A method for dyeing keratin hair fibers, which involves spraying a composition comprising a (poly)carbodiimide compound and a colorant onto the keratin hair fibers using an airbrush.

Abstract

The present invention relates to a method for dyeing keratinous hair fibers, which involves spraying, using an airbrush, onto the keratinous hair fibers at least one composition C comprising: - at least one (poly)carbodiimide compound; and - at least one colorant chosen from pigments, direct dyes and mixtures thereof.

Description

[Technical Field]

[0001] The present invention relates to a method for dyeing keratinous hair fibers, which involves spraying, using an airbrush, onto the keratinous hair fibers a composition C comprising at least one (poly)carbodiimide compound and a colorant. [Background technology]

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

[0003] There are three basic methods for dyeing keratin hair fibers: a) "Permanent" dyeing: its action makes it 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 dyes: do not use the oxidative condensation process and withstand 4-5 shampoo washes. This involves coloring keratin fibers with a coloring composition containing direct dyes. c) Temporary dyes: modify the natural color of the keratinous hair fiber, remain from one shampoo wash to the next, and serve to enhance or correct the shade already obtained. This can be associated with the "make-up" method.

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

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

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

[0007] One subject of the present invention is therefore a method for dyeing keratinous hair fibers, comprising using an airbrush: - at least one (poly)carbodiimide compound; - at least one colorant selected from pigments, direct dyes and mixtures thereof; The method involves spraying onto keratinous hair fibers at least one composition C comprising:

[0008] 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 types of keratin hair fiber and durable against shampooing while preserving the physical quality of the keratin hair fiber. This type of coating can withstand external stresses to which keratin hair fibers may be subjected, such as blow-drying and sweating. In particular, it allows for easy obtaining of a thin, uniform deposit without running and dries quickly.

[0009] Unlike conventional aerosol devices (in which a pressurized package of the composition is sprayed), the composition can be stored in a non-pressurized form (i.e., at atmospheric pressure) in a container held by or connected to the airbrush prior to use.

[0010] Another subject of the invention is a spray system comprising an airbrush and at least one compartment containing said composition C.

[0011] The invention can be more clearly understood by reading the following detailed description of an airbrush, non-limiting examples of its use, and by examining the accompanying drawings, in which: [Brief explanation of the drawings]

[0012] [Figure 1] 1 shows a schematic and partial representation of an example of an airbrush and a compressed air supply system for the airbrush. [Figure 2] Represents a perspective view of an airbrush. DETAILED DESCRIPTION OF THE INVENTION

[0013] For the purposes of the present invention, the term "colour that is durable to shampooing" means that the colour obtained persists after one shampooing, preferably after three shampooings.

[0014] The term "at least one" means one or more.

[0015] Unless otherwise specified, the boundaries of a range of values ​​are encompassed within the range, particularly the expressions "to" and "ranging from."

[0016] The invention is not limited to the illustrated embodiments, and features of the various embodiments may be combined in particular variations not illustrated.

[0017] For purposes of the present 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 refers to a linear or branched saturated C2-C4 hydrocarbon-based divalent group, such as methylene, ethylene or propylene; - a "cycloalkyl" or "alicycloalkyl" group refers to a cyclic saturated monocyclic or bicyclic, preferably monocyclic, hydrocarbon-based group containing 1 to 3 rings, preferably 2 rings, and containing 3 to 24 carbon atoms, in particular 3 to 20 carbon atoms, more particularly 3 to 13 carbon atoms, even more particularly 3 to 12 carbon atoms, preferably 5 to 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, where it is understood that the cycloalkyl group may be substituted with one or more (C1-C4)alkyl groups, such as methyl, in which case 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 unfused, unsaturated aromatic hydrocarbon-based cyclic 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 an aryl group representing phenyl; - an "arylene" group is a divalent aryl group with "aryl" as defined above, preferably arylene refers to phenylene; - "heterocyclic" group refers to 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 with "heterocyclic" defined above; - an "aryloxy" group refers to an aryloxy group with "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.

[0018] Unless otherwise specified, a reference in this application to a compound also includes its optical isomers, its geometric isomers, its tautomers or its salts, either alone or in mixtures.

[0019] 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 following description.

[0020] For the purposes of the present invention, the term "keratinous hair fibers" refers to keratinous hair fibers of the head. This term does not correspond to body hair, eyebrows or eyelashes.

[0021] Polycarbodiimide Compounds The composition C used in connection with the method according to the invention comprises at least one (poly)carbodiimide compound.

[0022] The composition may comprise at least two different (poly)carbodiimide compounds present as a mixture in the composition.

[0023] The term "(poly)carbodiimide compound" means a compound comprising one or more carbodiimide groups, preferably at least two carbodiimide groups, more preferentially at least three carbodiimide groups, in particular the number of carbodiimide groups does not exceed 200, preferably does not exceed 150, more preferentially does not exceed 100.

[0024] The term "carbodiimide group" refers to a divalent, linear, three-atom moiety of the general formula -(N=C=N)-.

[0025] The (poly)carbodiimide compounds according to the present invention may optionally comprise in their structure one or more reactive groups different from the carbodiimide groups, selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxides such as propylepoxide or butylepoxide, and azacyclopropane groups.

[0026] The reactive group other than the carbodiimide group may be a side group or a terminal group. Preferably, the (poly)carbodiimide compound comprises one or more terminal groups different from the carbodiimide group, preferably one or more terminal groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, such as propylepoxide or butylepoxide, and azacyclopropane group.

[0027] 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 one or a hydrocarbon-based group, preferably selected from alkyl, optionally interrupted by several 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:

[0028] 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 chain 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 group may be partially or fully fluorinated, and in this variation Z1 and Z2 comprise 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 chain or cycloaliphatic 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 denotes an integer equal to 0 or 1; m represents an integer ranging from 0 to 1000, preferably equal to 0 or 1; m' represents an integer ranging from 0 to 1000, preferably equal to 0 or 1; - n denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1, and m+(m' * n) ≥ 2) The compound is selected from the group consisting of:

[0029] 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.

[0030] Such (poly)carbodiimide compounds are sold, for example, by Stahl BV under the names Permutex XR or RelcaLink 10 or Picassian XL, and Nisshinbo sells compounds under the name Carbodilite in the series V-02, V-02-L2, SV-02, E-02, V-10, SW-12G, E-03A, E-04DG-T, E-05, V-04, V-02B, V-04PF, V-05.

[0031] 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:

[0032] The term "hydrocarbon-based group" means a saturated or unsaturated, straight-chain or branched-chain 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 straight-chain group.

[0033] The hydrocarbon-based group may contain one or more cyclic groups.

[0034] 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.

[0035] 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.

[0036] Preferably, X1 and X2 independently represent an oxygen atom.

[0037] Preferably, R1 and R2 are independently selected from dialkylamino alcohols from which the hydroxyl groups have been removed, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof.

[0038] In a preferred embodiment, R1 and R2 are independently 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), (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, and 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 is selected from.

[0039] Preferably, R1 and R2 independently represent a compound of formula (VI), 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 in the range of 4-30.

[0040] According to an alternative embodiment, R1 and R2 are different, and one of the R1 or R2 groups represents a compound of formula (IV) above, and the other of the R1 or R2 groups represents a compound of formula (VI) above.

[0041] 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.

