A method for dyeing keratin hair fibers, comprising applying a (poly)carbodiimide compound and a colorant, applying steam, and molding at a specific temperature.

Abstract

The present invention relates to a method for dyeing keratinous hair fibers, comprising: a) applying to the keratinous hair fibers at least one composition C comprising: - at least one (poly)carbodiimide compound; - at least one colorant selected from pigments, direct dyes and mixtures thereof; then b) applying steam to the keratinous hair fibers at a rate of at least 0.5 g / min by means of a device capable of generating steam; and c) shaping the keratinous hair fibers at a temperature of at least 100°C.

Description

[Technical Field]

[0001] The present invention relates to a method for dyeing keratinous hair fibers, which comprises applying a composition C comprising a (poly)carbodiimide compound and a colorant to the keratinous hair fibers, followed by applying steam and shaping at a specific temperature. [Background technology]

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

[0003] There are three basic methods for dyeing keratin hair fibers: a) "Permanent" dyeing: its action is possible to significantly modify the original color and uses oxidative dyes that penetrate the keratin hair fiber and generate pigments through an oxidative condensation process. b) Non-permanent, semi-permanent or direct dyeing: without using the oxidative condensation process and resistant to 4-5 shampoo washes. This involves dyeing keratin fibers with dyes containing direct dyes. c) Temporary dyeing: corrects the original color of the keratin hair fiber, remains from one shampoo wash to the next, and serves to enhance or correct the shade already obtained. This can also be associated with "make-up" methods.

[0004] Other dyeing methods involve the use of pigments. Specifically, the use of pigments on the surface of keratin fibers generally makes it possible to achieve visible coloring on dark keratin hair fibers, since the surface pigments mask the original color of the fibers. However, the colorings obtained by this dyeing method have the disadvantage that they are less resistant to shampooing, as well as to external agents such as sebum, sweat, brushing, and / or friction.

[0005] 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 with regard to the smooth feel of the keratin hair fiber.

[0006] Therefore, there remains a need for a method for dyeing keratin hair fibers that has the advantage of obtaining a uniform colored coating on the keratin hair fibers, while at the same time forming a durable coating without degrading the keratin hair fibers against the various stresses to which the keratin hair fibers may be subjected, such as shampooing and brushing and / or rubbing, and that provides improved keratin hair fiber conditioning properties, particularly with regard to the smooth feel of the keratin hair fibers. Summary of the Invention [Problem to be solved by the invention]

[0007] It is therefore an object of the present invention to develop a method for dyeing keratinous hair fibers, which obtains a smooth and uniform colored coating on the keratinous hair fibers, and at the same time forms a coating that is durable with respect to shampooing and with respect to the various stresses to which the keratinous hair fibers may be subjected, such as brushing and / or rubbing, without degrading the keratinous hair fibers, and which imparts improved keratinous hair fiber conditioning properties, in particular with respect to the smooth feel of the keratinous hair fibers. [Means for solving the problem]

[0008] One subject of the present invention is therefore a method for dyeing keratinous hair fibres, comprising: a) Keratin hair fibers, - at least one (poly)carbodiimide compound; - at least one colorant selected from pigments, direct dyes and mixtures thereof; applying at least one composition C comprising: b) applying steam to the keratinous hair fibers at a rate of 0.5 g / min or more by a device capable of generating steam; c) forming keratin hair fibers at a temperature of 100°C or higher; The method includes:

[0009] The method for dyeing keratin hair fibers according to the present invention allows obtaining a colored coating on the keratin hair fiber, which is visible on all keratin hair fiber types, is durable when washed with shampoo, and at the same time maintains the physical quality of the keratin hair fiber. Such a coating can withstand external stresses to which the keratin hair fiber may be subjected, such as blow-drying and sweating. This allows obtaining a particularly uniform deposit. DETAILED DESCRIPTION OF THE INVENTION

[0010] For purposes of the present invention, the term "colorant that lasts with respect to shampoo washes" means that the color obtained lasts after one shampoo wash, preferably after five shampoo washes.

[0011] The term "at least one" means one or more.

[0012] Unless otherwise specified, the limits of a range of values ​​are encompassed within the range, particularly the expressions "to" and "range of...to...".

[0013] The invention is not limited to the illustrated embodiments, and features of the various embodiments may be combined in particular variations not illustrated.

[0014] For purposes of this invention, unless otherwise specified: - "Alkyl" group refers to a linear or branched 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; - "Alkylene" group denotes 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 monocyclic or polycyclic, preferably monocyclic, hydrocarbon-based group containing 1 to 3 rings, preferably 2 rings, and containing 3 to 24 carbon atoms, in particular 3 to 20 carbon atoms, more particularly 3 to 13 carbon atoms, even more particularly 3 to 12 carbon atoms, preferably 5 to 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, wherein the cycloalkyl group can be substituted by 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" groups have the above-defined "cycloalkyl", preferably C3-C 12 refers to a divalent cycloalkyl group; - "aryl" group is a monocyclic, bicyclic or tricyclic, fused or non-fused, 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 the phenyl group may be substituted with one or more (C1-C4) alkyl groups such as methyl, preferably tolyl, xylyl or methylnaphthyl, preferably the aryl group represents phenyl; - an "arylene" group is a divalent aryl group with "aryl" as defined above, preferably arylene represents phenylene; - "heterocyclic" group is a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based group containing one or more heteroatoms, preferably 1 to 5 atoms selected from O, S or N, and containing 3 to 20 ring members, preferably 5 to 10 ring members, such as 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.

[0015] Unless otherwise specified, when a compound is referred to in this application, this also includes its optical isomers, its geometric isomers, its tautomers or its salts, either alone or in mixtures.

[0016] The term "hair keratin fibers" means keratin hair fibers or hair. In other words, the expressions "hair keratin fibers", "keratin hair fibers" and "hair" are equivalent in the remainder of the description.

[0017] For the purposes of the present invention, the term "keratinous hair fibers" means keratinous hair fibers of the head. This term does not correspond to body hair, eyebrows or eyelashes.

[0018] Polycarbodiimide Compounds The composition C according to the invention used in connection with the method of the invention comprises at least one (poly)carbodiimide compound.

[0019] The composition may comprise at least two different (poly)carbodiimide compounds present as a mixture in the composition.

[0020] 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 being not more than 200, preferably not more than 150, more preferentially not more than 100.

[0021] The term "carbodiimide group" refers to a divalent, linear, three-atom moiety of the general formula -(N=C=N)-.

[0022] The (poly)carbodiimide compound according to the present invention may optionally comprise in its structure one or more reactive groups different from the carbodiimide group selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, such as propylepoxide or butylepoxide, and azacyclopropane groups.

[0023] 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, alkylepoxides such as propylepoxide or butylepoxide, and azacyclopropane groups.

[0024] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (I): [ka] (In the formula, X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; R1 and R2 independently represent hydrocarbon-based groups optionally interrupted by one or more heteroatoms, preferably groups selected from alkyl, alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxides, such as propylepoxide or butylepoxide, and azacyclopropane groups, and represents a hydrocarbon-based group, preferably a group selected from alkyl, optionally interrupted by one or more heteroatoms and one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, such as propylepoxide or butylepoxide, and azacyclopropane groups; - n represents an integer ranging from 1 to 1000; and A is one of the following compounds: [ka] is a monomer selected from The compound is selected from the group consisting of:

[0025] According to another embodiment, the (poly)carbodiimide compound has the following formula (I'): [ka] (In the formula, X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; Y1 and Y2 are independently saturated C1 to C 36 Aliphatic group or C6~C 24 represents a divalent organic group selected from an aromatic or alkylaromatic group, wherein the aliphatic or aromatic group optionally contains one or more non-pendant heteroatoms such as nitrogen atoms, oxygen atoms, sulfur atoms, or combinations thereof; Z1 and Z2 independently represent a reactive end group or an inactive end group; As inert end groups, Z1 and Z2 are independently saturated, linear or branched or cyclic C1-C 50 Aliphatic group or C6~C 18 may represent an aromatic group, said aliphatic and aromatic groups optionally containing 1 to 10 heteroatoms selected from nitrogen, oxygen, sulfur and combinations thereof, and 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 or branched or cyclic aliphatic groups or aromatic groups or alkylaromatic groups linked via carbonate, ester, ether, amide, urethane or urea repeating bonds or combinations thereof; - A represents a divalent aliphatic, aromatic, alkylaromatic or straight-chain, saturated, branched or cyclic group containing 2 to 30 carbon atoms, which may optionally contain one or more non-pendant heteroatoms in the aliphatic or aromatic chain, such as nitrogen atoms, oxygen atoms, sulfur atoms or combinations thereof; - r represents an integer equal to 0 or 1; m represents an integer ranging from 0 to 1000, preferably equal to 0 or 1; m' represents an integer ranging from 0 to 1000, preferably equal to 0 or 1; - n represents an integer ranging from 0 to 1000, preferably equal to 0 or 1, where m+(m'*n)≧2. The compound is selected from the group consisting of:

[0026] 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.

[0027] Such (poly)carbodiimide compounds are sold, for example, by Stahl BV under the names Permutex XR, RelcaLink 10 and Picassian XL, and by Nisshinbo Chemicals under the name Carbodilite, including 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 and V-05.

[0028] Preferably, the (poly)carbodiimide compound is represented by the following formula (II): [ka] (In the formula, X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; - R1 and R2 independently represent a hydrocarbon-based group optionally interrupted by one or more heteroatoms; - n and z represent integers ranging from 1 to 20, where n+z≧2, and w represents an integer ranging from 1 to 3; L1 is independently a divalent C1 to C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 arylene groups and mixtures thereof; - E independently represents a group selected from -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms. The compound is selected from the group consisting of:

[0029] 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.

[0030] The hydrocarbon-based group may contain one or more cyclic groups.

[0031] The hydrocarbon-based group may be interrupted by one or more heteroatoms selected in particular from O, S or N, and / or may be substituted with one or more cations, anions or zwitterions, or cationic groups such as ammonium, anionic groups such as carboxylate, or zwitterionic groups, and / or may contain metal ions that can be incorporated in the form of salts.

[0032] 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.

[0033] Preferably, X1 and X2 independently represent an oxygen atom.

[0034] Preferably, R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, from which the hydroxyl groups have been removed, and mixtures thereof.

[0035] In a preferred embodiment, R1 and R2 are selected from the following groups (i) to (iv): (i) Formula (III): R7-OC(O)-C(R8)(H)- (III) (wherein R7 represents a C1-C3 alkyl group, and R8 represents a hydrogen atom or a C1-C3 alkyl group, preferably R7 is methyl, and R8 is a hydrogen atom or methyl). The compound (ii) Formula (IV): R9-[O-CH2-C(H)(R 10 )] p - (IV) (wherein R9 represents a C1-C4 alkyl group, R 10 represents a hydrogen atom or a C1-C4 alkyl group, p represents an integer ranging from 1 to 3, preferably R9 is methyl, ethyl or butyl, and R 10 is a hydrogen atom or methyl, and p is equal to 1. The compound (iii) Formula (V): (R 11 )2N-CH2-C(H)(R 12 )- (V) (In the formula, R 11 represents a C1-C4 alkyl group, and R 12 represents a hydrogen atom or a C1-C4 alkyl group; preferably, R 11 is methyl, ethyl or butyl, and R 12 is a hydrogen atom or methyl) The compound (iv) Formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) (In the formula, R 13 represents a C1-C4 alkyl group, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, q represents an integer ranging from 4 to 30, and preferably, R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl) Compounds of are independently selected from

[0036] 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.

