A method for coloring hair keratin fibers, comprising applying a composition comprising at least one (poly)carbodiimide compound and a composition comprising at least one associative polymer and a specific compound.

Abstract

The present invention relates to a method for coloring hair keratin fibers, in particular hair, comprising applying a composition A and a composition B to said hair keratin fibers: composition A comprises at least one (poly)carbodiimide compound and composition B comprises at least one associative polymer; and at least one compound different from the associative polymer, containing at least one carboxylic acid group; at least one compound, preferably at least two compounds, containing at least one hydroxyl functional group; composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof; and composition A and composition B are applied simultaneously or successively to hair keratin fibers. The present invention also relates to an apparatus for coloring hair keratin fibers.

Description

[Technical Field]

[0001] The present invention relates to a method for coloring hair keratinous fibers, comprising applying composition A and composition B to hair keratinous fibers, wherein composition A comprises at least one (poly)carbodiimide compound, composition B comprises at least one associative polymer, at least one compound different from the associative polymer that contains at least one carboxylic acid group, and at least one compound that contains at least one hydroxyl functional group, and composition A and / or composition B comprise at least one colorant selected from pigments, direct dyes, and mixtures thereof, and composition A and composition B are applied to hair keratinous fibers simultaneously or sequentially.

[0002] The present invention also relates to a device for coloring hair keratin fibers.

[0003] In the field of coloring keratinous fibers, in particular human keratinous fibers, it is already known practice to color the keratinous fibers by various techniques, using direct dyes or pigments to produce non-permanent colorings, or using color precursors to produce permanent colorings. [Background technology]

[0004] There are three basic methods for coloring hair: a) "Permanent" coloring: its action makes it possible to significantly modify the original color and uses oxidative dyes that penetrate the hair fiber and produce pigments through an oxidative condensation process. b) Non-permanent, semi-permanent or direct coloring: without using an oxidative condensation process and resistant to 4-5 shampoo washes; this involves coloring the hair keratin fibers with a coloring composition containing a direct dye. c) Temporary coloring: corrects the natural color of the hair, remains from one shampooing to the next, and serves to enhance or correct the color already obtained. This can also be related to the "make-up" method.

[0005] For the latter type of coloration, it is known to use colored polymers produced by grafting one or more dyes of azo, triphenylmethane, azine, indoamine or anthraquinone nature onto the polymer chain. Such colored polymers are not entirely satisfactory, particularly with regard to the uniformity of the color imparted and its durability, not to mention the problems associated with their production, particularly with regard to reproducibility.

[0006] Another coloring method is the use of pigments. Specifically, the use of pigments on the surface of hair keratin fibers generally makes it possible to achieve a color that is visible even on dark hair, since the pigments on the surface mask the original color of the fibers. However, the coloring obtained by this coloring method has the disadvantage that it is not only less resistant to shampooing, but also to external agents such as sebum, sweat, brushing and / or friction.

[0007] Moreover, temporary hair coloring compositions may also have working qualities that are not entirely satisfactory, especially with regard to texture, ease and / or evenness of spreading on the head of hair.

[0008] There is therefore still a need for a method for coloring hair keratin fibers that has the advantage of obtaining a smooth and uniform colored coating on the hair, while at the same time forming a durable coating against shampooing and the various attacking factors to which the hair may be subjected, such as brushing and / or rubbing, without degrading the hair, and in which the compositions used in the context of said method have good stability over time and good storage over time, i.e. good protection against microorganisms, as well as good working qualities.

[0009] The object of the present invention is therefore to develop a method for coloring hair keratin fibers, which has the advantage of obtaining a smooth and uniform colored coating on the hair, while at the same time forming a durable coating against shampooing and the various attacking factors to which the hair may be subjected, such as brushing and / or rubbing, without degrading the hair, and wherein the compositions used in the context of said method have good stability over time and good storage over time, i.e. good protection against microorganisms, as well as good working qualities. Summary of the Invention [Means for solving the problem]

[0010] Thus, one subject of the present invention is a method for coloring hair keratinous fibers, comprising applying a composition A and a composition B to the hair keratinous fibers, wherein: Composition A comprises at least one (poly)carbodiimide compound; Composition B is at least one associative polymer; at least one compound different from the associative polymer, containing at least one carboxylic acid group, and - comprising at least one compound, preferably at least two compounds, containing at least one hydroxyl functional group; Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof; and A method in which composition A and composition B are applied simultaneously or sequentially to hair keratin fibers.

