.

[0371] 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 equivalents 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) (wherein R1, X1, L1, n and E are as defined above) is obtained. According to a variant to obtain compound (4) from (3), it is possible to first add 0.5 equivalents of the reagent HEH, followed by 1 equivalent of the reagent R1-X1-H.

[0372] 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, followed by reaction with 1 equivalent 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) (wherein R1, X1, L1, n and E are as defined above) is obtained.

[0373] According to one variant to obtain compound (5) from (3), it is possible to first add 1 equivalent of the reagent R1-X1-H, followed by 0.5 equivalents of the reagent HEH.

[0374] In the third step, compound (5) is reacted with 1 equivalent of compound (6): R2-X2-C(O)-NH-L1-(N=C=N-L1) n -N=C=O (6) The compound (6) is reacted with the compound (3'). O=C=N-L1-(N=C=N-L1) z -N=C=O (3') (In formula (3'), L1 and z are as defined above.) which is reacted with one equivalent of a nucleophile R2-X2-H having L1, R2, X2 and z 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) (In formula (7), R1, X1, L1, R2, X2, n, z, and E are as defined above.) Give.

[0375] 1 molar equivalent of the compound O=C=N-L1-(N=C=N-L1) z -N=C=O(3') was reacted with 1 / w molar equivalent of HEH followed by 1 equivalent 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) (In formula (8), L1, R2, X2, z, and E are as defined above, and w is an integer of 1 to 3; more preferentially, w=1.) It is also possible to obtain

[0376] This final compound (8) is then reacted with 1 equivalent 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 equivalents of a nucleophilic reagent R1-X1-H with 1 equivalent 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 -NHC(O)-X2-R2(9) (In formula (9), L1, R1, X1, R2, X2, n, z, w, and E are as defined above.) can be obtained.

[0377] The (poly)carbodiimide compounds and all reaction intermediates and reagents as well may 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.

[0378] Example 1: Process for synthesizing (poly)carbodiimide compounds Into a 500 mL three-necked round-bottom flask equipped with a thermometer, a stirrer and a reflux condenser, 50 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphole 1-oxide were placed with stirring.

[0379] 2200-2300 cm by infrared spectroscopy -1 The reaction medium was heated under nitrogen at 140°C for 4 hours, and then cooled to 120°C, while the reaction was monitored by the absorption of isocyanate groups.

[0380] 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.

[0381] 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 give the desired product in the form of a translucent yellow liquid.

[0382] Example 2: Process for synthesizing aminosilicone of formula (XIII) To an aqueous emulsion containing 35% amodimethicone with 3-(2-aminoethylamino)propyl functionality, 1.1 equivalents of diethyl L-tartrate are added.

[0383] The resulting mixture is homogenized at room temperature to yield a white, smooth, low viscosity silicone emulsion.

[0384] Example 3: The compositions described below were prepared: Amounts are expressed as g / 100g of starting material obtained unless otherwise stated. In Table 2 below, "am" means active substance.

[0385] [Table 1]

[0386] [Table 2]

[0387] Three mixtures are then prepared: composition A is mixed with each of compositions B1, B2 and B3 in a 50 / 50 weight ratio to obtain three compositions C1, C2 and C3.

[0388] Therefore, the process using composition C1 is a comparative process, and the processes using compositions C2 and C3 are processes according to the invention.

[0389] The following composition D was then prepared: Amounts are expressed as g / 100g of starting material obtained.

[0390] [Table 3]

[0391] Example 4: Protocol for assessing resistance to shampoo washing: Each of the compositions C1 and C3 is applied to a dry tress of natural keratin hair fiber containing 90% white keratin hair fiber strands using a small brush at a rate of 0.8 grams of composition per gram of tress. The tress of keratin hair fiber is then detangled and dried with a hair dryer at medium temperature.

[0392] Composition D is then applied to said tresses of keratinous hair fibres pretreated with compositions C1 and C3 at a rate of 0.5 g of composition per gram of tress.