[0037] 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 set out above, and the other of the R1 or R2 groups represents a compound of formula (VI) as set out above.

[0038] 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.

[0039] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl, and q represents an integer ranging from 4 to 30.

[0040] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), wherein R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer in the range of 4-30.

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

[0042] Preferably, z represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0043] Preferably, w is equal to one.

[0044] Preferably, w is equal to 1 and n+z represents an integer in the range 4-10.

[0045] Preferably, L1 is a divalent C1-C alkyl group such as methylene, ethylene, and propylene. 18Aliphatic hydrocarbon groups, C3 to C such as cyclopentylene, cycloheptylene, and cyclohexylene 15 C3-C such as cycloalkylene groups, imidazole, 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.

[0046] 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.

[0047] Preferably, L1 is C3 to C 15 Cycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, such as those of the following formula (VII): [ka] is selected from.

[0048] Preferably, L1 is represented by the following formula (VIII): [ka] The corresponding 4,4-dicyclohexylenemethane is

[0049] 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 m-tetramethylxylylene, which is represented by

[0050] As previously mentioned, E independently represents a group selected from -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; and R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms.

[0051] Preferably, R3 and R4 independently represent a C6-C 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 The alkylene groups are selected from alkylene groups as well as mixtures thereof.

[0052] More preferentially, R3 and R4 independently represent linear or branched C1-C6 alkylenes, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms. 18 The alkylene group is selected from the group consisting of:

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

[0054] Preferably, R6 is a C6-C, such as phenylene, optionally interrupted by one or more heteroatoms. 14 C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 The alkylene groups are selected from alkylene groups as well as mixtures thereof.

[0055] 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 group is selected from alkylene groups and mixtures thereof.

[0056] More preferentially, E represents a -O-R3-O- group, where R3 is a linear or branched C1-C6 alkyl group, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms. 18 Represents an alkylene group.

[0057] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (X): [ka] (wherein R independently represents an alkyl group containing 1 to 24 carbon atoms, a cycloalkyl group containing 3 to 24 carbon atoms, or an aryl group containing 6 to 24 carbon atoms; and n represents an integer ranging from 2 to 100. It is a copolymer derived from α-methylstyryl isocyanate.

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

[0059] The term "cycloalkyl group" in this embodiment is as defined above.

[0060] 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.

[0061] 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

[0062] The "alkyl group", "cycloalkyl group" and "aryl group" are as defined above.

[0063] According to a preferred embodiment, the (poly)carbodiimide compound is selected from compounds of formula (I) or formula (II), wherein: X1 and X2 independently represent an oxygen atom; R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed, and more preferentially R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30; - n and z, if present, represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L1, if present, is a divalent C1-C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12Heterocycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, preferably C3-C 15 cycloalkylene groups; - A, if present, 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, independently represents a group selected from -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-, where R3 and R4 are independently 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; - when R5 is not a covalent bond, R5 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms, if present; 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; and R6, if present, 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 group is selected from alkylene groups and mixtures thereof.

[0064] 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, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, from which the hydroxyl groups have been removed, and mixtures thereof; - n and z represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L1 is divalent C1 to C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 arylene groups and mixtures thereof; - E independently represents a group selected from -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently a C-C alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; When R5 is not a covalent bond, R5 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; and R6 is a C-C group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 The alkylene group is selected from alkylene groups and mixtures thereof.

[0065] 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 the hydroxyl group has been removed; - n and z represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L1 is C3~C 15 is a cycloalkylene group; - E independently represents a group selected from -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently a C-C alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; When R5 is not a covalent bond, R5 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; and R6 is a C-C group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 The alkylene group is selected from alkylene groups and mixtures thereof.

[0066] 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 where R 13represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30; - n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10 and w is equal to 1; - L1 is a C3-C alkyl group such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane. 15 is a cycloalkylene group; and E represents a -O-R-O- group, where R is a C-C alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 The alkylene group is selected from alkylene groups and mixtures thereof.

[0067] Even more preferentially, the (poly)carbodiimide compounds are chosen from compounds of formula (II), 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 where R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30; - n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10 and w is equal to 1; - L1 is a C3-C alkyl group such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane. 15a cycloalkylene group, preferably 4,4-dicyclohexylenemethane; - E represents a -O-R3-O- group, where R3 is a linear or branched C1-C6 alkyl group, such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms. 18 Represents an alkylene group.

[0068] According to a preferred embodiment, the (poly)carbodiimide compound has the following formula (XII): [ka] wherein L1 is 4,4-dicyclohexylenemethane, n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10, and E represents an -O-R3-O group, where R3 is a linear or branched C1-C alkyl group, such as methylene, propylene, butylene, or ethylene, optionally interrupted by one or more heteroatoms. 18 represents an alkylene group, and r and s represent integers ranging from 4 to 30. is a compound of

[0069] 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 even better still from 1% to 6% by weight relative to the total weight of composition C.

[0070] coloring agent Composition C used in connection with the method of the present invention comprises one or more colorants selected from pigments, direct dyes and mixtures thereof.

[0071] Preferably, the composition C used in connection with the method according to the invention comprises one or more pigments.

[0072] 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.

[0073] Pigments that can be used are chosen in particular from organic and / or mineral pigments known in the art, in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and Ullmann's Encyclopedia of Industrial Chemistry.

[0074] These may be natural products of natural origin or non-natural products.

[0075] These pigments may be in the form of a pigment powder or a paste. They may be coated or uncoated.

[0076] The pigments may be selected, for example, from mineral pigments, organic pigments, special effect pigments such as lakes, pearlescent agents or glitter flakes, and mixtures thereof.

[0077] The pigment may be a mineral pigment. The term "mineral pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann's encyclopedia. Among the mineral pigments useful in the present invention are iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium oxide.

[0078] The pigment may be an organic pigment. The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann's Encyclopaedia.

[0079] 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.

[0080] 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 red pigments may be selected from those 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.

[0081] Examples of pigment pastes with organic pigments include those sold by Hoechst under the following names: - Cosmenyl Yellow 10G:Yellow 3 pigment (CI 11710); - Cosmenyl Yellow G:Yellow 1 pigment (CI 11680); - Cosmenyl Orange GR: Orange 43 pigment (CI 71105); - Cosmenyl Red R: Red 4 pigment (CI 12085); - Cosmenyl Carmine FB: Red 5 pigment (CI 12490); - Cosmenyl Violet RL: Violet 23 pigment (CI 51319); - Cosmenyl Blue A2R; Blue 15.1 pigment (CI 74160); - Cosmenyl Green GG: Green 7 pigment (CI 74260); - Cosmenyl Black R: Black 7 pigment (CI 77266).

[0082] 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.

[0083] Organic pigments can also be lakes, the term "lake" referring to dyes adsorbed onto insoluble particles so that the resulting composite remains insoluble during use.

[0084] The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

[0085] Among the dyes, mention may be made of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

[0086] An example of a lake is the product known by the following name: D&C Red 7 (CI 15 850:1).

[0087] Pigments can 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.

[0088] 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.

[0089] 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 include pearlescent agents such as Cellini (mica-TiO2-lake) sold by BASF, Prestige (mica-TiO2) sold by Eckart, Prestige Bronze (mica-Fe2O3) sold by Eckart, or Colorona (mica-TiO2-Fe2O3) sold by Merck.

[0090] Gold pearlescent agents, in particular those sold by BASF under the names Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); bronze pearlescent agents, in particular those sold by Merck under the names Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super Bronze (Cloisonne); orange pearlescent agents, in particular those sold by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion Orange (Colorona) and Matte Orange (17449) (Microna); brown pearlescent agents, in particular those sold by BASF under the names Nu-antique Copper copper-tinted pearlescent agents, in particular those sold by BASF under the name Copper 340A (Timica); red-tinted pearlescent agents, in particular those sold by Merck under the name Sienna Fine (17386) (Colorona); yellow-tinted pearlescent agents, in particular those sold by BASF under the name Yellow (4502) (Chromalite); gold-tinted red pearlescent agents, in particular those sold by BASF under the name Sunstone G012 (Gemtone); pink-tinted pearlescent agents, in particular those sold by BASF under the name Tan opale G005 (Gemtone); gold-tinted black pearlescent agents, in particular those sold by BASF under the name Nu antique Bronze 240 blue pearlescent agents, in particular those sold by Merck under the name Matte Blue (17433) (Microna); silvery white pearlescent agents, in particular those sold by Merck under the name Xirona Silver;Mention may also be made of gold-green to pink to orange-shifting pearlescent agents, in particular those sold under the name Indian Summer (Xirona) by Merck; and mixtures thereof.

[0091] Further examples of pearlescent agents include particles comprising a borosilicate substrate coated with titanium oxide.

[0092] Particles comprising a glass substrate coated with titanium oxide are sold in particular under the name Metashine MC1080RY by the company Toyal.

[0093] 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.

[0094] 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 that constitutes them, 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 a 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.

[0095] 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.

[0096] These particles may have various morphologies, in particular in the form of platelets or spheres, in particular in the form of spheres.

[0097] 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.

[0098] 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.

[0099] If the reflective particles have a multilayer structure, they may, for example, comprise 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 may be made of one or more organic and / or mineral materials.

[0100] More particularly, it may be chosen from glass, ceramic, graphite, metal oxides, alumina, silica, silicates, in particular aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, without being limited to this list.

[0101] The reflective material may include a metal or a layer of metallic material.

[0102] 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.

[0103] Further examples of reflective particles comprising an inorganic substrate coated with a metal layer include particles comprising a borosilicate substrate coated with silver.

[0104] 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.

[0105] 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.

[0106] Examples include SiO2 coated aluminum, bronze or copper powders sold under the name Visionaire by the company Eckart.

[0107] 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 (these are materials that either fluoresce in daylight or provide ultraviolet fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, such as those sold by Quantum Dots Corporation.

[0108] The variety of pigments that can be used in the present invention makes it possible to obtain a wide range of colors and also to obtain specific optical effects such as metallic or interference effects.

[0109] 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.

[0110] The pigment may be dispersed in the composition by a dispersant.

[0111] Dispersants protect dispersed particles from agglomeration or aggregation. They can be surfactants, oligomers, polymers, or mixtures of several of these, each containing one or more functional groups with a strong affinity for the surface of the particles to be dispersed. In particular, they can be physically or chemically bonded to the pigment surface. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid, especially C8-C20 fatty acids, and polyols such as glycerol or diglycerol, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g / mol, such as the product sold by Avecia under the name Solsperse 21000, 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.

[0112] 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.

[0113] The pigments used in the composition may be surface treated with an organic agent.

[0114] Thus, pre-surface-treated pigments useful in the present invention are pigments that have been completely or partially surface-treated with organic agents of a chemical, electronic, electrochemical, mechanochemical, or mechanical nature, such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, pp. 53-64, and then dispersed in the compositions of the present invention. These organic agents can be selected from waxes such as carnauba wax and beeswax; fatty acids, fatty alcohols, and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, and lauric acid and their derivatives; anionic surfactants; lecithin; sodium, potassium, magnesium, iron, titanium, zinc, or aluminum salts of fatty acids, such as aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, such as silicones, especially polydimethylsiloxane; organic fluorine compounds, such as perfluoroalkyl ethers; and fluorosilicone compounds.

[0115] 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.

[0116] Surface-treated pigments useful in connection with the present invention can be prepared according to surface treatment techniques well known to those skilled in the art, or can be commercially available as is.

[0117] Preferably, the surface-treated pigment is coated with an organic layer.