[0011] In one variant of the invention, composition C is obtained by extemporaneous mixing at the time of use of at least one composition A as defined above and at least one composition B as defined above. In this variant, composition C obtained by mixing composition A and composition B is applied to the hair keratin fibres.

[0012] In another variant, composition A as defined above and composition B as defined above are applied simultaneously to the hair keratin fibres.

[0013] In another variant, composition A and composition B are applied sequentially to the hair keratinous fibers, with composition A optionally being applied to the hair keratinous fibers before composition B, or vice versa.

[0014] The present invention also provides an apparatus for coloring hair keratin fibers, comprising: in a first compartment (E1), composition A as defined above; and in a second compartment (E2), composition B as defined above; optionally in a third compartment (E3), composition D as defined below The present invention also relates to a device comprising at least two compartments,

[0015] When this coloring method is used on hair keratin fibers, a colored coating is obtained on the hair that can be colored to a visible color on all types of hair, in a manner that is durable against shampooing and at the same time maintains the physical quality of the hair keratin fibers. This type of coating is able to withstand external aggressors to which the hair may be exposed, such as blow drying and perspiration. It is thereby possible to obtain a particularly smooth and uniform deposit.

[0016] Furthermore, the compositions used in the context of the coloring method according to the invention have good stability over time, in particular after a storage period at room temperature or at a temperature in the range from room temperature to 45° C. The compositions used in the context of the coloring method according to the invention also have good storage over time, i.e. good protection against microorganisms, in particular after a storage period of up to 2 months at room temperature or at a temperature in the range from room temperature to 55° C.

[0017] Furthermore, the compositions used in the context of the method according to the invention have good working qualities, in particular with regard to texture, ease and uniformity of spreading on the hair, while minimizing running problems.

[0018] 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, and more preferentially after five shampooings. DETAILED DESCRIPTION OF THE INVENTION

[0019] Other objects, features, aspects and advantages of the present invention will become more apparent from reading the following description and examples.

[0020] In the text below, unless otherwise specified, the limits of numerical ranges are encompassed within the ranges, in particular the expressions "between" and "ranging from".

[0021] The term "at least one" means one or more.

[0022] The invention is not limited to the illustrated embodiments, and features of the various embodiments may in particular be combined in variations not illustrated.

[0023] For purposes of this invention, unless otherwise specified: - "Alkyl" group refers to a saturated, straight or branched chain group containing, for example, 1 to 20 carbon atoms; - an "aminoalkyl" group refers to an alkyl group as defined above, wherein said alkyl group contains an NH group; - a "hydroxyalkyl" group refers to an alkyl group as defined above, wherein said alkyl group contains an OH group; - "Alkylene" group denotes a linear or branched saturated C2-C4 hydrocarbon-based divalent group, such as methylene, ethylene or propylene; - "cycloalkyl" or "alicycloalkyl" group refers to a cyclic saturated monocyclic or bicyclic, preferably monocyclic hydrocarbon-based group containing 1 to 3 rings, preferably 2 rings, and containing 3 to 24 carbon atoms, in particular 3 to 20 carbon atoms, more particularly 3 to 13 carbon atoms, even more particularly 3 to 12 carbon atoms, preferably 5 to 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, wherein the cycloalkyl group can be substituted by one or more (C1-C4) alkyl groups, such as methyl; in that case it is understood that the cycloalkyl group is preferably an isobornyl group; - "Cycloalkylene" group refers to a group having the above-defined "cycloalkyl", preferably C3-C 12 refers to a divalent cycloalkyl group; - "aryl" group is a monocyclic, bicyclic or tricyclic, fused or non-fused, unsaturated aromatic hydrocarbon-based ring group containing 6 to 14 carbon atoms, preferably 6 to 12 carbon atoms; preferably, the aryl group contains one ring having 6 carbon atoms, such as phenyl, naphthyl, phenanthryl, where it is understood that the phenyl group may be substituted with one or more (C1-C4) alkyl groups, such as methyl, preferably tolyl, xylyl or methylnaphthyl; preferably, the aryl group represents phenyl; - an "arylene" group is a divalent aryl group with "aryl" as defined above; preferably, arylene represents phenylene; - "heterocyclic" group is a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based group containing one or more heteroatoms, preferably 1 to 5 atoms selected from O, S or N, and containing 3 to 20 ring members, preferably 5 to 10 ring members, such as imidazolyl, pyrrolyl and furanyl; - a "heterocycloalkylene" group is a divalent heterocyclic group having the above-defined "heterocyclic" group; - an "aryloxy" group refers to an aryloxy group with the "aryl" 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.