[0042] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl, and q is an integer ranging from 4 to 30.

[0043] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; and q represents an integer in the range of 4-30.

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

[0045] Preferably, z represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0046] Preferably, w is equal to one.

[0047] Preferably, w is equal to 1 and n+z represents an integer in the range 4-10.

[0048] Preferably, L1 is a divalent C1-C6 alkyl group such as methylene, ethylene, and propylene. 18 Aliphatic hydrocarbon groups, C3-C such as cyclopentylene, cycloheptylene, and cyclohexylene 15 C3-C such as cycloalkylene groups, imidazolene, pyrrolene, and furanylene 12 C6-C such as heterocycloalkylene group or phenylene 14 The aryl group is selected from arylene groups as well as mixtures thereof.

[0049] 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.

[0050] Preferably, L1 is C3 to C 15 Cycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, such as compounds of formula (VII): [ka]

[0051] Preferably, L1 is 4,4-dicyclohexylenemethane, which corresponds to formula (VIII) below: [ka]

[0052] According to another embodiment, L1 is C6 to C 14When L1 is an arylene group, it is not a m-tetramethylxylylene group represented by the following formula (IX). [ka]

[0053] As above, 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.

[0054] Preferably, R3 and R4 are C6-C alkyl groups, such as phenylene, optionally interrupted by one or more heteroatoms. 14 C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 alkylene groups as well as mixtures thereof.

[0055] More preferentially, R3 and R4 are linear or branched C1-C6 alkylenes, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms. 18 alkylene groups.

[0056] 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 18The alkylene groups are selected from alkylene groups as well as mixtures thereof.

[0057] Preferably, R6 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.

[0058] Preferably, E represents a -O-R-O- group, where R is a C-C alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, straight or branched C1-C 18 The alkylene group is selected from alkylene groups and mixtures thereof.

[0059] 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.

[0060] 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.

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

[0062] In this embodiment, the term "cycloalkyl group" is as defined above.

[0063] 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.

[0064] 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

[0065] The "alkyl group", "cycloalkyl group" and "aryl group" are as defined above.

[0066] 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; - when n and z are present, they represent integers ranging from 1 to 20, where n+z≧2, and w is equal to 1; - If L1 is present, it is a divalent C1-C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, preferably C3-C 15 cycloalkylene groups; - If A is present, it is a divalent C1-C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, preferably C3-C 15 cycloalkylene groups; - if E is present, it is independently 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, straight or branched C1-C 18 alkylene groups and mixtures thereof; - R5 is not a covalent bond, and if R5 is present it is a C6-C6 bond optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, straight or branched C1-C 18 alkylene groups and mixtures thereof; and - if R6 is present, it is a C-C group optionally interrupted by one or more heteroatoms; 14 Arylene group, C3-C 12 Cycloalkylene group, straight or branched C1-C 18 The alkylene group is selected from alkylene groups and mixtures thereof.

[0067] Preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein X1 and X2 independently represent an oxygen atom; - R1 and R2 are independently selected from dialkylamino alcohols from which the hydroxyl groups have been removed, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof; - n and z represent integers ranging from 1 to 20, 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, straight or branched C1-C 18 alkylene groups and mixtures thereof; - when R5 is not a covalent bond, R5 is a C6-C optionally interrupted by one or more heteroatoms 14 Arylene group, C3-C 12 Cycloalkylene group, straight 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, straight or branched C1-C 18 The alkylene group is selected from alkylene groups and mixtures thereof.

[0068] More preferentially, the (poly)carbodiimide compound is chosen from compounds of formula (II), in which X1 and X2 independently represent an oxygen atom; R1 and R2 are independently a monoalkyl ether of a (poly)alkylene glycol from which a hydroxyl group has been removed; - n and z represent integers ranging from 1 to 20, 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, straight or branched C1-C 18 alkylene groups and mixtures thereof; - when R5 is not a covalent bond, R5 is a C6-C optionally interrupted by one or more heteroatoms 14 Arylene group, C3-C 12 Cycloalkylene group, straight 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, straight or branched C1-C 18 The alkylene group is selected from alkylene groups and mixtures thereof.

[0069] Even more preferentially, the (poly)carbodiimide compound is chosen from compounds of formula (II), in which X1 and X2 independently represent an oxygen atom; R1 and R2 independently represent the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) represents a compound of 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; - 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, straight or branched C1-C 18 The alkylene group is selected from alkylene groups and mixtures thereof.

[0070] 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 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; and - 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.

[0071] According to a preferred embodiment, the (poly)carbodiimide compound has the following formula (XII): [ka] wherein L1 is 4,4-dicyclohexylenemethane, n and z represent integers ranging from 1 to 20, n+z ranges from 4 to 10, E represents a -O-R3-O- group, R3 is a linear or branched C1-C alkyl group such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms. 18 represents an alkylene group, and r and s represent integers ranging from 4 to 30. is a compound of

[0072] 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.

[0073] coloring agent Composition C used in connection with the method according to the invention comprises one or more colorants chosen from pigments, direct dyes and mixtures thereof.

[0074] Preferably, the composition C used in connection with the method according to the invention comprises one or more pigments.

[0075] The term "pigment" refers to any pigment that colors keratin 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.

[0076] 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.

[0077] These may be natural products of natural origin or non-natural products.

[0078] These pigments may be in the form of pigment powder or paste. They may be coated or uncoated.

[0079] 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.

[0080] 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, mention may be made of iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium oxide.

[0081] 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.

[0082] 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.

[0083] In particular, white or colored organic pigments are carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments classified in the Color Index under the reference numbers CI 42090, 69800, 69825, 74100, 74160, yellow pigments classified in the Color Index under the reference numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, green pigments classified in the Color Index under the reference numbers CI 61565, 61570, 74260, orange pigments classified in the Color Index under the reference numbers CI 11725, 45370, 71105, red ... The pigments may be selected from the red pigments classified under the reference numbers 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, and from the pigments obtained by oxidative polymerization of indole or phenol derivatives described in French Patent No. 2 679 771.

[0084] 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).

[0085] 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.

[0086] The organic pigment may be a lake, the term "lake" referring to a dye adsorbed onto insoluble particles so that the resulting composite remains insoluble during use.

[0087] The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

[0088] Among the dyes, mention may be made of carminic acid. Mention may also be made of products known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

[0089] An example of a lake is the product known by the following name: D&C Red 7 (CI 15 850:1).

[0090] The pigments may 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.

[0091] 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.

[0092] Examples of special effect pigments that may be mentioned include pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxide, mica coated with iron oxide, mica coated with titanium, in particular with ferric blue or chromium oxide, mica coated with titanium and coated with the organic pigments defined above, and pearlescent pigments based on bismuth oxychloride. Pearlescent pigments include pearlescent agents such as Cellini (mica-TiO2-lake) sold by BASF, Prestige (mica-TiO2) sold by Eckart, Prestige Bronze (mica-Fe2O3) sold by Eckart, or Colorona (mica-TiO2-Fe2O3) sold by Merck.

[0093] 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, especially those sold by Merck under the name Matte blue (17433) (Microna); silvery white pearlescent agents, especially those sold by Merck under the name XironaMention may also be made of those sold under the name Silver, as well as gold-green to pink to orange-shifting pearlescent agents, in particular those sold under the name Indian summer (Xirona) by Merck, and mixtures thereof.