[0118] The organic agent with which to treat the pigment can be deposited on the pigment by evaporating the solvent, by chemical reaction between molecules of the surface treatment agent, or by forming a covalent bond between the surface treatment agent and the pigment.

[0119] 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.

[0120] Preferably, an organic agent is used that is covalently bonded to the pigment.

[0121] The agent used for the surface treatment may 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.

[0122] 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 treatment agents, such as the SI surface treatment agent 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 treatment agents, such as the MM surface treatment agent sold by LCW; - Aluminum dimyristate treatment agents, such as the MI surface treatment agent sold by Miyoshi; - Perfluoropolymethyl isopropyl ether treatments, such as the FHC surface treatment sold by LCW; - isostearyl sebacate treatment agents, such as the HS surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - perfluoroalkylphosphate treatment agents, such as the PF surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - acrylate / dimethicone copolymer and perfluoroalkylphosphate treatment agents, such as the FSA surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - Polymethylhydrogenosiloxane / perfluoroalkylphosphate treatment agents, such as FS01 surface treatment agent sold by Daito Chemical Industry 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.

[0123] According to a particular embodiment of the present invention, the dispersant is present together with the organic or mineral pigment in particulate form of submicron size.

[0124] The terms "submicron size" or "submicron" refer to pigments that have been micronized by a micronization process and have an average particle size of less than 1 micrometer (μm), particularly 0.1 to 0.9 μm, and preferably 0.2 to 0.6 μm.

[0125] According to one embodiment, the dispersant and the pigment are present in an amount (dispersant:pigment) of 1:4 to 4:1, in particular 1.5:3.5 to 3.5:1 or even better 1.75:3 to 3:1, by weight ratio.

[0126] Thus, the dispersant has a silicone backbone, for example a silicone polyether, and may be an aminosilicone type dispersant. Suitable dispersants include: aminosilicones, i.e. silicones containing one or more amino groups, such as those sold by BYK under the name BYK LPX 21879, and the names GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1 sold by Genesee Polymers; silicone acrylates, such as Tego® RC 902, Tego® RC 922, Tego® RC 1041 and Tego® RC 1043 sold by Evonik; - polydimethylsiloxane (PDMS) silicones with carboxyl groups, such as X-22162 and X-22370 from Shin-Etsu Chemical Co., Ltd., epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682 and GP-695 from Genesee Polymers or Tego® RC 1401, Tego® RC 1403, Tego® RC 1412 from Evonik.

[0127] According to a particular embodiment, the dispersant is of the aminosilicone type and is cationic.

[0128] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments or organic pigments.

[0129] In one variant of the invention, the pigment is an organic pigment, preferentially an organic pigment surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment is a mineral pigment.

[0130] Preferably, the pigment is selected from iron oxides, in particular red, brown or black iron oxides, such as those sold by SunChemical under the name SunPuro® Red Iron Oxide.

[0131] direct dye Composition C used in connection with the method according to the invention may comprise one or more direct dyes.

[0132] The term "direct dyes" refers to natural and / or synthetic dyes other than oxidation dyes. These are dyes that diffuse superficially onto the fiber.

[0133] These can be ionic or non-ionic, preferably cationic or non-ionic.

[0134] 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.

[0135] The direct dyes are preferably cationic direct dyes, such as hydrazonocationic dyes of the following formulae (XIII) and (XIV) and azocationic dyes of the following formulae (XV) and (XVI). Het + -N(Ra)-N=C(Rb)-Ar,Q- (XIII) Het + -C(Ra)=NN(Rb)-Ar,Q (XIV) Het + -N=N-Ar,Q- (XV) Ar + -N=N-Ar'',Q- (XVI) In formulas (XIII) to (XVI), - Het + represents a cationic heteroaryl group, preferentially having an intracyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted, preferentially with at least one (C1-C8) alkyl group, such as methyl; - Ar +represents an aryl group such as phenyl or naphthyl bearing an exocyclic cationic charge, preferentially ammonium, in particular tri(C1-C8)alkylammonium such as trimethylammonium; - Ar preferentially represents one or more electron-donating groups, such as i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8)(alkyl)amino, in which the alkyl group is optionally substituted with a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) an aryl group, in particular phenyl, optionally substituted with an optionally substituted N—(C1-C8) alkyl-N-aryl(C1-C8) alkylamino, or alternatively, Ar represents a julolidine group; Ar" represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, preferentially optionally substituted with one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups; Ra and Rb may be identical or different and represent a hydrogen atom or an optionally substituted (preferentially by a hydroxyl group) (C1-C8) alkyl group; or else the substituents Ra and Het+ and / or the substituents Rb and Ar, together with the atoms carrying them, form a (hetero)cycloalkyl, in particular Ra and Rb represent a (C1-C4) alkyl group optionally substituted with a hydrogen atom or a hydroxyl group; - Q- represents an organic or inorganic anionic counterion such as a halide or alkyl sulfate.

[0136] Mention may be made in particular of the azo and hydrazono direct dyes with an endocyclic cationic charge of the formulae (XIII) to (XVI) defined above, more particularly the cationic direct dyes with an endocyclic cationic charge described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954, preferentially the following direct dyes: [ka] In formulas (XVII) and (XVIII), -R 1 represents a (C1-C4) alkyl group such as methyl; -R 2 and R 3 may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl; -R 4 represents a hydrogen atom or an electron donating group, such as an optionally substituted (C1-C8) alkyl, an optionally substituted (C1-C8) alkoxy or a (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.

[0137] In particular, the dyes of formula (XV) and (XVI) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof, and Q′ is an anionic counterion as defined above, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0138] 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 derived from a metal or amine, or an ammonium ion). The anionic dye may be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethanoic acid dyes, indoamine acid dyes, anthraquinonic acid dyes, indigoid dyes, and natural acid dyes.

[0139] Acid dyes useful in the present invention include dyes of the following formulae (XIX), (XIX'), (XX), (XX'), (XXI), (XXI'), (XXII), (XXII'), (XXIII), (XXIV), (XXV) and (XXVI): a) diaryl anionic azo dyes of formula (XIX) or (XIX'): [ka] In formulas (XIX) and (XIX'), - R7, R8, R9, R 10 , R'7, R'8, R'9 and R' 10 may be the same or different and are hydrogen atoms or the following: - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be identical or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); - R"-S(O)2-, where R" represents a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group, preferentially a phenylamino or phenyl group; - R'''-S(O)2-X'-, where R''' represents an optionally substituted alkyl or aryl group and X' is as defined above; - (di)(alkyl)amino; - i) nitro; ii) nitroso; iii) (O)2S(O - )-, M + and iv) optionally substituted with one or more groups selected from alkoxy; M + aryl(alkyl)amino, wherein is as defined above; - 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 alternatively 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; + , R°, X, X′, X″ and Ar are as defined above; - W represents a sigma bond σ, an oxygen or sulfur atom or a divalent radical i) -NR-, in which R is as defined above, or ii) methylene -C(Ra)(Rb)-, where Ra and Rb may be identical or different and represent a hydrogen atom or an aryl group, or alternatively Ra and Rb together with the carbon atom carrying them form a spirocycloalkyl; preferentially W represents a sulfur atom or Ra and Rb together form a cyclohexyl; Formulas (XIX) and (XIX') contain at least one sulfonate group (O)S(O - )-,M + or one carboxylate group (O)CO - -,M + ; it is understood that it preferentially comprises sodium sulfonate.

[0140] Examples of dyes of formula (XIX) are Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or Sunset Yellow; Examples of the dye of formula (XIX') include Acid Red 111, Acid Red 134, and Acid Yellow 38.

[0141] b) Pyrazolone anionic azo dyes of formula (XX) and (XX'): [ka] In formulas (XX) and (XX'), -R 11 , R 12 and R 13 may be the same or different and are hydrogen or halogen atoms, alkyl groups 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, where R' 16 does not exist, or instead, R 15 is R 16 together to form a double bond; -R 17 and R 18 may be the same or different and represent a hydrogen atom or one of the following: - (O)2S(O - )-,M + (In the formula, M + is as defined above); - Ar-OS(O)2-, where Ar represents an optionally substituted aryl group, preferentially phenyl optionally substituted with one or more alkyl groups. represents a group selected from: -R 19 and R 20 together form either a double bond or an optionally substituted benzo group D'; - R' 16 , R' 19 and R' 20 may be the same or different and represent a hydrogen atom or an alkyl group or a hydroxyl group; -R 21 represents a hydrogen atom, an alkyl group, or an alkoxy group; Ra and Rb may be identical or different and are as defined above, and preferentially, Ra represents a hydrogen atom and Rb represents an aryl group; Y represents either a hydroxyl group or an oxo group; - [ka] represents a single bond when Y is an oxo group; represents a double bond when Y is a hydroxyl group; Formulas (XX) and (XX') contain at least one sulfonate group (O)S(O) on ring D or E. - )-,M + or one carboxylate group -C(O)O - ,M + ; it is understood that it preferentially comprises sodium sulfonate.

[0142] Examples of dyes of formula (XX) include Acid Red 195, Acid Yellow 23, Acid Yellow 27, and Acid Yellow 76; examples of dyes of formula (XX') include Acid Yellow 17.

[0143] c) Anthraquinone dyes of formula (XXI) and (XXI'): [ka] In formulas (XXI) and (XXI'), -R 22 , R 23 , R 24 , R 25 , R 26 and R 27 may be the same or different and represent a hydrogen or halogen atom, or one of the following: - alkyl; - hydroxyl, mercapto; - alkoxy, alkylthio; - Alkyl and (O)2S(O - ),M + optionally substituted aryloxy or arylthio, which are preferentially substituted by one or more groups selected from + is as defined above); - Alkyl and (O)2S(O - )-,M + (In the formula, M +is as defined above); - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino; - (O)2S(O - )-,M + (In the formula, M + is as defined above) represents a group selected from: Z' is a hydrogen atom or a group NR 28 R 29 (wherein R 28 and R 29 may be the same or different and are hydrogen atoms or the following: - alkyl; - polyhydroxyalkyl, such as hydroxyethyl; one or more groups, in particular i) alkyl, such as methyl, n-dodecyl, n-butyl; ii) (O)S(O - )-, M + (In the formula, M + is as defined above; iii) aryl optionally substituted with R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above and preferentially R° represents an alkyl group); - cycloalkyl; especially cyclohexyl represents a group selected from: - Z is hydroxyl and NR' 28 R' 29 (wherein R' represents a group selected from 28 and R' 29 may be the same or different and are R as defined above. 28 and R 29 represents the same atom or group as Formulas (XXI) and (XXI') contain at least one sulfonate group (O)S(O - )-,M + or one carboxylate group -C(O)O - ,M +, which is understood to comprise preferentially sodium sulfonate.

[0144] Examples of dyes of formula (XXI) include Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2, and an example of a dye of formula (XXI') is Acid Black 48.

[0145] d) Nitro dyes of formula (XXII) and (XXII'): [ka] In formulas (XXII) and (XXII'), -R 30 , R 31 and R 32 may be the same or different and represent a hydrogen or halogen atom, or - alkyl; - alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups; - hydroxyl, mercapto; - Nitro, nitroso; - polyhaloalkyl; - R°-C(X)-X′-, R°-X′-C(X)-, R°-X′-C(X)-X″- (wherein R°, X, X and X″ are as defined above); - (O)2S(O - )-,M + (In the formula, M + is as defined above) represents a group selected from: - (O)CO - -,M + (In the formula, M +is as defined above); - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino; - represents a group selected from heterocycloalkyl, such as piperidino, piperazino or morpholino; in particular R 30 , R 31 and R 32 represents a hydrogen atom; Rc and Rd may be identical or different and represent a hydrogen atom or an alkyl group; - W is as defined above; W represents, in particular, an -NH- group; - ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group; - n is 1 or 2; - p represents an integer between 1 and 5 (inclusive); - q represents an integer between 1 and 4 (inclusive); - u is 0 or 1; - when n is 1, J represents a nitro or nitroso group, in particular nitro; - when n is 2, J represents an oxygen or sulfur atom or a divalent -S(O)m- group, where m represents an integer 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 with Formulas (XXII) and (XXII') contain at least one sulfonate group (O)S(O - )-,M + or one carboxylate group -C(O)O - ,M + , which is understood to comprise preferentially sodium sulfonate.