[0393] The keratin hair fibres are then detangled and dried with a hair dryer at medium temperature, after which they are stored for 24 hours at a temperature of 22° C. and a humidity of 35%.

[0394] The tresses of keratinous hair fibres so dyed are then subjected to a repeated shampoo wash test in order to assess the fastness (durability) of the dye obtained to shampoo washes, according to the shampoo wash protocol described below.

[0395] Shampoo Wash Protocol: The dyed keratin hair fiber strands are combed, moistened with water at 35°C, and then passed through the fingers 5 times for 5 seconds. The keratin hair fiber strands are then squeezed between two fingers.

[0396] A standard shampoo (Garnier Ultra Doux) was applied evenly to the dyed hair tresses at a rate of 0.4 g of standard shampoo per gram of tress, and the keratin hair fiber tresses were gently massaged longitudinally from root to tip for 15 seconds (6 times).

[0397] The keratin hair fiber strand is then placed on a watch glass and left for 1 minute.

[0398] The keratin hair fiber strand is then rinsed with water (15 times) while passing it through the fingers, after which the keratin hair fiber strand is squeezed between two fingers to dry before the next shampoo wash.

[0399] After the test, which involves several shampoo washes, the keratin hair fibre strands are combed and dried with a hair dryer.

[0400] result The color durability of the tresses was evaluated in the CIE L*a*b* system using a Minolta Spectrophotometer CM3600A spectrophotometer (D65 illuminant, 10° angle, including specular reflection component).

[0401] 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.

[0402] The durability of the color is evaluated by the color difference ΔE between the dyed hair tress before shampooing and after shampooing five times according to the protocol described above. The lower the ΔE value, the better the color durability after shampooing. The ΔE value is calculated according to the following formula:

number

[0403] In this formula, L*a*b* represents the value measured after dyeing keratin hair fibers and washing with shampoo, and L0*a0*b0* represents the value measured after dyeing keratin hair fibers and before washing with shampoo.

[0404] [Table 4]

[0405] A tress of keratinous hair fibres treated with a process according to the invention and washed with five shampoos has a lower ΔE value than a tress of keratinous hair fibres treated with a comparative process.

[0406] Thus, the colored coatings obtained by the process according to the invention exhibit improved resistance to shampoo washing.

[0407] Example 5: Protocol for assessing smoothness and suppleness: Each of the compositions C1, C2 and C3 described in Example 3 is applied to a tress of natural chestnut-colored keratin hair fibers (tone level 4) at a rate of 0.8 grams of composition per gram of tress. The tresses of keratin hair fibers are then dried with a medium-heat hair dryer while combing them.

[0408] A blow-drying brush is then used to detangle the keratin hair fiber strands of the tress.

[0409] The keratin hair fibre tresses are then stored for 24 hours at a temperature of 22° C. and a humidity of 35%.

[0410] The properties of smooth feel and suppleness were then evaluated.

[0411] Evaluation of smooth feel The dyed keratin hair fiber tresses prepared as described above were evaluated for smooth feel performance by five experts. Performance was evaluated in a blind test, with each of the five experts assigning a score ranging from 0 (very poor smoothness) to 5 (very good smoothness) to each tress of keratin hair fiber.

[0412] To assess smoothness, the expert takes a strand of keratin hair fiber between the thumb and index finger and runs the finger along the strand from top to end. The expert assesses whether the keratin hair fiber is rough or whether the finger catches on the keratin hair fiber.

[0413] The results obtained are summarized in Table 5 below.

[0414] [Table 5]

[0415] It can be clearly seen that the keratinous hair fibre strands treated with the process according to the invention feel significantly smoother to the touch than the keratinous hair fibre strands treated with the comparative process.

[0416] Thus, the colored coating obtained by the process according to the invention has an improved smooth feel.