[0094] Further examples of pearlescent agents include particles comprising a borosilicate substrate coated with titanium oxide.

[0095] Particles comprising a glass substrate coated with titanium oxide are sold in particular under the name Metashine MC1080RY by the company Toyal.

[0096] 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.

[0097] The special effect pigments can also be chosen from reflective particles, i.e. particles that, due to their size, structure, in particular the thickness of the layer of which they are composed, as well as their physical and chemical properties and surface condition, are able to reflect incident light. This reflection can, where appropriate, be strong enough to produce, when applied to 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 shiny and therefore stands out from its surroundings.

[0098] 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.

[0099] These particles may have various morphologies, in particular in the form of platelets or spheres, in particular in the form of spheres.

[0100] 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.

[0101] 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.

[0102] If the reflective particles have a multilayer structure, they may comprise, for example, a natural or synthetic substrate, in particular a synthetic substrate, at least partially coated with at least one layer of a reflective material, in particular at least one metal or metallic material. The substrate can be made from one or more organic and / or mineral materials.

[0103] More particularly, it can be chosen from glass, ceramic, graphite, metal oxides, alumina, silica, silicates, especially aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, without being limited to this list.

[0104] The reflective material may include a metal or a layer of metallic material.

[0105] 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.

[0106] Further examples of reflective particles comprising an inorganic substrate coated with a metal layer may include particles comprising a borosilicate substrate coated with silver.

[0107] Platelet-shaped silver-coated glass-based particles 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.

[0108] 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.

[0109] Examples include SiO2 coated aluminum, bronze or copper powders sold under the name Visionaire by the company Eckart.

[0110] Also included are interference pigments that are not bound to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic bright flakes (Geometric Pigments or Spectra f / x from Spectratek).Special effect pigments also include fluorescent pigments (which are either materials that fluoresce in daylight or that provide ultraviolet fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, such as those sold by Quantum Dots Corporation.

[0111] The variety of pigments that can be used in the present invention makes it possible to obtain a wide range of colors and also specific optical effects such as metallic or interference effects.

[0112] 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.

[0113] The pigment may be dispersed in the composition by a dispersant.

[0114] 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 become physically or chemically bound to the pigment surface. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid, especially C8-C20 fatty acids, and polyols such as glycerol or diglycerol, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g / mol, such as the product sold by Avecia under the name Solsperse 21000, or polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold by Henkel under the trade name Dehymyls PGPH, or other polyhydroxystearic acids, such as the product sold by Uniqema under the trade name Arlacel P100, and mixtures thereof, are used.

[0115] 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.

[0116] The pigments used in the composition may be surface treated with an organic agent.

[0117] Thus, pre-surface-treated pigments useful in the context of 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, for example, from waxes such as carnauba wax and beeswax, fatty acids, fatty alcohols, and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, and lauric acid, and derivatives thereof, 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.

[0118] 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.

[0119] 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.

[0120] Preferably, the surface-treated pigment is coated with an organic layer.

[0121] The organic agent for treating the pigment may be deposited onto the pigment by evaporating the solvent, by chemical reaction between molecules of the surface treatment agent, or by forming a covalent bond between the surface treatment agent and the pigment.

[0122] 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.

[0123] Organic agents that are covalently bonded to the pigment are preferably used.

[0124] The agent used for the surface treatment can account for 0.1% to 50% by mass, preferably 0.5% to 30% by mass, and more preferentially 1% to 20% by mass of the total mass of the pigment to be surface treated.

[0125] Preferably, the surface treatment of the pigment is one of the following treatments: PEG-silicone treatments, such as the AQ surface treatment sold by LCW; - methicone treatments, such as the SI surface treatment sold by LCW, - dimethicone treatments, such as Covasil 3.05 surface treatment sold by LCW; - dimethicone / trimethylsiloxysilicate treatments, such as Covasil 4.05 surface treatment sold by LCW; - magnesium myristate treatment agents, such as the MM surface treatment agent sold by LCW; - aluminum dimyristate treatments, such as the MI surface treatment sold by Miyoshi; - perfluoropolymethyl isopropyl ether treatments, such as the FHC surface treatment sold by LCW; - isostearyl sebacate treatment agents, such as the HS surface treatment agent sold by Miyoshi Kasei Co., Ltd. - perfluoroalkylphosphate treatment agents, such as the PF surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - acrylate / dimethicone copolymer and perfluoroalkylphosphate treatment agents, such as the FSA surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - polymethylhydrogenosiloxane / perfluoroalkylphosphate treatment agents, such as the FS01 surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - acrylate copolymer / dimethicone treatment agents, such as the ASC surface treatment agent sold by Daito Kasei Kogyo Co., Ltd. - isopropyl titanium triisostearate treatment agents, such as the ITT surface treatment agent sold by Daito Kasei Kogyo 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] Thus, the dispersant may be an aminosilicone type dispersant other than the above alkoxysilanes, which has a silicone backbone, such as a silicone polyether. Suitable dispersants include: aminosilicones, i.e. silicones containing one or more amine groups, such as those sold by BYK under the name BYK LPX 21879, and the products 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.

[0130] According to a particular embodiment, the dispersant is of the aminosilicone type other than the silicones described below and is cationic.

[0131] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments or organic pigments.

[0132] 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.

[0133] Preferably, the pigment is selected from iron oxides, in particular red, brown or black iron oxides. Examples of iron oxides that may be mentioned include those sold under the name SunPuro® Red Iron Oxide by Sun Chemical Company.

[0134] direct dye Composition C used in connection with the method according to the invention may comprise one or more direct dyes.

[0135] The term "direct dyes" refers to natural and / or synthetic dyes other than oxidation dyes. These are dyes that diffuse superficially onto the fiber.

[0136] These may be ionic or non-ionic, preferably cationic or non-ionic.

[0137] Examples of suitable direct dyes include azo direct dyes, (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, either alone or in mixtures.

[0138] The direct dye is preferably a cationic direct dye, such as the hydrazonocationic dyes of the following formulae (XIII) and (XIV) and the azocationic dyes of the following formulae (XV) and (XVI). [ka] 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 an aryl group, in particular phenyl, optionally substituted with 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) 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 a (C1-C8) alkyl group optionally substituted, preferentially with a hydroxyl group; or Instead, Het + The substituents Ra bearing a substituent and / or the substituents Rb bearing an Ar substituent together with the atoms carrying them form a (hetero)cycloalkyl, in particular Ra and Rb represent a hydrogen atom or a (C1-C4) alkyl group optionally substituted with a hydroxyl group; - Q- represents an organic or inorganic anionic counterion such as a halide or alkyl sulfate.

[0139] Mention may in particular be made of 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; and -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 in which the alkyl group is optionally substituted with a hydroxyl group, in particular R 4 is a hydrogen atom; Z represents a CH group or a nitrogen atom, preferentially CH; Q- is an anionic counterion as defined above, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0140] 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.

[0141] The direct dye may be selected from anionic direct dyes. The anionic direct dyes of the present invention are dyes commonly referred to as "acid" direct dyes due to their affinity for alkaline substances. The term "anionic direct dye" refers to a direct dye containing at least one COR or SOR substituent in its structure (wherein R represents a hydrogen atom or a cation or ammonium ion derived from a metal or amine). The anionic dye may be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes, and natural acid dyes.