[0146] Examples of dyes of formula (XXII) include Acid Brown 13 and Acid Orange 3; examples of dyes of formula (XXII') include Acid Yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4'-N,N-2''-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7.

[0147] e) Triarylmethane dyes represented by formula (XXIII): [ka] In formula (XXIII), -R 33 , R 34 , R 35 and R 36 may be identical or different and represent a hydrogen atom or a group selected from alkyl, optionally substituted aryl and optionally substituted arylalkyl; in particular alkyl groups and optionally (O) m S(O - )-, M + group (in the formula, M + and m represents a benzyl group substituted with (as defined above); -R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 may be the same or different and are hydrogen atoms or the following: - alkyl; - alkoxy, alkylthio; - (di)(alkyl)amino; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be identical or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); or - two adjacent groups R 41 and R 42 or R 42 and R 43 or R 43 and R 44 together form a fused benzo group: I'; I' is i) nitro; ii) nitroso; iii) (O)S(O - )-,M + iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; and ix) R°-X'-C(X)-X''-, where M + , R°, X, X' and X'' are as defined above). optionally substituted with one or more groups selected from In particular, R 37 ~R 40 represents a hydrogen atom, and R 41 ~R 44 may be the same or different and are hydroxyl groups or (O)S(O - )-,M + represents;R 43 and R 44 together to form a benzo group, this is preferentially (O)S(O - )-group; At least one of the rings G, H, I, or I′ contains at least one sulfonate group (O)S(O -)- or one carboxylate group C(O)O - -; it is understood to preferentially include sulfonates.

[0148] Examples of dyes of formula (XXIII) include Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid Green 3, Acid Green 5 and Acid Green 50.

[0149] f) Xanthene dyes of formula (XXIV): [ka] In formula (XXIV), -R 45 , R 46 , R 47 and R 48 may be the same or different and represent a hydrogen or halogen atom; -R 49 , R 50 , R 51 and R 52 may be the same or different and represent a hydrogen or halogen atom, or one of the following: - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); represents a group selected from: In particular, R 49 , R 50 , R 51 and R 52 represents a hydrogen or halogen atom; G represents an oxygen or sulfur atom or an NRe group, where Re is as defined above, in particular G represents an oxygen atom; - L is alkoxide O - , M + , thioalkoxide S - , M + or an NRf group (wherein Rf represents a hydrogen atom or an alkyl group, and M + is as defined above, and M + is in particular sodium or potassium); L' is an oxygen or sulfur atom or an ammonium group: N + RfRg, where Rf and Rg may be identical or different and represent a hydrogen atom or an optionally substituted alkyl or aryl group; L' represents, in particular, an oxygen atom or one or more alkyl or (O) m S(O - )-, M + Groups (wherein m and M + represents a phenylamino group optionally substituted with (as defined above); Q and Q', which may be identical or different, represent an oxygen or sulfur atom; in particular, Q and Q' represent an oxygen atom; -M + is as defined above.

[0150] Examples of dyes of formula (XXIV) include Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; and Acid Violet 9.

[0151] g) Indole dyes of formula (XXV): [ka] In formula (XXV), -R 53 , R 54 , R 55 , R 56 , R 57 , R58 , R 59 and R 60 may be the same or different and are hydrogen atoms or the following: - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be identical or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above) represents a group selected from: G represents an oxygen or sulfur atom or an NRe group, where Re is as defined above, in particular G represents an oxygen atom; Ri and Rh may be identical or different and represent a hydrogen atom or an alkyl group; Formula (XXIII) 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.

[0152] An example of a dye of formula (XXV) is Acid Blue 74.

[0153] h) Quinoline dyes of formula (XXVI): [ka] In formula (XXVI), -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 alternatively, R 61 and R 62 or R 61 and R 64 together form one or more (O)S(O - )-, M + group (in the formula, M + represents a hydrogen atom or a cationic counterion), forming a benzo group optionally substituted with Formula (XXVI) contains at least one sulfonate group (O)S(O - )-,M + , which is understood to comprise preferentially sodium sulfonate.

[0154] Examples of dyes of formula (XXVI) include Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0155] 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 can also be used, in particular poultices or extracts based on henna dye.

[0156] Preferably, the direct dye is selected from anionic direct dyes.

[0157] The colorants may be present in a total amount ranging from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, relative to the total amount of composition C; preferably, the colorants are chosen from pigments.

[0158] The pigments may be present in a total amount of from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight, and even better still from 0.5% to 10% by weight relative to the total amount of composition C.

[0159] The dyes may be present in a total amount ranging from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight, relative to the total weight of composition C.

[0160] Compounds containing at least one carboxylic acid functional group Composition C used in connection with the method according to the invention may also comprise at least one compound containing at least one carboxylic acid function.

[0161] Preferably, composition C used in connection with the method according to the invention comprises at least one compound containing at least one carboxylic acid function.

[0162] Preferably, the compound containing at least one carboxylic acid functional group is selected from silicone compounds, polyurethanes, acrylic polymers and mixtures thereof, all of which contain at least one carboxylic acid group.

[0163] Polyurethane and acrylic polymers According to a preferred embodiment, composition C comprises at least one compound containing at least one carboxylic acid functional group chosen from polyurethanes, acrylic polymers and mixtures thereof.

[0164] Preferably, the compound containing at least one carboxylic acid functional group is in the form of an aqueous dispersion of particles of a polymer selected from polyurethanes, acrylic polymers and mixtures thereof.

[0165] Preferably, composition C comprises at least one compound containing at least one carboxylic acid functional group in the form of an aqueous dispersion of particles of polyurethanes, acrylic polymers and mixtures thereof.

[0166] The dispersion may be a simple dispersion of the cosmetic composition in an aqueous medium. A particular example of a dispersion is a latex.

[0167] The aqueous dispersion of polymer particles may be selected from aqueous dispersions of polyurethane particles.

[0168] More particularly, 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 a radical of a low molecular weight diol optionally substituted with one or more ionic groups; n represents an integer ranging from 1 to 5, and - m is greater than 1) and a prepolymer of; - the following formula (B): H2N-R4-NH2(B) wherein R4 represents an alkylene or alkylene oxide group that is not substituted with one or more ionic or potentially ionic groups. with at least one chain extender according to the formula: - the following formula (C): H2N-R5-NH2(C) wherein R5 represents an alkylene group substituted with one or more ionic or potentially ionic groups. and at least one chain extender according to It is obtained by the reaction:

[0169] Among the dihydroxylated compounds that can be used according to the present invention, mention may be made in particular of compounds containing two hydroxyl groups and having a number average molecular weight of about 700 to about 16,000, preferably about 750 to about 5,000. Examples of dihydroxylated compounds having high molecular weights include polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadiene, polyhydroxylated polythioethers, and mixtures thereof. Preferably, the hydroxylated compound is selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0170] 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.

[0171] 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.

[0172] 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 diphenylmethane 2,4-diisocyanate isomer, optionally with diphenylmethane 2,2'-diisocyanate, naphthalene 1,5-diisocyanate and mixtures thereof.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] The prepolymers are extended by two families of chain extenders: The first group of chain extenders corresponds to compounds of general formula (B):

[0179] 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.

[0180] 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.

[0181] The ionic or potentially ionic groups may preferably be selected from tertiary or quaternary ammonium groups or groups that can be converted into such groups, carboxyl groups, carboxylate groups, sulfonic acid groups and sulfonate groups. The conversion of at least a portion of the groups that can be converted into salts of tertiary or quaternary ammonium groups may be carried out before or during mixing with water.

[0182] 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.

[0183] The polyurethanes that can be used according to the invention can also optionally contain compounds (chain terminators) located at each chain end that 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.

[0184] 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 even better less than 1000. Even more preferably, the glass transition temperature of the aqueous dispersion of polyurethane particles is less than 0°C.

[0185] Also preferably, the polyurethane (or active substance or solids) content of the aqueous polyurethane dispersion is from 20% to 60% by weight, more preferentially from 25% to 55% by weight, and even better from 30% to 50% by weight, based on the weight of the dispersion. This is intended to mean that the polyurethane content (dry matter) of the aqueous dispersion is preferably from 20% to 60% by weight, more preferentially from 25% to 55% by weight, and even better from 30% to 50% by weight, relative to the total weight of the dispersion.

[0186] Also preferably, the glass transition temperature (Tg) of the aqueous dispersion of polyurethane particles is less than or equal to -25°C, preferably less than -35°C and more preferentially less than -40°C.

[0187] The average size of the polyurethane particles can be up to about 1000 nm, for example, in the range of about 50 nm to about 800 nm, and 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).

[0188] 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).

[0189] 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).

[0190] 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.

[0191] Preferably, the compound containing at least one carboxylic acid functional group is in the form of an aqueous dispersion of particles of an acrylic polymer, more preferably in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0192] For the purposes of the present invention, the term "polymer" refers to a compound corresponding to the repetition of one or more units (these units are derived from compounds known as monomers), where this or these units are repeated at least twice, preferably at least three times.

[0193] The term "film-forming polymer" refers to a polymer that is capable of forming a macroscopically continuous, preferably a coherent, film on a substrate, in particular keratin hair fibers, either alone or in the presence of an auxiliary film-forming agent.

[0194] 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.

[0195] 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.

[0196] 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 to C 10 Alkyl (meth)acrylates, aryl (meth)acrylates, especially C6-C 10 It is selected from aryl (meth)acrylates and hydroxyalkyl (meth)acrylates, in particular C2 to C6 hydroxyalkyl (meth)acrylates.

[0197] 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.

[0198] Among the hydroxyalkyl(meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0199] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0200] Particularly preferred (meth)acrylic acid esters are alkyl, preferably C1-C 30 , and more preferentially C1~C 20 , and even better C1 to C 10 More specifically, it is a C1 to C4 alkyl (meth)acrylate.

[0201] According to the present invention, the alkyl group of the ester may be fluorinated or even perfluorinated, ie some or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms.

[0202] 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.

[0203] The acrylic polymer according to the invention may be a homopolymer or a copolymer, advantageously a copolymer, and even better a copolymer of (meth)acrylic acid and of a (meth)acrylic acid ester.

[0204] 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 to C 10 , more particularly C1-C4 alkyl (meth)acrylate Contains one or more units derived from

[0205] Preferably, the aqueous dispersion of acrylic polymer particles is surfactant-free.

[0206] The term "surfactant" refers to any agent that can modify the surface tension between two surfaces.

[0207] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and ethyl acrylate, such as the compound sold by BASF under the trade name Luvimer MAE, or the compound sold by Lubrizol under the trade name Fixate Superhold Polymer, such as polyacrylate-2 crosspolymer, or the compound sold by Daito Chemical Industry Co., Ltd. under the trade name Daitosol 3000VP3, or the compound sold by Daito Chemical Industry Co., Ltd. under the trade name Daitosol 3000 SLPN-PE1, such as acrylate copolymer.