[0024] The term "hair keratin fibres" means hair.

[0025] For the purposes of the present invention, the expression "hair" means hair on the head. This does not refer to eyelashes, eyebrows or body hair.

[0026] Polycarbodiimide Compounds Composition A according to the invention used in the context of the coloring method according to the invention comprises at least one (poly)carbodiimide compound.

[0027] The composition may comprise at least two different (poly)carbodiimide compounds present as a mixture in the composition.

[0028] 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.

[0029] The term "carbodiimide group" refers to a divalent, linear, three-atom moiety of the general formula -(N=C=N)-.

[0030] The (poly)carbodiimide compound according to the present invention may optionally contain in its structure one or more reactive groups different from the carbodiimide group selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, such as propylepoxide or butylepoxide, and azacyclopropane group.

[0031] The reactive group other than the carbodiimide group may be a side group or a terminal group. Preferably, the (poly)carbodiimide compound comprises one or more terminal groups, preferably one or more terminal groups, different from the carbodiimide group, selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, such as propylepoxide or butylepoxide, and an azacyclopropane group.

[0032] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (I): [ka] (In the formula, -X1 and X2 independently represent an oxygen atom O, a sulfur atom S, or an NH group; R1 and R2 independently represent hydrocarbon-based groups optionally interrupted by one or more heteroatoms, preferably groups selected from alkyl, alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxides, such as propylepoxide or butylepoxide, and azacyclopropane groups, and represents a hydrocarbon-based group, preferably a group selected from alkyl, optionally interrupted by one or more heteroatoms and one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide, such as propyl epoxide or butyl epoxide, and azacyclopropane groups; -n represents an integer ranging from 1 to 1000; and A is the following compound: [ka] The monomer is selected from the group consisting of:

[0033] According to another embodiment, the (poly)carbodiimide compound has the following formula (Ia): [ka] (In the formula, -X1 and X2 independently represent an oxygen atom O, a sulfur atom S, or an NH group; -Y1 and Y2 are independently saturated C1 to C 36 Aliphatic group or C6~C 24 represents a divalent organic group selected from an aromatic or alkylaromatic group, wherein the aliphatic or aromatic group optionally contains one or more non-pendant heteroatoms such as nitrogen atoms, oxygen atoms, sulfur atoms, or combinations thereof; -Z1 and Z2 independently represent a reactive end group or an inactive end group; As inert end groups, Z1 and Z2 are independently saturated, linear or branched or cyclic C1-C 50 Aliphatic group, or C6~C 18 may represent an aromatic group, said aliphatic and aromatic groups optionally containing 1 to 10 heteroatoms selected from nitrogen, oxygen, sulfur and combinations thereof, and wherein the aliphatic or aromatic group may be partially or fully fluorinated; in this variation, Z1 and Z2 comprise a linking group CG connecting Z1 to Y1 and Z2 to Y2, wherein the group CG is optionally a single covalent bond, a saturated C-C bond, an unsaturated covalent C-C bond, an amide group, an ester group, a carbonate group, a thioester group, an ether group, a urethane group, a thiourethane group or a urea group; as reactive end groups, Z1 and Z2 may be selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxides such as propylepoxide or butylepoxide and azacyclopropane groups; -Q represents an organic polymer or oligomer comprising repeating units of saturated, linear or branched or cyclic aliphatic groups, or aromatic or alkylaromatic groups, linked via carbonate, ester, ether, amide, urethane or urea repeating bonds or combinations thereof; -A represents a divalent aliphatic, aromatic, alkylaromatic, or straight-chain, saturated, branched, or cyclic group containing 2 to 30 carbon atoms, which may optionally contain one or more non-pendant heteroatoms in the aliphatic or aromatic chain, such as nitrogen atoms, oxygen atoms, sulfur atoms, or combinations thereof; - r 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 represents an integer ranging from 0 to 1000, preferably equal to 0 or 1, and m+(m'*n) is 2 or greater.