[0142] 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).

[0143] a) diaryl anionic azo dyes of formula (XIX) or (XIX'): [ka] [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 a hydrogen atom, or - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be 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'- (wherein 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 represents a group selected from Alternatively, two adjacent groups R7 and R8 or R8 and R9 or R9 and R 10 together form a fused benzo group A', and R'7 and R'8 or R'8 and R'9 or R'9 and R' 10 together form a fused benzo group B', and 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; M + , R°, X, X′, X″ and Ar are as defined above; - W represents a sigma bond σ, an oxygen atom or a sulfur atom or a divalent radical: i) -NR-, where R is as defined above, or ii) methylene-C(Ra)(Rb)-, where Ra and Rb may be identical or different and represent a hydrogen atom or an aryl group, or alternatively Ra and Rb together with the carbon atom to which they are attached form a spirocycloalkyl, and preferentially W represents a sulfur atom or Ra and Rb together form a cyclohexyl; Formulas (XIX) and (XIX') contain at least one sulfonate group (O)S(O) on one of the rings A, A', B, B' or C. - )-,M + or one carboxylate group (O)CO - -,M + , which is understood to comprise preferentially sodium sulfonate.

[0144] 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, and examples of dyes of formula (XIX′) may include Acid Red 111, Acid Red 134 and Acid Yellow 38.

[0145] 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, in which case R' 16 does not exist, or instead, R 15 is R 16 together to form a double bond; -R 17 and R 18 may be the same or different and are a hydrogen atom, or - (O)2S(O - )-,M + (In the formula, M + is as defined above); - Ar-OS(O)2-, where Ar represents an optionally substituted aryl group, and preferentially a phenyl 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, and represents a double bond when Y is a hydroxyl group; Formulas (XX) and (XX') contain at least one sulfonate group (O)S(O) on one of the rings D or E. - )-,M + or one carboxylate group -C(O)O - ,M + , which is understood to comprise preferentially sodium sulfonate.

[0146] Examples of dyes of formula (XX) include Acid Red 195, Acid Yellow 23, Acid Yellow 27, and Acid Yellow 76, and an example of dyes of formula (XX') may include Acid Yellow 17.

[0147] 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 are hydrogen or halogen atoms, or - alkyl; - hydroxyl, mercapto; - alkoxy, alkylthio; - Alkyl and (O)2S(O - ),M + Optionally substituted aryloxy or arylthio, preferentially substituted by one or more groups selected from + is as defined above); - Alkyl and (O)2S(O - )-,M + (M +is as defined above); - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino; - (O)2S(O - )-,M + (In the formula, M + is as defined above) represents a group selected from: Z' is a hydrogen atom or a group NR 28 R 29 wherein R 28 and R 29 may be the same or different and are a hydrogen atom, or - alkyl; - polyhydroxyalkyl, such as hydroxyethyl; one or more groups, in particular i) alkyl, such as methyl, n-dodecyl, n-butyl, ii) (O)S(O - )-,M + (In the formula, M + is as defined above), iii) aryl optionally substituted with R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above and preferentially R° represents an alkyl group); - cycloalkyl, especially cyclohexyl represents a group selected from: - Z is hydroxyl and NR' 28 R' 29 (wherein R' represents a group selected from 28 and R' 29 may be the same or different, and R 28 and R 29 represents the same atom or group as Formulas (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.

[0148] 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, and EXT Violet No. 2, and an example of dyes of formula (XXI') may include Acid Black 48.

[0149] 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 are hydrogen or halogen atoms, or - alkyl; - alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups; - hydroxyl, mercapto; - Nitro, nitroso; - polyhaloalkyl; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above); - (O)2S(O - )-,M + (In the formula, M + is as defined above); - (O)CO - -,M + (In the formula, M + is as defined above); - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino; heterocycloalkyl, such as piperidino, piperazino or morpholino In particular, R 30 , R 31 and R 32 represents a hydrogen atom; Rc and Rd may be identical or different and represent a hydrogen atom or an alkyl group; - W is as defined above; W represents, in particular, an -NH- group; - ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group; - n is 1 or 2; - p represents an integer between 1 and 5 (inclusive); - q represents an integer between 1 and 4 (inclusive); - u is 0 or 1; - when n is 1, J represents a nitro or nitroso group, in particular nitro; - when n is 2, J is an oxygen or sulfur atom or a divalent -S(O) m - group, where m represents an integer of 1 or 2; preferentially, J represents a -SO2- group; M' represents a hydrogen atom or a cationic counterion; - [ka] may be present or absent and may be one or more groups R as defined above 30 represents a benzo group optionally substituted by Formulas (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.

[0150] Examples of dyes of formula (XXII) include Acid Brown 13 and Acid Orange 3, and 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, and EXT D&C Yellow 7.

[0151] e) Triarylmethane dyes of formula (XXIII): [ka] In formula (XXIII), -R 33 , R 34 , R 35 and R 36 may be the same or different and are hydrogen atoms or alkyl, optionally substituted aryl and optionally substituted arylalkyl, in particular alkyl and optionally (O) m S(O - )-,M + group (in the formula, M + and m represents a group selected from benzyl groups 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 a hydrogen atom, or - alkyl; - alkoxy, alkylthio; - (di)(alkyl)amino; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be 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 represents a group selected from - Alternatively, 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' being 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''- (wherein M + , R°, X, X′, and X″ are as defined above); In particular, R 37 ~R 40 represents a hydrogen atom, and R 41 ~R 44 may be the same or different and are hydroxyl groups or (O)S(O - )-,M + represents R 43 and R 44 together form a benzo group, this is preferentially (O)S(O - )-group; At least one of the rings G, H, I, or I′ contains at least one sulfonate group (O)S(O- )- or one carboxylate group C(O)O - -, and preferentially sulfonates.

[0152] As examples of dyes of formula (XXIII), mention may be made of Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid Green 3, Acid Green 5 and Acid Green 50.

[0153] 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 are hydrogen or halogen atoms, or - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above) represents a group selected from: In particular, R 49 , R 50 , R 51 and R 52 represents a hydrogen 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 the same or different and represent a hydrogen atom or an optionally substituted alkyl or aryl group, and 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.

[0154] 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, Acid Violet 9.

[0155] 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 a hydrogen atom, or - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be 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 + , which is understood to comprise preferentially sodium sulfonate.

[0156] As an example of a dye of formula (XXV), Acid Blue 74 may be mentioned.

[0157] 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 Instead, R 61 and R 62 or R 61 and R 64 together form one or more (O)S(O - )-,M + group (in the formula, M + represents a hydrogen atom or a cationic counterion), forming a benzo group optionally substituted with Formula (XXVI) contains at least one sulfonate group (O)S(O - )-,M + , which is understood to comprise preferentially sodium sulfonate.

[0158] As examples of dyes of formula (XXVI), mention may be made of Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0159] 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.

[0160] Preferably, the direct dye is selected from anionic direct dyes.

[0161] The colorants may be present in a total amount ranging from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, relative to the total weight of composition C; preferably, the colorants are chosen from pigments.

[0162] The pigments may be present in a total amount of from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight, and even better still from 0.5% to 10% by weight relative to the total weight of composition C.

[0163] The direct dyes may be present in a total amount ranging from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight, relative to the total weight of composition C.