[0417] Flexibility evaluation The dyed keratin hair fibers prepared as described above were evaluated for tress slack performance by five experts. Performance was evaluated in a blind test, with each of the five experts assigning a score ranging from 0 (very poor slack) to 5 (very good slack) to each tress of keratin hair fiber.

[0418] To assess the flexibility properties, the expert folds a strand of keratin hair fiber twice between the palms of his hands and squeezes it three times at a rate of one second per squeeze.

[0419] The easier it is to fold or bend a keratin hair fiber, the more flexible it is.

[0420] The results obtained are summarized in Table 6 below.

[0421] [Table 6]

[0422] It can be clearly seen that the strands of keratinous hair fibres treated by the process according to the invention have significantly higher flexibility than the strands of keratinous hair fibres treated by the comparative process.

[0423] Thus, the colored coatings obtained by the process according to the invention exhibit improved flexibility.

Claims

1. 1. A method for dyeing keratinous hair fibers, comprising: a) at least one (poly)carbodiimide compound; b) at least one compound containing at least one carboxylic acid group; and c) a compound represented by the following formula (XIII): 【Chemistry 1】 (In the formula, R1 independently represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms; R2 independently represents a group of formula -C ｑ H ２ｑ represents a monovalent group of L, where q is a number ranging from 2 to 8, and L is optionally selected from the group: -N(R3) ２ ; -N ＋ (R3) ３ A － ; -NR3-Y-N(R3) ２ 、and -NR-Y-N ＋ (R3) ３ A － is a quaternized amine group selected from In the formula, R3 may be the same or different and is a hydrogen atom, a phenyl group, a benzyl group, or a monovalent saturated hydrocarbon group, such as C １ ~C ２０ represents an alkyl group; Y represents a group of formula C ｒ H ２ｒ where r is an integer ranging from 2 to 6, preferably from 2 to 4; A － represents a cosmetically acceptable anion, especially a halide, such as fluoride, chloride, bromide, or iodide; X is of the following formula (XIV): 【Chemistry 2】 represents a group corresponding to the formula: A independently represents a linear or branched alkylene group containing 1 to 10 carbon atoms, optionally interrupted by at least one heteroatom selected from O, S, NH, or a carbonyl group (CO), preferably NH; Q represents an alkylene group containing 1 to 20 carbon atoms, said alkylene group optionally being substituted with at least one alkoxy group containing 1 to 10 carbon atoms, a hydroxyl group, or an aminoalkyl group containing 1 to 20 carbon atoms; - n represents an integer ranging from 0 to 500, m represents an integer ranging from 1 to 500, o represents an integer ranging from 0 to 500, and n + m + o represents an integer ranging from 250 to 500) and at least one aminosilicone of the formula: d) at least one colorant selected from pigments, direct dyes, and mixtures thereof; applying to said keratinous hair fibres at least one composition C containing

2. 2. The method according to claim 1, wherein the (poly)carbodiimide compound is selected from the compounds of formula (I): 【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 are independently hydrocarbon-based groups optionally interrupted by one or more heteroatoms, preferably alkyl; groups 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, and one or more 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, alkylepoxide, such as propylepoxide or butylepoxide, and azacyclopropane groups; n represents an integer ranging from 1 to 1000; A is the following compound: 【Chemistry 4】 (wherein the monomer is selected from the group consisting of

3. 2. The method according to claim 1, wherein the (poly)carbodiimide compound is selected from the compounds of formula (II): 【Transformation 5】 (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, with 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 an arylene group and a mixture thereof, E is independently -O-R ３ -O-;-S-R ４ -S-;-R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - In these formulae, 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).

4. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ each independently represents an oxygen atom, -R １ and R ２ are independently selected from dialkylamino alcohols from which the hydroxyl groups have been removed, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof; n and z represent integers ranging from 1 to 20, with n+z≧2 and w equal to 1; - L1 is a 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 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 group selected from 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 a 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 ６ 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 4. The method according to claim 3.

5. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ each independently represents 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, with n+z≧2 and w 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 these formulas, R represents a group selected from 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 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 ６ 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 5. The method according to claim 3 or 4.

6. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ each independently represents 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) wherein 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; q represents an integer ranging from 4 to 30; n and z represent integers ranging from 1 to 20, n+z ranging 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, - E is -O-R ３ -O- group (in the formula, R ３ is a 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) The method according to any one of claims 3 to 5, characterized in that

7. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ each independently represents 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) wherein 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; q represents an integer ranging from 4 to 30; n and z represent integers ranging from 1 to 20, n+z ranging from 4 to 10, and w is equal to 1; - L １ However, 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 linear or branched C alkyl group such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms; １ ~C １８ represents an alkylene group) The method according to any one of claims 3 to 6, characterized in that

8. The (poly)carbodiimide compound is represented by the following formula (XII): 【Transformation 6】 (In the formula, L １ is 4,4-dicyclohexylenemethane, n and z represent integers ranging from 1 to 20, n+z is in the range of 4 to 10, and E is -O-R ３ represents an —O— group, and 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 represents an alkylene group, and r and s represent integers ranging from 4 to 30.

8. The method according to claim 3, wherein the compound is selected from the group consisting of:

9. 9. The method according to any one of claims 1 to 8, characterized in that 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.

10. 10. The method according to any one of claims 1 to 9, characterized in that the compound comprising at least one carboxylic acid group is selected from silicone compounds, polyurethanes, acrylic polymers and mixtures thereof, which contain at least one carboxyl group, preferably from polyurethanes, acrylic polymers and mixtures thereof.

11. 11. The method according to any one of claims 1 to 10, characterized in that the compound containing at least one carboxylic acid group 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.

12. 12. Method according to any one of claims 1 to 11, characterized in that the total amount of compounds comprising at least one carboxylic acid group ranges from 0.1% to 30% by weight, more preferentially from 0.5% to 20% by weight, even better from 0.5% to 15% by weight and even more preferentially from 1% to 10% by weight relative to the total weight of composition C.

13. The aminosilicone of formula (XIII) is R1 independently represents a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms; R2 independently represents a group of formula -C ｑ H ２ｑ represents a monovalent group of L, where q is a number ranging from 2 to 8, and L is optionally a group -N(R3) ２ ; -N(R3)-CH ２ -CH ２ -N(R3) ２ ; is a quaternized amine group selected from In the formula, R3 may be the same or different and is a hydrogen atom, a phenyl group, a benzyl group, or a monovalent saturated hydrocarbon group, such as C １ ~C ２０ represents an alkyl group; X is of the following formula (XIV): 【Transformation 7】 represents a group corresponding to the formula: A independently represents a linear or branched alkylene group containing 1 to 6 carbon atoms, optionally interrupted by at least one heteroatom selected from O, S, NH, or a carbonyl group (CO), preferably NH; Q represents an alkylene group containing 1 to 10 carbon atoms, said alkylene group being optionally substituted with at least one alkoxy group containing 1 to 10 carbon atoms, a hydroxyl group, or an aminoalkyl group containing 1 to 20 carbon atoms; n represents an integer ranging from 0 to 500, m represents an integer ranging from 1 to 500, o represents an integer ranging from 0 to 500, and n+m+o is in the range of 250 to 500. The method according to any one of claims 1 to 12, characterized in that