[0034] Preferably, Z1 and Z2 independently represent a reactive end group; more preferably, Z1 and Z2 can 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 group.

[0035] Such (poly)carbodiimide compounds are sold, for example, by Stahl BV under the names Permutex XR, RelcaLink 10, Picassian XL, and by Nisshinbo Chemicals under the name Carbodilite with the series V-02, V-02-L2, SV-02, E-02, V-10, SW-12G, E-03A, E-04DG-T, E-05, V-04, V-02B, V-04PF, V-05.

[0036] 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 is independently - -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- (wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; -R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms. represents a group selected from The compound is selected from the group consisting of:

[0037] The term "hydrocarbon-based group" means a saturated or unsaturated, linear or branched group containing 1 to 300 carbon atoms, preferably 1 to 250 carbon atoms, more preferentially 1 to 200 carbon atoms. Preferably, the hydrocarbon-based group is a saturated linear group.

[0038] The hydrocarbon-based group can contain one or more cyclic groups.

[0039] 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.

[0040] 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.

[0041] Preferably, X1 and X2 independently represent an oxygen atom.

[0042] Preferably, R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, from which the hydroxyl groups have been removed, and mixtures thereof.

[0043] In a preferred embodiment, R1 and R2 are selected from the following groups (i) to (iv): (i) Formula (III): R7-OC(O)-C(R8)(H)- (III) (wherein R7 represents a C1-C3 alkyl group, and R8 represents a hydrogen atom or a C1-C3 alkyl group; preferably, R7 is methyl, and R8 is a hydrogen atom or methyl) (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 (iii) Formula (V): (R 11 )2N-CH2-C(H)(R 12 )- (V) (In the formula, R 11 represents a C1-C4 alkyl group, and R 12 represents a hydrogen atom or a C1-C4 alkyl group; preferably, R 11 is methyl, ethyl or butyl, and R 12 is a hydrogen atom or methyl) (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, and q represents an integer ranging from 4 to 30; preferably, R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl).

[0044] Preferably, R1 and R2 independently represent a compound of formula (VI), wherein R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R14 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.

[0045] According to an alternative embodiment, R1 and R2 are different, and one of the R1 or R2 groups represents a compound of formula (IV) as described above, and the other of the R1 or R2 groups represents a compound of formula (VI) as described above.

[0046] 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.

[0047] 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.

[0048] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), wherein R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; and q represents an integer in the range of 4-30.

[0049] Preferably, n represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0050] Preferably, z represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0051] Preferably, w is equal to one.

[0052] Preferably, w is equal to 1 and n+z represents an integer ranging from 4 to 10.

[0053] Preferably, L1 is a divalent C1-C6 alkyl group such as methylene, ethylene, and propylene. 18Aliphatic hydrocarbon groups, C3-C such as cyclopentylene, cycloheptylene, and cyclohexylene 15 C3-C such as cycloalkylene groups, imidazolene, pyrrolene, and furanylene 12 C6-C such as heterocycloalkylene group or phenylene 14 The aryl group is selected from arylene groups as well as mixtures thereof.

[0054] For example, L1 can 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.

[0055] Preferably, L1 is C3 to C 15 Cycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, such as those of the following formula (VII): [ka] is selected from.

[0056] Preferably, L1 is represented by the following formula (VIII): [ka] The corresponding 4,4-dicyclohexylenemethane is

[0057] According to another embodiment, L1 is C6 to C 14 When L1 is an arylene group, it is represented by the following formula (IX): [ka] It is not an m-tetramethylxylylene group represented by the formula:

[0058] As mentioned earlier, E is independently - -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- (wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; -R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; and -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms. represents a group selected from

[0059] 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.

[0060] 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.

[0061] Preferably, when R5 is not a covalent bond, R5 is a C6-C6 alkyl group, such as phenylene, optionally interrupted by one or more heteroatoms. 14 C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 The alkylene groups are selected from alkylene groups as well as mixtures thereof.

[0062] Preferably, R6 is a C6-C, such as phenylene, optionally interrupted by one or more heteroatoms. 14 C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 The alkylene groups are selected from alkylene groups as well as mixtures thereof.

[0063] Preferably, E represents a -O-R-O- group, where R is a C-C alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 The alkylene group is selected from alkylene groups and mixtures thereof.