[0164] 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.

[0165] Preferably, the compound containing at least one carboxylic acid functional group is selected from silicone compounds, polyurethanes, acrylic polymers and mixtures thereof, which contain at least one carboxyl group.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] The dispersion may be a simple dispersion of the cosmetic composition in an aqueous medium. A particular example of a dispersion is a latex.

[0170] The aqueous dispersion of polymer particles may be selected from aqueous dispersions of polyurethane particles.

[0171] More specifically, the polyurethane present in the aqueous dispersion used in the present invention is - the following formula (A): [ka] (In the formula, R1 represents a divalent radical of a dihydroxylated compound; R2 represents the radical of an aliphatic or cycloaliphatic polyisocyanate; R3 represents 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 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 is obtained from the reaction

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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, 1,4-bis(isocyanatomethyl)cyclohexane, 1,5-bis(isocyanatomethyl)cyclohexane, 1,6-bis(isocyanatomethyl)cyclohexane, 1,5-bis(isocyanatomethyl)cyclohexane, 1,6-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 1,5 ... bis(4-isocyanatomethyl)cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)methane, isomers of toluene diisocyanate (TDI), such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, diphenylmethane 4,4'-diisocyanate and mixtures of its isomers diphenylmethane 2,4-diisocyanate, optionally with diphenylmethane 2,2'-diisocyanate, naphthalene 1,5-diisocyanate and mixtures thereof.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] The prepolymers are extended by two families of chain extenders: The first group of chain extenders corresponds to compounds of general formula (B):

[0182] The chain extender of formula (B) is preferably an alkylenediamine such as hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine, 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 the like. The ether-amine may be selected from the DPA series of ether-amines available from Epson Corporation, Milton, Wis., such as dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropylene glycol, dipropylamine poly(propylene glycol), dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propanediol, dipropylamine 2-methyl-1,3-propanediol, dipropylamine 1,4-butanediol, dipropylamine 1,3-butanediol, dipropylamine 1,6-hexanediol, and dipropylamine cyclohexane-1,4-dimethanol, and mixtures thereof.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] Preferably, the viscosity of the aqueous dispersion of polyurethane particles is less than 2000 mPa.s at 23°C, more preferentially less than 1500 and better still less than 1000. Even more preferably, the glass transition temperature of the aqueous dispersion of polyurethane particles is less than 0°C.

[0188] 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.

[0189] 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.

[0190] 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).

[0191] 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).

[0192] 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, e.g. Luviset® PUR, BASF), polyurethanes of polycarbonate, polyurethanes of aliphatic polyesters and aliphatic polyurethanes (e.g. Neorez® or DSM series, e.g. Neorez® R989 and Neorez® R-2202).

[0193] 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.

[0194] Preferably, the compound containing at least one carboxylic acid function is in the form of an aqueous dispersion of particles of an acrylic polymer, more preferentially in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0195] For the purposes of the present invention, the term "polymer" means a compound corresponding to the repetition of one or more units (these units are derived from compounds known as monomers) that are repeated at least twice, preferably at least three times.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] Among the hydroxyalkyl(meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0202] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0203] Particularly preferred (meth)acrylic acid esters are alkyl, preferably C1-C 30 , and more preferentially C1~C 20 , or better C1 to C 10 and even more particularly C1 to C4 alkyl (meth)acrylates.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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 It contains one or more units derived from

[0208] Preferably, the aqueous dispersion of acrylic polymer particles is surfactant-free.

[0209] The term "surfactant" refers to any agent that can modify the surface tension between two surfaces.

[0210] 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, 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, acrylate copolymer.

[0211] The acrylic polymer may optionally include one or more additional monomers other than (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide monomers.

[0212] Additional monomers may include, for example, styrene monomers, particularly styrene and alpha-methylstyrene, preferably styrene.

[0213] 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.

[0214] 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.

[0215] Among the acrylic polymers, mention may be made of styrene / (meth)acrylate copolymers sold under the names Joncryl 77 by BASF, Yodosol GH41F by Akzo Nobel and Syntran 5760 CG by Interpolymer.

[0216] Preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles.

[0217] 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 The present invention comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more units derived from

[0218] 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.

[0219] Silicone Acrylic Copolymer According to a particular embodiment, the silicone compound comprising at least one carboxyl group is chosen from silicone acrylic copolymers.

[0220] Thus, according to a particular embodiment, the compound comprising at least one carboxylic acid functional group is chosen from silicone acrylic copolymers.

[0221] Preferably, the silicone acrylic copolymer comprises: - at least one acrylic or methacrylic or croton unit; - at least one polydimethylsiloxane (PDMS) unit; Includes.

[0222] For the purposes of the present invention, the term "polydimethylsiloxane" (also abbreviated as PDMS) means, according to the generally accepted definition, any organosilicon polymer or oligomer of linear structure, of variable molecular weight, obtained by polymerization and / or polycondensation of suitably functional silanes, and consisting essentially of repeating main units in which the silicon atoms are linked together by oxygen atoms (siloxane bonds -Si-O-Si-) and which contain methyl groups bonded directly to said silicon atoms via carbon atoms.

[0223] The PDMS chains that can be used to obtain the copolymers used in accordance with the present invention preferably contain at least one polymerizable group located at at least one of the chain ends, i.e., the PDMS can have, for example, a polymerizable group at each of the two ends of the chain, or one polymerizable group at one end of the chain and one trimethylsilyl end group at the other end of the chain.

[0224] The term "polymerizable group" means a group that can be polymerized with other polymerizable groups or monomers. Preferably, the polydimethylsiloxane unit comprises at least one polymerizable group.

[0225] Preferably, the polymerizable group comprises at least one vinyl group.

[0226] Preferably, the polydimethylsiloxane (PDMS) unit comprises at least one polymerizable group comprising at least one vinyl group, preferably at least two polymerizable groups comprising at least one vinyl group, preferably located at at least one of the chain ends.

[0227] As mentioned above, the silicone acrylic copolymer preferably comprises at least one acrylic or methacrylic or crotonic unit, ie, at least one unit containing a carboxylic acid group.

[0228] The term "carboxyl group" refers to COOH or COO - It means functional group, COO - The counterions of the groups can be selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0229] 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; - at least one polydimethylsiloxane (PDMS) unit; Includes.

[0230] More preferentially, the composition comprises: - at least one unit selected from at least one croton unit and an alkyl crotonate unit, wherein the alkyl group is a linear or branched saturated group containing 1 to 20 carbon atoms, vinyl acetate units; vinyl alkyl ester units, wherein the alkyl group is a linear or branched saturated group containing 2 to 20 carbon atoms, and mixtures thereof; - at least one polydimethylsiloxane (PDMS) unit; The composition comprises one or more silicone acrylic copolymers including:

[0231] The term "crotonic unit" means a unit derived from a crotonic acid monomer or a salt thereof.

[0232] The term "alkyl crotonate unit" means a unit derived from a crotonic acid ester monomer having a saturated linear or branched alkyl group containing from 1 to 20 carbon atoms.

[0233] The term "vinyl alkyl ester unit" means a unit derived from a vinyl ester monomer unit having a saturated, straight or branched chain alkyl group containing from 2 to 20 carbon atoms.

[0234] The term "vinyl acetate units" means units derived from vinyl acetate monomer.