[0208] 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.

[0209] Additional monomers may include, for example, styrene monomers, particularly styrene and alpha-methylstyrene, preferably styrene.

[0210] 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.

[0211] 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.

[0212] Acrylic polymers include styrene / (meth)acrylate copolymers sold under the name Joncryl 77 by BASF, Yodosol GH41F by Akzo Nobel and Syntran 5760 CG by Interpolymer.

[0213] Preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles.

[0214] 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 to C 10 , more particularly C1-C4 alkyl (meth)acrylate and at least one aqueous dispersion of acrylic polymer particles comprising one or more units derived from

[0215] Preferably, the acrylic polymer (or active substance or solids) content of the aqueous dispersion of acrylic polymer particles is between 20% and 60% by weight, more preferentially between 22% and 55% by weight, and even better still between 25% and 50% by weight, based on the weight of the dispersion.

[0216] Silicone Acrylic Copolymer According to a particular embodiment, the silicone compound comprising at least one carboxylic acid group is chosen from silicone acrylic copolymers.

[0217] Thus, according to a particular embodiment, the compound containing at least one carboxylic acid functional group is chosen from silicone acrylic copolymers.

[0218] Preferably, the silicone acrylic copolymer comprises: - at least one acrylic or methacrylic or crotonic unit; and - at least one polydimethylsiloxane (PDMS) unit Includes.

[0219] For the purposes of the present invention, the term "polydimethylsiloxane" (also abbreviated as PDMS) denotes, according to the generally accepted practice, any organosilicon polymer or oligomer of linear structure of variable molecular weight, obtained by polymerization and / or polycondensation of appropriately functionalized silanes, and consisting essentially of repeating main units in which silicon atoms are bonded to one another through oxygen atoms (siloxane bonds Si-O-Si), containing methyl groups bonded directly to said silicon atoms through carbon atoms.

[0220] The PDMS chains that can be used to obtain the copolymers used according to the invention preferably contain at least one polymerizable radical group located at at least one of the 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.

[0221] The term "polymerizable radical group" means a group that can polymerize with other polymerizable radical groups or monomers. Preferably, the polydimethylsiloxane unit comprises at least one polymerizable radical group.

[0222] Preferably, the polymerizable radical group comprises at least one vinyl group.

[0223] 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.

[0224] As previously mentioned, the silicone acrylic copolymer comprises at least one acrylic or methacrylic or crotonic unit, i.e., at least one unit containing a carboxylic acid group.

[0225] The term "carboxyl group" refers to COOH or COO - It means functional group, COO - The counterions of the groups may be selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0226] 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.

[0227] 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 from 1 to 20 carbon atoms; vinyl acetate units; vinyl alkyl ester units, wherein the alkyl group is a linear or branched saturated group containing from 2 to 20 carbon atoms; and mixtures thereof; and - one or more silicone acrylic copolymers containing at least one polydimethylsiloxane (PDMS) unit; Includes.

[0228] The term "crotonic unit" means a unit derived from a crotonic acid monomer or a salt thereof.

[0229] The term "alkyl crotonate unit" means a unit derived from a crotonate ester monomer containing a saturated, linear or branched alkyl group containing from 1 to 20 carbon atoms.

[0230] 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.

[0231] The term "vinyl acetate units" means units derived from vinyl acetate monomer.

[0232] 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 - preferably at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable radical group containing at least one vinyl group; Includes.

[0233] According to a particularly preferred embodiment, the silicone acrylic copolymer comprises - at least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, wherein the alkyl group is a linear or branched saturated 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; Includes.

[0234] 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:

[0235] Even more preferentially, the composition comprises: - at least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, wherein the alkyl group is 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 polymer comprises one or more silicone acrylic polymers including:

[0236] Among the silicone acrylic copolymers that may be used in connection with the present invention, mention may be made of the compound sold by Wacker Chemie AG under the trade name Belsil® P1101, which has the INCI name Crotonic Acid / Vinyl C8-12 Isoalkyl Ester / VA / Bis-Vinyl Dimethicone Crosspolymer.

[0237] The total amount of compounds containing at least one carboxylic acid functional group is preferably in the range of 0.1% to 30% by weight, more preferentially 0.5% to 20% by weight, even more preferentially 1% to 15% by weight, and even more preferentially 2% to 10% by weight, relative to the total weight of composition C.

[0238] The total amount of aqueous dispersion of particles of polymer chosen from polyurethanes, acrylic polymers and mixtures thereof preferably ranges from 0.1% to 40% by weight, more preferentially from 0.5% to 30% by weight, even more preferentially from 1% to 25% by weight, and even more preferentially from 2% to 20% by weight, relative to the total weight of composition C.

[0239] According to a particular embodiment, the total amount of the aqueous dispersion of acrylic polymer particles preferably ranges from 0.1% to 40% by weight, more preferentially from 0.5% to 30% by weight, even better from 1% to 25% by weight and even more preferentially from 2% to 20% by weight relative to the total weight of composition C.

[0240] Advantageously, the total amount of silicone acrylic copolymer ranges from 0.1% to 30% by weight, more preferably from 0.5% to 20% by weight, even more preferentially from 1% to 15% by weight, and even more preferentially from 2% to 10% by weight relative to the total weight of composition C.

[0241] Non-carboxylate anionic thickener Composition C used in connection with the method according to the invention may also comprise at least one non-carboxylate anionic thickener.

[0242] For purposes of the present invention, the term "non-carboxylic acid agent" refers to an agent that does not contain a carboxylic acid functional group (-COOH) or a carboxylate functional group (-COO - ) means a drug that does not contain

[0243] For the purposes of the present invention, the term "thickener" means a thickener that, when present at a concentration of 0.05% by weight, thickens the composition into which it is incorporated at room temperature (25°C) and atmospheric pressure at a shear rate of 1 s -1 (Viscosity can be measured using a cone and plate viscometer such as a Haake R600 rheometer).

[0244] Preferably, the non-carboxylic acid anionic thickener is chosen from non-carboxylic acid anionic polymers, more preferentially from anionic polymers containing sulfonic groups.

[0245] For purposes of the present invention, the term "anionic polymer" means a polymer that contains one or more anionic groups or anionic groups and no cationic groups or cationic groups.

[0246] Advantageously, the non-carboxylic acid anionic thickener is chosen from anionic polymers comprising at least one ethylenically unsaturated monomer bearing a sulfonic group, in free form or in partially or completely neutralized form.

[0247] The polymers may be crosslinked or non-crosslinked. They are preferably crosslinked.

[0248] These polymers can be associative or non-associative, preferably non-associative.

[0249] Recall that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0250] Its chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0251] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon chain containing at least 8 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms, more preferentially 18 to 30 carbon atoms.

[0252] Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also represent a hydrocarbon-based polymer (for example, polybutadiene).

[0253] The ethylenically unsaturated monomer having a sulfonic acid group is, in particular, vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylamide (C1-C 22 ) Alkyl sulfonic acid, N-(C1-C 22 ) Alkyl (meth)acrylamide (C1-C 22 ) alkyl sulfonic acids (such as undecylacrylamido methane sulfonic acid) and also partially or fully neutralized forms thereof.

[0254] More preferentially, (meth)acrylamides (C1-C 22) Alkyl sulfonic acids such as acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, as well as partially or fully neutralized forms thereof may be used.

[0255] More specifically, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or fully neutralized forms are used.

[0256] Among the 2-acrylamido-2-methylpropanesulfonic acid copolymers, mention may be made of partially or completely neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide, and particular mention may be made of the products described in Example 1 of EP 503853, to which reference may be made with regard to these polymers.

[0257] Mention may also be made of copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts and hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT 10 by the company SEPPIC (INCI name: Hydroxyethyl acrylate / Sodium acryloyldimethyltaurate copolymer).

[0258] Associative AMPS polymers are particularly suitable for C6-C 22They may be selected from statistical associative AMPS polymers modified by reaction with n-mono- or di-n-alkylamines, such as those described in patent application WO 00 / 31154, the content of which forms an integral part. These polymers may also contain other ethylenically unsaturated hydrophilic monomers, such as (meth)acrylic acid derivatives, for example their esters with monohydric alcohols, or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidones, or mixtures of these compounds.

[0259] Preferred polymers of this family are selected from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0260] These same copolymers may also contain one or more ethylenically unsaturated monomers not containing a fatty chain, such as (meth)acrylic acid derivatives, in particular their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone or mixtures of these compounds.

[0261] These copolymers are described in particular in EP-A-750899, U.S. Pat. No. 5,089,578 and the following publications from Yotaro Morishima: - Self-assembling amphiphilic polyelectrolytes and their nanostructures,Chinese Journal of Polymer Science,Vol.18,No.40,(2000),323-336; - Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering-Macromolecules,Vol.33,No.10(2000),3694-3704; - Solution properties of micelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte::salt effects on rheological behavior-Langmuir,Vol.16,No.12,(2000)5324-5332; - Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers-Polym.Preprint, Div.Polym.Chem.40(2), (1999), 220-221.

[0262] Among these polymers, mention may be made of: - 15% to 60% by mass of AMPS units and 40% to 85% by mass of (C8 to C9 16 ) alkyl (meth) acrylamide or (C8-C 16 ) alkyl (meth)acrylate units, crosslinked or non-crosslinked, neutralized or non-neutralized copolymers, such as those described in EP-A-750899; - 10 mol% to 90 mol% of acrylamide units, 0.1 mol% to 10 mol% of AMPS units, and 5 mol% to 80 mol% of n-(C6 to C 18) terpolymers containing alkylacrylamide units, such as those described in U.S. Pat. No. 5,089,578.

[0263] Mention may also be made of fully neutralized copolymers of AMPS and dodecyl methacrylate and also crosslinked and non-crosslinked copolymers of AMPS and n-dodecyl methacrylamide, such as those described in the abovementioned Morishima paper.

[0264] Preferably, the non-carboxylic anionic thickener is chosen from sodium 2-acrylamido-2-methylpropanesulfonate / hydroxyethyl acrylate copolymers sold by SEPPIC (INCI name Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer).

[0265] Advantageously, the total amount of non-carboxylate anionic thickeners ranges from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even better from 0.1% to 5% by weight and even better still from 0.1% to 3% by weight relative to the total weight of composition C.

[0266] Associative Polymers Composition C according to the invention may also comprise at least one associative polymer containing at least one carboxylic acid functional group and different from the compound different from the non-carboxylic acid anionic thickener defined above.

[0267] Recall that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0268] Its chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0269] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon chain containing at least 10 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms, more preferentially 18 to 30 carbon atoms.

[0270] Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also represent a hydrocarbon-based polymer (for example, polybutadiene).

[0271] Associative polymers can be nonionic, anionic, cationic or amphoteric.

[0272] Preferably, the associative polymer is selected from anionic associative polymers.

[0273] Among the associative polymers of the anionic type, mention may be made of: (a) those comprising at least one hydrophilic unit and at least one fatty chain allyl ether unit, more particularly those in which the hydrophilic unit is made from an anionic ethylenically unsaturated monomer, even more particularly those formed from a vinyl carboxylic acid, most particularly those formed from acrylic acid or methacrylic acid or a mixture thereof;

[0274] Among these anionic associative polymers, those particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and / or methacrylic acid, 5% to 60% by weight of lower alkyl (meth)acrylate, 2% to 50% by weight of aliphatic allyl ether, and 0 to 1% by weight of a crosslinker (a well-known copolymerizable unsaturated polyethylenic monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, or methylene bisacrylamide).