[0064] 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.

[0065] 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.

[0066] The term "alkyl group" in this embodiment is as defined above.

[0067] The term "cycloalkyl group" in this embodiment is as defined above.

[0068] 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.

[0069] 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

[0070] The "alkyl group", "cycloalkyl group" and "aryl group" are as defined above.

[0071] According to a preferred embodiment, the (poly)carbodiimide compound is selected from compounds of formula (I) or formula (II), wherein: -X1 and X2 independently represent an oxygen atom; R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed, and more preferentially R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30; - n and z, if present, represent integers ranging from 1 to 20, where n + z ≥ 2 and w is equal to 1; -L1, if present, is a divalent C1-C 18 Aliphatic hydrocarbon group, C3-C 15Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, preferably C3-C 15 cycloalkylene groups; -A, if present, is a divalent C1-C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, preferably C3-C 15 cycloalkylene groups; -E, if present, may be independently - -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- wherein R3 and R4 independently represent a C6-C 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; - R5 is not a covalent bond, and if R5 is present, it is a C6-C 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups, and mixtures thereof; and -R6, if present, may be a C6-C 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof) represents a group selected from

[0072] Preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein -X1 and X2 independently represent an oxygen atom; R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, from which the hydroxyl groups have been removed, and mixtures thereof; - n and z represent integers ranging from 1 to 20, where n + z ≥ 2 and w is equal to 1; -L1 is 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 is independently - -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- wherein R3 and R4 independently represent a C6-C 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; If R5 is not a covalent bond, R5 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; and -R6 is a C-C group optionally interrupted by one or more heteroatoms 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof) represents a group selected from

[0073] 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 is independently - -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- wherein R3 and R4 independently represent a C6-C 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; If R5 is not a covalent bond, R5 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; and -R6 is a C-C group optionally interrupted by one or more heteroatoms 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof) represents a group selected from

[0074] 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 are independently selected from the group consisting of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) (In the formula, 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. represents the compound of - n and z represent integers ranging from 2 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 is an -O-R-O- group, where R is a C-C alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof).

[0075] 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 are independently selected from the group consisting of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) (In the formula, R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30. represents the compound of - n and z represent integers ranging from 1 to 20, preferably from 2 to 20, where n + z is in the range from 4 to 10 and w is equal to 1; -L1 is a C3-C alkyl group such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane.15 a cycloalkylene group, preferably 4,4-dicyclohexylenemethane; -E is a -O-R-O- group, where R is a straight or branched C-C alkyl group such as methylene, propylene, butylene, or ethylene, optionally interrupted by one or more heteroatoms. 18 represents an alkylene group).

[0076] 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, preferably from 2 to 20, where n+z is in the range of 4 to 10, and E is an -O-R3-O- group, where R3 is a linear or branched C1-C alkyl group such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms. 18 an alkylene group), and r and s represent integers ranging from 4 to 30. is a compound of

[0077] The total amount of (poly)carbodiimide compounds present in the composition A according to the invention is preferably in the range of 0.01% to 40% by weight, more preferentially 0.1% to 30% by weight, better still 0.5% to 25% by weight, and even better still 2% to 20% by weight, relative to the total weight of the composition A.

[0078] The total amount of (poly)carbodiimide compounds present in the composition C according to the invention preferably ranges from 0.01% to 30% by weight, more preferentially from 0.1% to 25% by weight, better still from 0.2% to 20% by weight and even better still from 1% to 10% by weight, relative to the total weight of the composition C.

[0079] Non-carboxylate anionic thickener Composition A may also include a non-carboxylate anionic thickener.

[0080] For purposes of the present invention, the term "non-carboxylic acid agent" refers to an agent that does not contain a carboxylic acid functional group (-COOH) or a carboxylic acid ester functional group (-COO - ) means a drug that does not contain

[0081] For the purposes of the present invention, the term "thickener" means a thickener that, when present at a concentration of 0.05% by weight, thickens the composition into which it is incorporated at room temperature (25°C) and atmospheric pressure at a shear rate of 1 s -1 The term "viscosity" refers to a compound that increases the viscosity of a composition by at least 20 cps, preferably at least 50 cps (viscosity can be measured using a cone / plate viscometer such as a Haake R600 rheometer).