[0235] 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, wherein the alkyl group is a saturated linear or branched group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms, - at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable group, preferably containing at least one vinyl group; Includes.

[0236] 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, - at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable group containing at least one vinyl group; Includes.

[0237] 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 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms; - at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable group containing at least one vinyl group; The composition comprises one or more silicone acrylic copolymers including:

[0238] 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 6 to 16 carbon atoms; - at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable group containing at least one vinyl group; The composition comprises one or more silicone acrylic copolymers including:

[0239] 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.

[0240] The total amount of compounds containing at least one carboxylic acid function preferably ranges from 0.1% to 30% by weight, more preferentially from 0.5% to 20% by weight, better still 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] 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 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.

[0242] 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.

[0243] Advantageously, the total amount of silicone acrylic copolymer ranges from 0.1% to 30% by weight, more preferentially from 0.5% to 20% by weight, even better from 1% to 15% by weight and even more preferentially from 2% to 10% by weight relative to the total weight of composition C.

[0244] organic solvents Composition C according to the invention may comprise one or more organic solvents.

[0245] 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 monoethyl ether and monomethyl ether, as well as aromatic alcohols, in particular aromatic monoalcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0246] The organic solvents may be present in a total amount of from 0.01% to 75% 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.

[0247] 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.

[0248] additives Composition C used in connection with the method according to the invention may contain any adjuvant or additive normally used.

[0249] Among the additives that may be contained in the composition are reducing agents, emollients, antifoaming agents, moisturizing agents, UV screening agents, peptizing agents, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, thickeners, preservatives, silicones, oils, non-silicone waxes in wax form and mixtures thereof.

[0250] 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.

[0251] 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.

[0252] airbrush As mentioned above, the composition C used in connection with the method according to the invention is sprayed onto the keratin hair fibres using an airbrush.

[0253] To spray the composition, an airbrush system 1 shown in FIG. 1 is used.

[0254] The airbrush system 1 may, as shown, comprise an airbrush 2 connected to a compressed gas source, for example comprising an air compressor 4 connected to the airbrush 2 via a pressure regulator 5 and a hose 15 in a manner known per se. The compressed gas source may also be a replaceable or refillable capsule of compressed gas, for example compressed air.

[0255] The airbrush 2 comprises, in a manner known per se, a grip defined, for example, by the elongated body of the airbrush if the airbrush is pen-like, or by a handle 10 if the handle is pistol-like as shown in FIG.

[0256] The airbrush 2 may carry a container 11 containing the composition C to be sprayed, for example in the form of a detachable bottle. The airbrush may include a connection device 30 at the top for receiving the container 11, as shown.

[0257] During operation of the airbrush 2, product is drawn up and flows into the airbrush via a collection channel before being sprayed.

[0258] The container 11 may be transparent or may be provided with graduations so that the user can more easily visualize the amount of product available. The volume of product contained in the container 11 is, for example, 1 to 5000 mL, preferably 1 to 1000 mL, and even more preferentially 1 to 500 mL.

[0259] Preferably, the hose 15 connecting the airbrush to the compressor 4, in particular the air regulator 5, is no more than 5 m long and has an internal diameter of, for example, 4 mm. The hose 15 is preferably equipped with a quick connect coupling.

[0260] The airbrush 2 may be offered to the user with several stoppered pre-filled containers 11, as shown in Figure 1, which for example all contain the same product so that the user can quickly exchange empty containers for full containers, for example to treat different people.

[0261] The container 11 may further contain different products, e.g. products of different compositions, intended to perform different treatments complementary or otherwise, allowing the user to select the container 11 corresponding to the procedure to be performed.

[0262] The spraying parameters, in particular the flow rate of the carrier gas (preferably air) and / or the flow rate of the sprayed product, can be adapted manually by the user as needed each time the container 11 is changed or during use to obtain the desired visual effect.

[0263] The relative pressure of the compressed air entering the airbrush 2 may be between 0.2 and 3 bar, preferably between 0.4 and 1 bar, for example about 0.5 bar.

[0264] The nozzle 21 attached to the airbrush is preferably selected so that the average size of the droplets of sprayed product is centered between 10 and 35 μm, for example about 23 μm (size measured at a distance of 15 cm from the nozzle outlet).

[0265] The nozzle 21 may have an outlet diameter in the range of, for example, 0.1 to 1 mm, preferably 0.2 to 0.7 mm.

[0266] A suitable connection device 30 for a container 11 in the form of a bottle including a neck to which a collar and stopper 120 are attached includes, in the example shown, an end piece for fastening to the body of the airbrush, for example of the quick-fit type, to enable detachable fastening to the body of the airbrush.

[0267] Of course, it would not depart from the invention if the connection device 30 were removably secured to the remainder of the airbrush, or if it were removably secured using means other than a quick coupling.

[0268] When the connection device 30 is in place on the airbrush, the axis of the nozzle may be vertical or may be angled towards the front or rear of the airbrush.

[0269] The connection device 30 may further be made in the form of a part of the body of the airbrush, the connection device 30 not necessarily protruding relative to the body of the airbrush.

[0270] The container 11 is leak-tightly secured to the connecting device and an air return circuit is provided to allow air to return into the container when it is emptied. Except for the product recovery and air return circuit, the container is closed.

[0271] To use the airbrush 2 , the user places the container 11 on the connection device 30 .

[0272] Before being placed on the airbrush, the container 11 is fitted with a stopper 120, for example a nipple or closure cap, which is then separated from the container.

[0273] The airbrush 2 may include optional spray activation means in the form of a control member, for example a lever 13, which is actuated by the fingers of the user's hand holding the airbrush, as shown in Figure 2. In this figure, the airbrush is a gravity airbrush. It is not outside the scope of the present invention to use a suction airbrush. In the latter case, it is sufficient for the connection device 30 to be equipped with a system (for example a tube 200, as shown in dashed lines in Figure 1) for connecting the first orifice to the inlet of the airbrush to enable suction.

[0274] Examples of airbrushes to which the present invention can be applied include the Azteck reference A4700, the Iwata reference Kustom micron CM, and the Harder and Steenbeck reference "Evolution Infinity 2 in 1", which are of the pen grip type. The Iwata "Kustom REVOLUTION TR" or "Studio Series" airbrushes or the Harder & Steenbeck Colani® airbrushes can also be used.

[0275] Of course, other configurations are possible, for example the same compressor can be used for several airbrushes, this compressor being located, for example, outside the room in which the treatment takes place, in order to reduce noise pollution.

[0276] Preferably the spray is round, but various nozzles can be used to have a flat spray or a spray with another shape depending on the visual effect to be achieved.

[0277] The compressor may be replaced with a source of compressed air, such as bottled compressed air or compressed or liquefied gas cartridges, which may be mounted on the airbrush and carried therewith during use.

[0278] If desired, multiple containers may be attached to the airbrush.

[0279] The tank mounted on the airbrush can be replaced with a tank connected to the airbrush by a pipe, and the product is drawn into the airbrush by the negative pressure created by the Venturi effect due to the circulation of the carrier gas within the airbrush. A pump can also be used to supply the product to be sprayed to the airbrush.