[0275] Among the latter polymers, the most preferred are crosslinked terpolymers of methacrylic acid, ethyl acrylate and polyethylene glycol (10EO) stearyl alcohol ether (Steareth-10), in particular the aqueous 30% emulsion of crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10 allyl ether (40 / 50 / 10) sold by Ciba under the names Salcare SC 80® and Salcare SC 90®.

[0276] - (b) those comprising i) at least one hydrophilic unit of the unsaturated olefinic carboxylic acid type, and ii) at least one hydrophobic unit of the type (C10-C30) alkyl ester of an unsaturated carboxylic acid, etc.

[0277] The unsaturated carboxylic acids useful in the present invention (C 10 ~C 30 ) Alkyl esters include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, and dodecyl acrylate, and the corresponding methacrylic acid esters, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

[0278] Anionic polymers of this type are described and prepared, for example, by US Pat. No. 3,915,921 and US Pat. No. 4,509,949.

[0279] Among this type of anionic associative polymer, 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C 10 ~C 30 alkyl acrylate (hydrophobic unit) and 0 to 6% by mass of a cross-linkable polymerizable monomer, or the above-mentioned, 98% to 96% by mass of acrylic acid (hydrophilic unit), 1% to 4% by mass of C 10 ~C 30More particularly, one consisting of alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of a cross-linking polymerizable monomer will be used.

[0280] Among the above-mentioned polymers, those most particularly preferred according to the invention are Pemulen TR1®, Pemulen TR2®, Carbopol 1382®, and even more preferentially the product sold by Goodrich under the trade name Pemulen TR1® and the product sold by SEPPIC under the name Coatex SX®.

[0281] Mention may also be made of the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer sold under the name Acrylidone LM by the company ISP.

[0282] - (c) Maleic anhydride / C 30 ~C 38 α-olefin / alkyl maleate terpolymers, such as those sold by Newphase Technologies under the trade name Performa V 1608® (maleic anhydride / C 30 ~C 38 α-olefin / isopropyl maleate copolymer); (d) Acrylic terpolymers, including: i) approximately 20% by mass to 70% by mass of an α,β-monoethylenically unsaturated carboxylic acid [A]; ii) approximately 20% to 80% by weight of an α,β-monoethylenically unsaturated non-surfactant monomer other than [A]; iii) a nonionic monourethane which is a reaction product of approximately 0.5% to 60% by weight of a surfactant having one hydroxyl group with a monoethylenically unsaturated monoisocyanate; For example, the terpolymer described in EP-A-0 173 109, more particularly in Example 3, namely an aqueous 25% dispersion of terpolymer of methacrylic acid / methyl acrylate / behenyl alcohol dimethyl-meta-isopropenyl benzyl isocyanate ethoxylate (40EO). (e) copolymers comprising, among these monomers, α,β-monoethylenically unsaturated carboxylic acids and esters of α,β-monoethylenically unsaturated carboxylic acids with oxyalkylenated fatty alcohols.

[0283] Preferentially, these compounds further comprise, as monomers, esters of α,β-monoethylenically unsaturated carboxylic acids and of C1-C4 alcohols.

[0284] Examples of this type of compound include Aculyn 22®, sold by Roehm & Haas, which is a terpolymer of methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate, and Aculyn 88, also sold by Roehm & Haas.

[0285] Advantageously, the associative polymer, different from the compound containing at least one carboxylic acid function and different from the aforementioned non-carboxylic acid anionic thickener, is chosen from acrylic associative polymers, more preferentially carboxylic acrylic associative polymers.

[0286] Particularly preferably, the associative polymer is different from a compound containing at least one carboxylic acid function, different from the aforementioned non-carboxylic acid anionic thickeners, and is chosen from copolymers which contain among their monomers α,β-monoethylenically unsaturated carboxylic acids and esters of α,β-monoethylenically unsaturated carboxylic acids with oxyalkylenated fatty alcohols.

[0287] Advantageously, the total amount of associative polymers different from the compounds containing at least one carboxylic acid function and different from said non-carboxylic anionic thickeners ranges from 0.05% to 15% by weight, preferably from 0.05% to 10% by weight, more preferentially from 0.1% to 5% by weight and even more preferentially from 0.1% to 1% by weight relative to the total weight of composition C.

[0288] organic solvents Composition C according to the invention may comprise one or more organic solvents.

[0289] Examples of organic solvents include C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monomethyl ether, as well as aromatic alcohols, in particular aromatic monoalcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0290] The organic solvents may be present in a total amount of from 0.01% to 60% by weight, preferably from 0.05% to 50% by weight and more preferentially from 0.1% to 45% by weight relative to the total weight of composition C.

[0291] 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.

[0292] additives Composition C used in connection with the method according to the invention may contain any adjuvant or additive normally used.

[0293] Among the additives that may be contained in the composition, mention may be made of reducing agents, emollients, antifoaming agents, moisturizing agents, UV screening agents, peptizing agents, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than those previously described, preservatives, silicones different from the compounds previously described, oils, waxes and mixtures thereof.

[0294] The composition C used in connection with the method of the invention may in particular be in the form of a suspension, a dispersion, a gel, an emulsion, in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion or a multiphase emulsion (W / O / W or polyol / O / W or O / W / O), a cream, a mousse, a stick, a vesicle, in particular a dispersion of ionic or non-ionic lipids or a two-phase or multiphase lotion.

[0295] A person skilled in the art will be able, based on his general knowledge, to select a suitable presentation form as well as a method for preparing it, taking into account first the properties of the components used, in particular their solubility in the carrier, and then the intended use of the composition.

[0296] Application of steam to keratin hair fibres and shaping According to steps b) and c) of the method according to the invention, steam is applied to the keratin hair fibres in an amount of at least 0.5 g / min by means of a device capable of generating steam, and the keratin hair fibres are moulded at a temperature of at least 100°C.

[0297] According to a particular embodiment, step b) of applying steam is separated from step c) of shaping the keratinous hair fibers. Preferably, step b) of applying steam is followed by step c) of shaping.

[0298] According to another particular embodiment, step b) of applying steam and step c) of shaping the keratinous hair fibers are carried out simultaneously.

[0299] The application of steam can be carried out using any device known per se, capable of producing steam in an amount of 0.5 g / min or more. The device comprises at least one tank containing heatable water.

[0300] According to certain embodiments, the device is portable, i.e., the tank may be in contact with the portion of the device that contains the vapor dispensing orifice.

[0301] Preferably, the device used in the method according to the invention is a handpiece, which may include at least one arm and at least one tank containing heatable water.

[0302] Preferably, the device comprises two arms that can be moved relative to each other between a proximity configuration for treating the head of a keratinous hair fiber and a dispersion configuration in which the keratinous hair fiber to be treated is engaged.

[0303] The arms are hinged to one another by hinge pins.

[0304] A resilient return member may be provided to return the arms to the extended configuration.

[0305] The arms define between them a keratin hair fiber treatment zone intended to receive the lock of keratin hair fibers to be treated, along which the handpiece is moved during treatment. The device can be moved, for example, in a direction from the root to the end of the keratin hair fiber strand of the lock. Such a device allows for easy application of steam to the keratin hair fibers.

[0306] The keratin hair fiber shaping means can be carried out using any kind of means known in the art that allows heating to temperatures of 100° C. or higher. The keratin hair fiber shaping means is, for example, a device having a heated surface that is in contact with the keratin hair fiber and is able to apply a slight tension to the keratin hair fiber, in particular allowing the keratin hair fiber to be straightened, styled or detangled.

[0307] Shaping of keratinous hair fibers can be carried out using conventional shaping devices such as straightening or curling irons, or by blow-drying with a hair dryer and brush. This shaping is generally carried out at temperatures between 100° C. and 250° C., preferably between 150° C. and 230° C. According to a preferred embodiment, shaping is carried out with a straightening iron.

[0308] The application and shaping of steam may be carried out in the same device comprising a tank initially containing a liquid, preferably water, a means for heating the tank to form steam, and a system for delivering steam to keratinous hair fibers, which may be placed in a straightening iron. Such a device is known as a Steampod.

[0309] Thus, in addition to the system for emitting steam described above, each arm may include means for heating the keratin hair fibers, in particular in the form of a plate made of a heat-conducting material or a light-emitting system of the IR or LED type, defining a contact surface with the keratin hair fibers and bringing the keratin hair fibers to a temperature of, for example, 100°C or higher, allowing them to be shaped.

[0310] Advantageously, the amount of steam ranges from 0.5 to 60 g / min, preferably from 0.5 to 20 g / min, more preferentially from 0.5 to 10 g / min, even more preferentially from 0.5 to 5 g / min and even more preferably from 0.5 to 1 g / min.

[0311] Advantageously, the molding temperature during step c) ranges from 100 to 250°C, preferably from 150 to 250°C, more preferentially from 150 to 230°C and even more preferentially from 180 to 220°C.

[0312] Application of Composition G The dyeing method according to the invention may comprise, after the step b) of applying steam and the step c) of shaping have been carried out, the application to the keratinous hair fibres of at least one composition G, which composition G comprises: - at least one (poly)carbodiimide compound; - optionally at least one compound containing at least one carboxylic acid functional group Includes.

[0313] The (poly)carbodiimide compound is as defined above and is as preferred as indicated for composition C.

[0314] The (poly)carbodiimide compound used in composition G may be the same as or different from that used in composition C, and is preferably the same.

[0315] Advantageously, the total amount of (poly)carbodiimide compounds in composition G ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferentially from 0.2% to 10% by weight, even more preferentially from 0.5% to 8% by weight and even better from 1% to 6% by weight relative to the total weight of composition G.

[0316] The compounds containing at least one carboxylic acid function are as defined above and are preferred as indicated for composition C.

[0317] The compound containing at least one carboxylic acid functional group used in connection with composition G may be the same as or different from that used in composition C, preferably the same.

[0318] Advantageously, the total amount of compounds comprising at least one carboxylic acid function ranges from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferentially from 1% to 15% by weight and even better still from 2% to 10% by weight relative to the total weight of composition G.

[0319] Composition G may also contain a colorant selected from the pigments, direct dyes and mixtures thereof described above.

[0320] Preferably, composition G does not contain any colorant selected from pigments, direct dyes and mixtures thereof.

[0321] Composition G may also include a non-carboxylate anionic thickener and / or an associative polymer as defined above.

[0322] According to a particularly preferred embodiment, composition G comprises the same (poly)carbodiimide compound as composition C and the same compound comprising at least one carboxylic acid functional group as composition C, and preferably composition G does not comprise a colorant.

[0323] The application of this composition G can be followed by a step of applying heat, for example a step of drying at a temperature of 50 to 110°C, a step of straightening the keratin hair fibers with a straightening iron or a step of applying steam at a rate of 0.5 g / min or more with a device capable of generating steam and shaping at a temperature of 100°C or more, these steps being identical to the steps b) and c) above.

[0324] According to a particular embodiment, the method according to the invention comprises, after step c), a further step: d) applying to said keratinous hair fibres at least one composition G comprising at least one (poly)carbodiimide compound as previously described; then e) optionally drying the keratinous hair fibers; and then f) applying steam to the keratinous hair fibers at a rate of 0.5 g / min or more by means of a device capable of generating steam; g) forming the keratin hair fibers at a temperature of 100°C or higher, preferably between 150°C and 230°C; Includes.

[0325] According to a particular embodiment, the step f) of applying steam is separated from the step γ) of shaping the keratinous hair fibers; preferably, the step f) of applying steam is followed by the shaping step g).

[0326] According to another particular embodiment, step f) of applying steam and step g) of shaping the keratinous hair fibers are carried out simultaneously.