14. The at least one aminosilicone of formula (XIII) R1 independently represents a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms; R2 independently represents a group of formula -C ｑ H ２ｑ L represents a monovalent group, where q is a number ranging from 2 to 8, and L is a group represented by the following formula: -N(R3)-CH ２ -CH ２ -N(R3) ２ is an amine group having In the formula, R3 represents a hydrogen atom; X is of the following formula (XV): 【Transformation 8】 represents a group corresponding to the formula: Q represents an alkylene group containing 1 to 10 carbon atoms, said alkylene group being optionally substituted with at least one alkoxy group containing 1 to 10 carbon atoms, a hydroxyl group, or an aminoalkyl group containing 1 to 20 carbon atoms; n represents an integer ranging from 0 to 500, m represents an integer ranging from 1 to 500, o represents an integer ranging from 0 to 500, and n+m+o is in the range from 250 to 500; The method according to any one of claims 1 to 13, characterized in that

15. The method according to any one of claims 1 to 14, characterized in that the aminosilicone of formula (XIII) is of formula (XVI) below: 【Chemistry 9】 (In the formula, R1 independently represents a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms; Q represents an alkylene group containing 1 to 10 carbon atoms, said alkylene group being optionally substituted with at least one alkoxy group containing 1 to 10 carbon atoms, a hydroxyl group or an aminoalkyl group containing 1 to 20 carbon atoms, n represents an integer ranging from 0 to 500, m represents an integer ranging from 1 to 500, o represents an integer ranging from 0 to 500, and n+m+o is in the range from 250 to 500).

16. 16. Method according to any one of the preceding claims, characterized in that the aminosilicone of formula (XIII) is present in a total amount ranging from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight and even more preferentially from 0.25% to 8% by weight relative to the total weight of composition C.

17. The composition preferably comprises one or more block silicone copolymers derived from dimethylvinylsiloxypolydimethylsiloxane (or divinyldimethicone) and preferably C as an emulsifier. １２ ~C １３ Palace-6 and C １２ ~C １３ Compound of formula (XVIII) obtained in the form of a particle dispersion in the presence of Pareth-23: 【Chemistry 10】 wherein n is an integer greater than 1, preferably greater than 10, for example in the range of 10 to 30, preferably n=20. The method according to any one of claims 1 to 16, characterized in that it comprises

18. 18. Method according to claim 17, characterized in that the block silicone copolymer is present in a total amount ranging from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, more preferentially from 0.1% to 8% by weight and even more preferentially from 0.25% to 5% by weight relative to the total weight of composition C.

19. 19. The method according to any one of claims 1 to 18, characterized in that it also comprises a step of applying to the keratinous hair fibres a composition D comprising at least one silicone compound containing at least one carboxylic acid group.

20. 20. The method according to claim 19, characterized in that the total amount of silicone compounds comprising at least one carboxylic acid group ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferentially from 0.5% to 10% by weight and better still from 1% to 5% by weight, relative to the total weight of composition D.

21. Composition D is preferably ８ ~C １６ 21. The method according to claim 19 or 20, characterized in that it also comprises one or more oils chosen from alkanes, more preferentially from isododecane, isohexadecane, tetradecane and / or mixtures thereof.

22. At the time of use, the method comprises extemporaneously mixing at least two compositions A and B to obtain a composition C, and applying the composition C to the keratinous fibers, 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 group according to any one of claims 1, 10 and 11, Composition A and / or Composition B comprises at least one aminosilicone of formula (XIII) according to any one of claims 1 and 13 to 15, Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof. The method according to any one of claims 1 to 18, characterized in that

23. 1. A device for dyeing keratinous hair fibers, comprising a plurality of compartments, - in a first compartment, a) Composition A comprising at least one (poly)carbodiimide compound according to any one of claims 1 to 8 Including; - in a second compartment, b) Composition B comprising at least one compound containing at least one carboxylic acid group according to any one of claims 1, 10 or 11. Including; Compositions A and / or B are c) at least one aminosilicone of formula (XIII) according to any one of claims 1 and 13 to 15 Including; Composition A and / or Composition B d) at least one colorant selected from pigments, direct dyes, and mixtures thereof; Including; optionally comprising in a third compartment a composition D comprising at least one silicone compound containing at least one carboxyl group according to any one of claims 19 to 21; device.

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