[0280] The use of an airbrush allows the user to easily modify its operating parameters in order to change the effect produced during use at his discretion, for example by adjusting the flow rate of the product jet as a function of the desired visual effect. Furthermore, if the airbrush is connected to a compressor, the amount of gas (preferably air) used as a vector is unlimited. The product to be sprayed can be easily renewed, and different products can easily be used successively with the same airbrush.

[0281] The flow rate of the sprayed composition is advantageously less than or equal to 10 g / min.

[0282] protocol Composition C described above can be used on wet or dry keratinous fibers and can also be used on any type of keratinous hair fiber, whether light or dark, natural or dyed, permanently waved, bleached or straightened.

[0283] According to a particular embodiment of the invention, the keratinous hair fibers are washed before applying composition C.

[0284] Preferably, a washing, rinsing, spin-drying or drying step is carried out after applying composition C to the keratinous hair fibre.

[0285] More preferentially, a drying step is carried out after spraying composition C onto the keratin hair fibres.

[0286] As above, Composition C is sprayed using an airbrush as described above.

[0287] Composition C is generally sprayed onto the keratin hair fibres at room temperature (15-25°C).

[0288] After spraying composition C onto keratinous hair fibers, it can be left for 1 minute to 6 hours, in particular 1 minute to 2 hours, more particularly 1 minute to 1 hour and more preferentially 1 minute to 30 minutes, for example before a washing, rinsing, spin-drying or drying step.

[0289] After spraying with composition C, the keratin hair fibres can be allowed to dry naturally or can be dried at a temperature of, for example, 30° C. or higher.

[0290] Thus, the method according to the present invention may comprise the step of applying heat to the keratinous hair fibres using a heating appliance.

[0291] The heat application step of the method of the present invention can be carried out using a hood dryer, a hair dryer, a straightener, a crimson hood, or the like.

[0292] Preferably, the step of applying heat of the method of the present invention is carried out using a hair dryer.

[0293] When the method of the present invention includes the step of applying heat to the keratinous hair fibers, the step of applying heat to the keratinous hair fibers is carried out after applying composition C to the keratinous hair fibers.

[0294] During the process of applying heat to the keratinous hair fibers, the hair strands may be subjected to mechanical action such as combing, brushing or hand combing.

[0295] If the step of applying heat to the keratinous hair fibres is carried out using a hood dryer or a hair dryer, the temperature is preferably between 30°C and 110°C, preferentially between 50°C and 90°C.

[0296] If the step of applying heat to the keratin hair fibres is carried out using a straightening iron, the temperature is preferably between 110°C and 220°C, preferably between 140°C and 200°C.

[0297] In a particular variant, the method of the invention comprises a step (c1) of applying heat using a hood dryer, hair dryer or crimson hood, preferably a hair dryer, and a step (c2) of applying heat using a straightening iron or curling iron, preferably a straightening iron.

[0298] Step (c1) may be carried out before step (c2).

[0299] During the implementation of step (c1), also referred to as the drying step, the keratinous hair fibers can be dried, for example, at a temperature of at least 30° C. According to a particular embodiment, this temperature is greater than 40° C. According to a particular embodiment, this temperature is greater than 45° C. and less than 110° C.

[0300] Preferably, when drying the keratinous hair fibers, in addition to the supply of heat, it is done by using an air current, which makes it possible to improve the separation of the coating of the strands during drying.

[0301] During drying, the hair strands may be subjected to mechanical action such as combing, brushing or hand combing.

[0302] In step (c2), the temperature at which the straightening iron or curling iron is slid may preferably be in the range of 110°C to 220°C, and more preferably 140°C to 200°C.

[0303] After the heating step, a shaping step can be carried out, for example, with a straightening iron, and the temperature in the shaping step can be 110°C to 220°C, preferably 140°C to 200°C.

[0304] Preferably, the present invention relates to a method for dyeing keratinous hair fibres, comprising the steps of: i) Using the airbrush above, - at least one (poly)carbodiimide compound as defined above, and at least one colorant selected from pigments, direct dyes and mixtures thereof; spraying onto keratinous hair fibers at least one composition C comprising: ii) optionally, a leaving time of said composition C on the keratin hair fibres for 1 minute to 30 minutes, preferably 1 to 20 minutes; then iii) optionally washing, rinsing, dewatering and / or drying the keratinous hair fibers; The method includes:

[0305] Preferably, composition C also includes at least one compound containing at least one carboxylic acid functional group.

[0306] Advantageously, the step of spraying composition C onto the keratinous hair fibers is repeated several times.

[0307] According to a preferred embodiment, the dyeing method according to the invention is a method for dyeing keratinous hair fibers, which method in use comprises extemporaneously mixing at least two compositions A and B to obtain a composition C, and spraying composition C onto the keratinous hair fibers using an airbrush as described above, - composition A comprises at least one (poly)carbodiimide compound as defined above; Composition B comprises at least one colorant chosen from pigments, direct dyes and mixtures thereof.

[0308] Composition A and / or Composition B may optionally include at least one compound containing at least one carboxylic acid functional group.

[0309] Preferably, composition B comprises at least one compound containing at least one carboxylic acid functional group.

[0310] Preferably, composition A does not contain at least one colorant selected from pigments, direct dyes and mixtures thereof.

[0311] According to this embodiment, the mixing of compositions A and B is preferably carried out less than 15 minutes before spraying onto the keratin hair fibers, more preferentially less than 10 minutes before spraying, and even better still less than 5 minutes before spraying.

[0312] 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, and even from 0.6 to 1.5. In a particular embodiment, the weight ratio of composition A to composition B is equal to 1.

[0313] The total amount of the (poly)carbodiimide compounds is preferably in the range of 0.01% by mass to 40% by mass, more preferentially 0.1% by mass to 30% by mass, even better 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.

[0314] If present, the total amount of compounds containing at least one carboxylic acid function preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 40% by weight, even better still from 1% to 30% by weight and even more preferentially from 2% to 20% by weight relative to the total weight of composition B.

[0315] Spraying System The present invention provides - Airbrush; - at least one compartment, a) at least one (poly)carbodiimide compound as defined above; b) at least one colorant selected from pigments, direct dyes, and mixtures thereof; At least one compartment containing a composition C comprising The present invention also relates to a spray system comprising:

[0316] The present invention provides - Airbrush; - several compartments, In the first section, a) a composition A comprising at least one (poly)carbodiimide compound as described above; In the second section, b) Composition B comprising at least one colorant selected from pigments, direct dyes and mixtures thereof. Several compartments that house The present invention also relates to a spray system comprising:

[0317] 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]

[0318] The (poly)carbodiimides of the present invention can be obtained via synthetic methods known to those skilled in the art, starting from commercially available products or reagents that can be synthesized according to chemical reactions known to those skilled in the art, for example, in the book Sciences of Synthesis - Houben-Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag KG, Rüdigerstrasse 14, D-70469 Stuttgart, or in U.S. Pat. No. 4,284,730 or Canadian Patent Application No. 2,509,861.

[0319] 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.) To deactivate the catalyst, a benzoyl halide such as benzoyl chloride may be added.

[0320] 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 equivalents of the reagent HEH, followed by 1 equivalent of the reagent R1-X1-H.

[0321] In the second step of this preparation process, to obtain an "unsymmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 eq.) of the nucleophilic reagent R1-X1-H, and then with 1 eq. of the reagent HEH (wherein R1, X1 and E are as defined above), to give compound (5): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EH (5) (In formula (5), R1, X1, L1, n, and E are as defined above.) get.