[0327] According to another particular embodiment, the method according to the invention comprises, after step c), the further step: d) applying to said keratinous hair fibres at least one composition G comprising at least one (poly)carbodiimide compound as previously described; then e) drying the keratin hair fibers; and then f) optionally applying steam to the keratinous hair fibers in an amount of 0.5 g / min or more by means of a device capable of generating steam; d) optionally shaping the keratin hair fibers at a temperature above 100°C, preferably between 150°C and 230°C; Includes.

[0328] protocol Composition C as described above can be used on wet or dry keratinous hair fibers, and on all types of keratinous hair fibers, whether light or dark, natural or dyed, permanently waved, bleached or straightened.

[0329] According to a particular embodiment of the invention, the keratinous hair fibers are washed before applying composition C.

[0330] Preferably, application of composition C to keratinous hair fibers is followed by a washing, rinsing, draining or drying step.

[0331] More preferentially, a drying step is carried out after the application of composition C to the keratinous hair fibres. Preferably, the method according to the invention therefore comprises a drying step between steps a) and b).

[0332] The application of composition C to keratinous hair fibers can be carried out by any conventional means, in particular with a comb, a fine-toothed brush, a wide-toothed brush, a sponge or the fingers.

[0333] The application of composition C to keratinous hair fibers is generally carried out at room temperature (15 to 25° C.).

[0334] After application of composition C to keratinous hair fibers, it is possible to wait, for example, from 1 minute to 6 hours, in particular from 1 minute to 2 hours, more particularly from 1 minute to 1 hour, and more preferentially from 1 minute to 30 minutes before the washing, rinsing or draining and / or drying steps.

[0335] After applying composition C, the keratin hair fibres are dried or dried, for example, using a hair dryer, at a temperature of, for example, 30° C. or higher.

[0336] During the process of drying keratinous hair fibers, mechanical action such as combing, brushing or running fingers through the strands can be exerted.

[0337] If the step of drying the keratinous hair fibers 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.

[0338] Preferably, when drying the keratinous hair fibers, in addition to the supply of heat, it is dried by using an air current, which makes it possible to improve the strand separation of the coating.

[0339] After the drying step, if performed, step b) of the method of the invention is carried out.

[0340] Preferably, the present invention relates to a method for dyeing keratinous hair fibers, comprising the following steps: i) to keratin hair fibers, - at least one (poly)carbodiimide compound as described above; at least one colorant selected from the aforementioned pigments, direct dyes and mixtures thereof; applying at least one composition C comprising: ii) optionally, leaving said composition C on the keratin hair fibres for a period of 1 minute to 30 minutes, preferably 1 to 20 minutes; then iii) optionally drying the keratinous hair fibers; and then iv) applying steam to the keratinous hair fibers in an amount of at least 0.5 g / min by means of a device capable of generating steam; v) forming keratin hair fibers at a temperature of 100°C or higher; The method includes:

[0341] The method of the invention may comprise additional steps, in particular steps comprising applying a composition G comprising at least one (poly)carbodiimide compound as described above.

[0342] Advantageously, the (poly)carbodiimide compound used in connection with this composition G is the same or different, preferably the same, as that used in connection with composition C. It may also comprise a compound containing at least one carboxylic acid function as defined above.

[0343] The compound containing at least one carboxylic acid functional group used in connection with composition G may be the same as or different from that used in connection with composition C, preferably the same.

[0344] Composition G may also include a colorant selected from pigments, direct dyes, and mixtures thereof.

[0345] Preferably, composition G does not contain any colorant selected from pigments, direct dyes and mixtures thereof.

[0346] Composition G may also include a non-carboxylate anionic thickener and / or an associative polymer as defined above.

[0347] According to one embodiment, the application of composition G is followed by a step of e) drying the keratin hair fibers, and / or f) applying steam to the keratin hair fibers in an amount of 0.5 g / min or more by means of a device capable of generating steam, and g) shaping the keratin hair fibers at a temperature of 100°C or more as described above.

[0348] According to a particular embodiment, step f) is dissociated from step g); preferably, step f) is followed by step g).

[0349] According to another particular embodiment, steps f) and g) are carried out simultaneously.

[0350] According to a preferred embodiment, composition G does not contain any of the aforementioned colorants.

[0351] Preferably, composition C also comprises at least one compound containing at least one carboxylic acid functional group as described above, preferably an acrylic polymer.

[0352] Preferably, composition C also comprises at least one non-carboxylic anionic thickener as described above, preferably chosen from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0353] Preferably, composition C also comprises at least one associative polymer, preferably an acrylic associative polymer and more preferentially a carboxylic acrylic associative polymer, as defined above, different from the compound containing at least one carboxylic acid function and different from the non-carboxylic acid anionic thickeners defined above.

[0354] Advantageously, the step of applying composition C to the keratinous hair fibres is repeated several times.

[0355] According to a preferred embodiment, step a) comprises, in use, extemporaneously mixing at least two compositions A and B to obtain a composition C, and applying composition C to keratinous hair fibres, - composition A comprises at least one (poly)carbodiimide compound as defined above; - composition B comprises at least one compound containing at least one carboxylic acid functional group as defined above; Composition A and / or Composition B comprise at least one colorant selected from pigments, direct dyes and mixtures thereof as defined above.

[0356] According to a preferred embodiment, the dyeing method according to the invention is a method for dyeing keratinous hair fibers, comprising: a) in use, extemporaneously mixing at least two compositions A and B to obtain composition C, and applying composition C to keratinous hair fibers, - composition A comprises at least one (poly)carbodiimide compound as defined above; - composition B comprises a compound containing at least one carboxylic acid functional group as defined above; applying composition A and / or composition B, which contains at least one colorant selected from pigments, direct dyes and mixtures thereof as defined above; and then drying the keratinous hair fibers by applying heat and / or air currents; and then b) applying steam to the keratinous hair fibers at a rate of 0.5 g / min or more by means of a device capable of generating steam; c) forming keratin hair fibers at a temperature of 100°C or higher; The method includes:

[0357] According to a particular embodiment, step b) is dissociated from step c); preferably, step b) is followed by step c).

[0358] According to another particular embodiment, steps b) and c) are carried out simultaneously.

[0359] Composition A and / or Composition B may optionally comprise at least one non-carboxylic acid anionic thickener as described above and / or at least one associative polymer as described above, which is different from the compound containing at least one carboxylic acid functional group and different from the non-carboxylic acid anionic thickener defined above.

[0360] Advantageously, composition A comprises at least one non-carboxylate anionic thickener as described above.

[0361] Advantageously, composition B also comprises at least one associative polymer as defined above, different from the compound containing at least one carboxylic acid function and different from the non-carboxylic acid anionic thickeners defined above.

[0362] Preferably, composition B comprises at least one colorant selected from the pigments, direct dyes and mixtures thereof previously described.

[0363] Preferably, Composition A does not contain any colorant selected from the previously mentioned pigments, direct dyes and mixtures thereof.

[0364] According to this embodiment, the mixing of compositions A and B is preferably carried out less than 15 minutes before application to the keratinous hair fibre, more preferentially less than 10 minutes and even better less than 5 minutes before application.

[0365] The weight ratio of composition A to composition B preferably ranges from 0.1 to 10, preferentially from 0.2 to 5, even better from 0.5 to 2, or even from 0.6 to 1.5. In a particular embodiment, the weight ratio of composition A to composition B is equal to 1.

[0366] The total amount of (poly)carbodiimide compounds is preferably in the range of 0.01% by mass to 40% by mass, more preferentially 0.1% by mass to 30% by mass, even better still 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.

[0367] The total amount of compounds containing at least one carboxylic acid functional group is preferably in the range of 0.2% to 60% by weight, more preferentially 1% to 40% by weight, even more preferably 1% to 30% by weight, and even more preferentially 2% to 20% by weight, relative to the total weight of composition B.

[0368] According to a particular embodiment, the method according to the invention comprises, after step c), a further step: d) applying to the keratin hair fiber composition G as described above; and then e) optionally drying the keratinous hair fibers as described above; and then f) applying steam as previously described; g) shaping said keratin hair fibers as described above; Includes.

[0369] According to a particular embodiment, step f) is dissociated from step g); preferably, step f) is followed by step g).

[0370] According to another particular embodiment, steps f) and g) are carried out simultaneously.

[0371] According to a particular embodiment, the method according to the invention further comprises, after step c), a further step: d) applying to the keratin hair fiber composition G as described above; and then e) drying the keratin hair fibers as described above; and then f) optionally applying steam to the keratinous hair fibers in an amount of 0.5 g / min or more by means of a device capable of generating steam; g) optionally shaping the keratin hair fibers at a temperature above 100°C, preferably between 150°C and 230°C; Includes.

[0372] According to a particular embodiment, the method according to the invention comprises, in the following order: d) applying the composition G as defined above; and then e) drying with an air current, in particular a hair dryer; then f) applying steam; and g) shaping the keratin hair fibers as described for steps b) and c). Includes.

[0373] The total amount of aqueous dispersion of particles of polymer chosen from polyurethanes, acrylic polymers and mixtures thereof preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 50% by weight, even more preferably from 1% to 40% by weight, and even more preferentially from 2% to 30% by weight, relative to the total weight of composition B.

[0374] According to a particular embodiment, the total amount of the aqueous dispersion of acrylic polymer particles preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 50% by weight, even better from 1% to 40% by weight and even more preferentially from 2% to 30% by weight relative to the total weight of composition B.

[0375] The present invention will now be explained in more detail by means of examples, which in no way limit the scope of the invention, but which make it possible to support certain features, variants and preferred embodiments of the invention. [Example]

[0376] 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, Rudigerstrasse 14, D-70469 Stuttgart, or in U.S. Pat. No. 4,284,730 or Canadian Patent Application No. 2,509,861.

[0377] More specifically, the method for preparing the (poly)carbodiimide of the present invention comprises, in a first step, reacting a diisocyanate reagent (1): O=C=N-L1-N=C=O (1) (In formula (1), 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 give a carbodiimide diisocyanate compound (3): O=C=N-L1-(N=C=N-L1) n -N=C=O (3) (In formula (3), L1 and n are as defined above.) A benzoyl halide, such as benzoyl chloride, may be added to deactivate the catalyst.

[0378] In the second step of this preparation process, to obtain a "symmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 eq.) of the nucleophilic reagent R1-X1-H, followed by 0.5 eq. of the reagent HEH (wherein R1, X1 and E are as defined above), to give the "symmetric" compound (4) according to the invention: [R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)]2-E (4) (In formula (4), R1, X1, L1, n, and E are as defined above.) According to one variant to obtain compound (4) from (3), it is possible to first add 0.5 eq. of the reagent HEH, followed by 1 eq. of the reagent R1-X1-H.

[0379] In the second step of this preparation process, to obtain an "unsymmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 eq.) of the nucleophilic reagent R1-X1-H, and then with 1 eq. of the reagent HEH, where R1, X1 and E are as defined above, to give compound (5): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EH (5) (In formula (5), R1, X1, L1, n, and E are as defined above.) get.

[0380] According to one variant to obtain compound (5) from (3), it is possible to first add 1 eq. of reagent R1-X1-H, followed by 0.5 eq. of reagent HEH.

[0381] In the third step, compound (5) is reacted with 1 equivalent of compound (6): R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O (6) (The compound (6) is a compound (3'): O=C=N-L1-(N=C=N-L1) z -N=C=O (3') (In formula (3'), L1 and z are as defined above.) with 1 eq. of a nucleophile R2-X2-H (wherein L1, R2, X2 and z are as defined above). (prepared in advance by reacting with 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.) get.