[0322] 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.

[0323] In the third step, compound (5) is reacted with 1 eq. 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.) (prepared in advance from which reacts with one equivalent of a nucleophile R2-X2-H having L1, R2, X2 and z as defined above to give the asymmetric compound (7): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EC(O)-NH-L1-(N=C=N-L1) z -NH-C(O)-X2-R2(7) (In formula (7), R1, X1, L1, R2, X2, n, z, and E are as defined above.) results.

[0324] 1 molar equivalent of the compound O=C=N-L1-(N=C=N-L1) z -N=C=O(3') was reacted with 1 / w molar equivalent of HEH followed by 1 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

[0325] This final compound (8) is then reacted with 1 equivalent of compound (4'): R1-X1~C(O)-NH-L1-(N=C=N-L1) n -N=C=O (4') (The compound (4') can be synthesized by reacting 0.5 equivalents of a nucleophilic reagent R1-X1-H with 1 equivalent of compound (3).) to obtain the (poly)carbodiimide (9) of the present invention: R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NHC(O)-X2-R2(9) (In formula (9), L1, R1, X1, R2, X2, n, z, w, and E are as defined above.) can be obtained.

[0326] 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.

[0327] 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.

[0328] Infrared spectroscopy reveals that the -1The 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.

[0329] 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.

[0330] 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.

[0331] Example 2 Compositions A and B were prepared as described in Tables 1 and 2 below. Amounts are expressed as g / 100g of the resulting starting material unless otherwise stated. In the tables below, "am" means "active substance."

[0332] [Table 1]

[0333] [Table 2]

[0334] Composition A was then mixed with composition B in a 50 / 50 weight ratio to obtain composition C according to the present invention.

[0335] protocol Two application methods were used.

[0336] According to a first method, known as Method P1, Composition C was applied manually with a brush to dry natural keratin fiber tresses comprising 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 then combed.

[0337] This is therefore a comparative method.

[0338] According to a second method, known as Method P2, Composition C was introduced into a cup, and the cup was inserted into an airbrush (Iwata Studio Series Airbrush). Pressure was applied to the trigger, and the composition was dispensed via 0.5 bar compressed air at a distance of 5 cm or less for a time sufficient to coat a bundle of dry natural keratin hair fibers containing 90% white keratin hair fiber strands. Composition C was thus sprayed onto the bundle of keratin hair fibers. The bundle of keratin hair fibers was then detangled, dried with a hair dryer, and then combed.

[0339] This is therefore the method according to the invention.

[0340] Shampoo Wash Protocol: A strand of dry keratin hair fibres is combed, moistened with water at 35°C and then passed through the fingers 5 times for 5 seconds. The strand of keratin hair fibres is then squeezed between two fingers and dried.

[0341] A standard shampoo (Garnier Ultra Doux) was applied evenly to the dyed hair tresses at a ratio of 0.4 g of standard shampoo per gram of tress and gently massaged (6 times) along the length of the keratin hair fiber tress from root to tip for 15 seconds.

[0342] The keratin hair fiber strand is then placed on a watch glass and left for 1 minute.

[0343] The keratin hair fibre strands are then rinsed with water while passing them through the fingers (15 times).The keratin hair fibre strands are then squeezed dry between two fingers before the next shampoo wash.

[0344] After the test, which involves several shampoo washes, the keratin hair fibre strands are combed and dried with a hair dryer.

[0345] result The color durability of the tresses was evaluated in the CIE L*a*b* system using a Minolta Spectrophotometer CM3600A spectrophotometer (D65 illuminant, 10° angle, including specular reflection component).

[0346] 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.

[0347] The durability of the color is evaluated by the color difference ΔE between the colored hair strand before shampooing and after shampooing three times according to the procedure described above. The lower the ΔE value, the better the color durability after shampooing.

[0348] The ΔE value is calculated according to the following formula:

number

[0349] In this formula, L*a*b* represents the value measured after dyeing keratin hair fibers and after shampooing, and L0*a0*b0* represents the value measured after dyeing keratin hair fibers and before shampooing.

[0350] [Table 3]

[0351] A lock of keratinous hair fibres treated by the method P2 according to the invention and washed with shampoo three times has a lower ΔE value than a lock of keratinous hair fibres treated by the comparative method P1.

[0352] The colored coating obtained by the method according to the invention therefore has improved durability against shampooing.

Claims

1. 1. A method of dyeing keratinous hair fibers, comprising using an airbrush: one or more (poly)carbodiimide compounds; at least one colorant selected from pigments, direct dyes and mixtures thereof; A method comprising spraying onto said keratinous hair fibers at least one composition C 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 represents a hydrocarbon-based group, preferably a group selected from alkyl, optionally interrupted by a number of 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 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 from which the hydroxyl groups have been removed, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof; n and z represent integers ranging from 1 to 20, 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, straight 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, straight 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, straight 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 are independently monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed; n and z represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L １ 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, straight 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, straight 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, straight 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, and R ３ is a C optionally interrupted by one or more heteroatoms ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, straight 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, and R ３ is a straight or branched C alkyl group such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms; １ ~C １８ 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, and R ３ is a straight or branched C alkyl group such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms; １ ~C １８ represents an alkylene group, and r and s represent integers ranging from 4 to 30.

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

9. 9. The method according to any one of claims 1 to 8, characterized in that the total amount of (poly)carbodiimide compounds ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferentially from 0.2% to 10% by weight, even more preferentially from 0.5% to 8% by weight and 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 ranges from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, relative to the total weight of composition C; preferably, said colorants are chosen from pigments.

11. 11. The method according to any one of claims 1 to 10, characterized in that composition C also comprises at least one compound containing at least one carboxylic acid function.

12. 12. The method of claim 11, wherein the compound containing at least one carboxylic acid functional group is selected from silicone compounds, polyurethanes, acrylic polymers and mixtures thereof containing at least one carboxyl group.

13. 13. The method according to claim 11 or 12, 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.

14. The acrylic polymer may be composed of the following monomers: a) (meth)acrylic acid; and b) C １ ~C ３０ , more preferentially C １ ~C ２０ , and even better C １ ~C １０ , and more particularly C １ ~C ４ Alkyl (meth)acrylate 14. The method of claim 13, comprising one or more units derived from:

15. 15. Method according to any one of claims 11 to 14, 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.

16. In use, the method comprises extemporaneously mixing at least two compositions A and B to obtain composition C, and spraying composition C onto said keratinous hair fibers, composition A comprises at least one (poly)carbodiimide compound according to any one of claims 1 to 8; - Method according to any one of claims 1 to 8, characterized in that composition B comprises at least one colorant chosen from pigments, direct dyes and mixtures thereof.

17. - Airbrush; at least one compartment, a) at least one (poly)carbodiimide compound according to any one of claims 1 to 9; b) at least one colorant selected from pigments, direct dyes, and mixtures thereof; At least one compartment containing a composition C comprising A spray system including:

18. - Airbrush; - several compartments, In the first section, a) at least one (poly)carbodiimide compound according to any one of claims 1 to 8 Composition A comprising: In the second section, b) at least one colorant selected from pigments, direct dyes, and mixtures thereof; Composition B comprising Several compartments that house A spray system including:

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