[0382] 1 molar equivalent of the compound O=C=N-L1-(N=C=N-L1) z -N=C=O (3') is reacted with 1 / w molar equivalent of HEH, followed by reaction with 1 eq. of nucleophile R2-X2-H to give compound (8): H-[EC(O)-NH-L1-(N=C=N-L1)z ] w -NH-C(O)-X2-R2(8) (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

[0383] The final compound (8) is then reacted with 1 eq. of compound (4'): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -N=C=O (4') (The compound (4') can be synthesized by reacting 0.5 eq. of a nucleophilic reagent R1-X1-H with 1 eq. of compound (3).) to obtain the (poly)carbodiimide (9) of the present invention: R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NH-C(O)-X2-R2(9) (In formula (9), L1, R1, X1, R2, X2, n, z, w, and E are as defined above.) can be obtained.

[0384] The (poly)carbodiimide compounds and all reaction intermediates and reagents as well can be purified by conventional methods known to those skilled in the art, such as extraction with water and water-immiscible organic solvents, precipitation, centrifugation, filtration and / or chromatography.

[0385] Example 1: Method for synthesizing (poly)carbodiimide compounds A 500 mL three-necked round-bottom flask equipped with a thermometer, a stirrer, and a reflux condenser is charged with 50 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphole 1-oxide with stirring.

[0386] Infrared spectroscopy reveals that the-1 The reaction medium is heated under nitrogen at 140°C for 4 hours, and then cooled to 120°C, while the reaction is monitored by the absorption of isocyanate groups.

[0387] 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.

[0388] After cooling to room temperature, the reaction medium is added dropwise, with vigorous stirring, to a 500 mL glass beaker containing 85 g of distilled water, to obtain the desired product in the form of a translucent yellow liquid.

[0389] Example 2 Compositions A and B were prepared as described in Tables 1 and 2 below. Amounts are expressed as g / 100g of starting material obtained unless otherwise stated.

[0390] [Table 1]

[0391] (1) Synthesized according to the synthesis method described in Example 1 (containing 40% active substance in water) (2) Sold by SEPPIC under the name Sepinov EMT10 (containing 90% active material). (3) Sold by Wacker under the name Belsil ADM LOG 1 (containing 15% active material).

[0392] [Table 2]

[0393] (4) Daito Kasei Kogyo Co., Ltd., sold under the trade name Daitosol 3000SLPN-PE1 (aqueous dispersion containing 30% active substance) (5) Sold by Roehm & Haas under the trade name Aculyn 22® (oxyalkylenated methacrylic acid / ethyl acrylate / stearyl methacrylate terpolymer containing 30% active material)

[0394] Composition A was then mixed with composition B in a 50 / 50 weight ratio to obtain composition C according to the present invention.

[0395] protocol Two application methods were used.

[0396] According to a first method, known as Method P1, Composition C was applied manually using a brush to tresses of dry natural keratin hair fibers containing 90% white keratin hair fiber strands at a rate of 0.8 g of composition per gram of tress. The keratin hair fiber tresses were then detangled, dried with a hair dryer, and combed.

[0397] Therefore, this is a method for comparison.

[0398] According to a second method, known as Method P2, Composition C was applied manually using a brush to tresses of dry natural keratin hair fibers containing 90% white keratin hair fiber strands at a rate of 0.8 g of composition per gram of tress. The keratin hair fiber tresses were then detangled, dried with a hair dryer, and combed.

[0399] The keratin hair fiber tresses were then subjected to steam at a rate of 0.8 g / min to form or straighten the keratin hair fiber tresses at a temperature of 210°C.

[0400] Steam application and shaping were carried out separately using a steam generating straightening iron sold under the name Steampod 3. Two passes were made with this device.

[0401] This is therefore the method according to the invention.

[0402] The methods applied are summarized in Table 3 below.

[0403] [Table 3]

[0404] The keratin hair fibre tresses treated by steps P1 and P2 were then subjected to a test consisting of several repeated shampoo washes to assess the resistance (durability) of the colouring agent obtained to shampoo washes, according to the shampoo wash protocol described below.

[0405] Shampoo Wash Protocol: The keratin hair fiber tresses are combed, moistened with water at 35°C, and then passed through the fingers 5 times for 5 seconds. The keratin hair fiber tresses are then squeezed between two fingers and dried.

[0406] A standard shampoo (Garnier Ultra Doux) is applied evenly to the dyed tresses at a rate of 0.4 g of standard shampoo per gram of tress and gently massaged for 15 seconds along the length (6 passes) of the keratin hair fiber locks from root to end.

[0407] The keratin hair fiber tress is then placed on a watch glass and left for 1 minute.

[0408] The keratin hair fiber tresses are then rinsed with water while passing it through the fingers (15 passes).The keratin hair fiber tresses are then squeezed dry between two fingers before the next shampoo wash.

[0409] After several shampoo washes have been tested, the keratin hair fibre tresses are combed and dried with a hair dryer.

[0410] result The color persistence of the tresses was evaluated using the CIE L*a*b* system using a Minolta CM3610A spectrophotometer (illuminant D65, angle 10°, including specular component).

[0411] 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.

[0412] The durability of the coloration is evaluated by the color difference ΔE between measurements taken on a dyed tress before shampooing and then after 5 shampooings according to the protocol described above.

[0413] The ΔE value is calculated according to the following formula:

number

[0414] where L*, a*, b* represent measurements taken on keratin hair fibres after dyeing and after shampooing, and L0*, a0*, b0* represent measurements taken on keratin hair fibres after dyeing and before shampooing.

[0415] [Table 4]

[0416] A tress of keratinous hair fibres treated by the method P2 according to the invention and washed with 5 shampoo washes has a significantly lower colour difference than a tress of keratinous hair fibres treated by the comparative method P1.

[0417] The pigmented coatings obtained by the process according to the invention therefore exhibit improved resistance to shampoo washing.

[0418] Example 3 In this example, tresses of keratinous hair fibres were treated by a method according to the invention, hereinafter referred to as method P2'.

[0419] At the end of the aforementioned protocol P2 (after applying steam and shaping), a mixture obtained from composition A described in example 2 and composition B' corresponding to composition B described in example 2 but without pigment (red iron oxide) was applied to keratin hair fibers under the same conditions as those described in example 2.

[0420] After drying and combing, the tresses were treated with steam and shaped according to the protocol of Example 2.

[0421] The tresses were then shampooed according to the shampooing protocol described above and the color was evaluated according to the shampooing protocol described above.

[0422] The results are summarized in Table 7 below.

[0423] [Table 5]

[0424] A tress of keratinous hair fibres treated by the method P2' according to the invention and washed with five shampoo washes has a very small colour difference.

[0425] As a result, the colored coatings obtained by the method according to the invention show very good durability with respect to shampooing.

[0426] In both examples, there is also a very good cosmetic effect on the keratin hair fibres, feeling smooth when running a finger along the fibre, making the keratin hair fibres supple and allowing them to move in a manner similar to untreated keratin hair fibres.

Claims

1. 1. A method for dyeing keratinous hair fibers, comprising: a) applying to said keratinous hair fibres at least one (poly)carbodiimide compound; at least one colorant selected from pigments, direct dyes and mixtures thereof; applying at least one composition C comprising: b) applying steam to said keratinous hair fibers in an amount of 0.5 g / min or more by a device capable of generating steam; c) shaping said keratin hair fibers at a temperature of 100°C or higher; A method comprising:

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

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

2. The method of claim 1, wherein the compound is selected from the group consisting of:

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

5. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ independently represent an oxygen atom; -R １ and R ２ is 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, where n+z≧2 and w is equal to 1; - L １ is C ３ ~C １５ is a cycloalkylene group; E is independently —O—R ３ -O-; -S-R ４ -S-;-R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ represents a group selected from Here, R ３ and R ４ are independently C optionally interrupted by one or more heteroatoms ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups and mixtures thereof; -R ５ is not a covalent bond, R ５ is 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; and -R ６ 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 5. The method according to claim 3 or 4, characterized in that the alkylene radicals are selected from alkylene radicals and mixtures thereof.

6. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ independently represent an oxygen atom; -R １ and R ２ are independently represented by the following formula (VI): R １３ -[O-H ２ -C(H)(R １４ )] ｑ - (VI) represents a compound of Here, R １３ is C １ ~C ４ alkyl group or phenyl, preferably C １ ~C ４ represents an alkyl group, more preferably methyl, R １４ is a hydrogen atom or C １ ~C ４ represents an alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30; n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10 and w is equal to 1; - L １ is C such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylenemethane ３ ~C １５ is a cycloalkylene group; and - E is -O-R ３ represents an —O— group, where 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 6. The method according to claim 3, wherein the alkylene radicals are selected from alkylene radicals and mixtures thereof.

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

8. The (poly)carbodiimide compound is represented by the following formula (XII): 【Chemistry 4】 (In the formula, L １ is 4,4-dicyclohexylenemethane, n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10, and E is -O-R ３ represents an —O— group, where 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 even better 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 total amount of colorants chosen from pigments, direct dyes and mixtures thereof ranges from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, relative to the total weight of composition C.

11. 11. The method according to any one of claims 1 to 10, characterized in that composition C comprises at least one compound containing at least one carboxylic acid functional group, preferably chosen from silicone compounds, polyurethanes, acrylic polymers and mixtures thereof, containing at least one carboxyl group.

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

13. 13. The method according to claim 11 or 12, characterized in that the total amount of compounds comprising at least one carboxylic acid function ranges from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferentially from 1% to 15% by weight and even better still from 2% to 10% by weight relative to the total weight of composition C.

14. 14. The method according to any one of claims 1 to 13, characterized in that the step b) of applying steam is separated from the step c) of shaping the keratinous hair fibres; preferably the step b) of applying steam is followed by the step c) of shaping.

15. 14. The method according to any one of claims 1 to 13, characterized in that step b) of applying steam and step c) of shaping the keratinous hair fibres are carried out simultaneously.

16. 16. The method according to any one of the preceding claims, characterized in that the amount of steam ranges from 0.5 to 60 g / min, preferably from 0.5 to 20 g / min, more preferentially from 0.5 to 10 g / min, even more preferentially from 0.5 to 5 g / min and even better from 0.5 to 1 g / min.

17. 17. The method according to any one of claims 1 to 16, characterized in that the temperature during step b) ranges from 100 to 250°C, preferably from 150 to 250°C, more preferentially from 150 to 230°C, even more preferentially from 180 to 220°C.

18. The method according to any one of claims 1 to 17, comprising a drying step between steps a) and b).

19. Step a) comprises, in use, extemporaneously mixing at least two compositions A and B to obtain a composition C, and applying composition C to said keratinous hair fibres, composition A comprises at least one (poly)carbodiimide compound according to any one of claims 1 to 8; composition B comprises at least one compound containing at least one carboxylic acid function according to claim 11 or 12, 19. The method according to any one of claims 11 to 18, characterized in that composition A and / or composition B comprise at least one colorant selected from the pigments, direct dyes and mixtures thereof according to claim 1.

20. After step c), further steps: d) applying to said keratinous hair fibres at least one composition G comprising at least one (poly)carbodiimide compound according to any one of claims 1 to 8; and then e) drying the keratinous hair fibers; and then f) optionally applying steam to said keratinous hair fibers in an amount of 0.5 g / min or more by means of a device capable of generating steam; d) optionally shaping said keratin hair fibers at a temperature of 100°C or higher, preferably between 150°C and 230°C; The method of any one of claims 1 to 19, comprising:

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