[0082] Preferably, the non-carboxylic acid anionic thickener is chosen from non-carboxylic acid anionic polymers, more preferentially from anionic polymers containing sulfonic groups.

[0083] For purposes of the present invention, the term "anionic polymer" means a polymer that contains one or more anionic or anionizable groups and no cationic or cationic groups.

[0084] Advantageously, the non-carboxylic acid anionic thickener is chosen from anionic polymers comprising at least one ethylenically unsaturated monomer bearing a sulfonic group, in free form or in partially or completely neutralized form.

[0085] The polymer may be crosslinked or non-crosslinked, preferably crosslinked.

[0086] These polymers can be associative or non-associative, preferably non-associative.

[0087] Recall that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0088] Its chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0089] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon chain containing at least 8 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms, more preferentially 18 to 30 carbon atoms.

[0090] Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also refer to a hydrocarbon-based polymer (such as polybutadiene).

[0091] The ethylenically unsaturated monomer having a sulfonic acid group is, in particular, vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylamide (C1-C 22 ) Alkyl sulfonic acid, N-(C1-C 22 ) Alkyl (meth)acrylamide (C1-C 22 ) alkyl sulfonic acids (such as undecylacrylamido methane sulfonic acid) and also partially or fully neutralized forms thereof.

[0092] (Meth)acrylamide (C1-C 22 ) Alkyl sulfonic acids, such as acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also their partially or completely neutralized forms, are more preferentially used.

[0093] More particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and also its partially or fully neutralized forms are used.

[0094] Among the 2-acrylamido-2-methylpropanesulfonic acid copolymers, mention may be made of partially or completely neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide; particular mention may be made of the products described in Example 1 of EP 503853, to which reference may be made with regard to these polymers.

[0095] Mention may also be made of copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts and hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT 10 by the company SEPPIC (INCI name: Hydroxyethyl acrylate / Sodium acryloyldimethyltaurate copolymer).

[0096] Associative AMPS polymers are particularly suitable for C6-C 22 They can be selected from statistical associative AMPS polymers modified by reaction with n-mono- or di-n-alkylamines, such as those described in patent application WO 00 / 31154, the content of which forms an integral part. These polymers can also contain other ethylenically unsaturated hydrophilic monomers, such as (meth)acrylic acid derivatives, for example their esters with monohydric alcohols, or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidones, or mixtures of these compounds.

[0097] Preferred polymers of this family are selected from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0098] These same copolymers may also contain one or more ethylenically unsaturated monomers not containing a fatty chain, such as (meth)acrylic acid derivatives, in particular their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, or mixtures of these compounds.

[0099] These copolymers are described in particular in EP-A-750899, U.S. Pat. No. 5,089,578 and the following publications from Yotaro Morishima: - Self-assembling amphiphilic polyelectrolytes and their nanostructures,Chinese Journal of Polymer Science,Vol.18,No.40,(2000),323-336; - Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering,Macromolecules,Vol.33,No.10(2000),3694-3704; - Solution properties of micelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte: salt effects on rheological behavior - Langmuir, Vol.16,No.12,(2000)5324-5332; - Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers - Polym.Preprint, Div. Polym.Chem.40(2), (1999), 220-221.

[0100] Among these polymers, mention may be made of: -15% to 60% by mass of AMPS units and 40% to 85% by mass of (C8 to C9 16 ) alkyl (meth) acrylamide or (C8-C 16 ) alkyl (meth)acrylate units, crosslinked or non-crosslinked, neutralized or non-neutralized copolymers, such as those described in EP-A-750899; 10 mol% to 90 mol% of acrylamide units, 0.1 mol% to 10 mol% of AMPS units, and 5 mol% to 80 mol% of n-(C6 to C 18 ) terpolymers containing alkylacrylamide units, such as those described in U.S. Pat. No. 5,089,578.

[0101] Mention may also be made of fully neutralized copolymers of AMPS and dodecyl methacrylate and also crosslinked and non-crosslinked copolymers of AMPS and n-dodecylmethacrylamide, such as those described in the Morishima paper mentioned above.

[0102] Preferably, the non-carboxylic anionic thickener is chosen from sodium 2-acrylamido-2-methylpropanesulfonate / hydroxyethyl acrylate copolymers sold by the company SEPPIC (INCI name Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer).

[0103] Advantageously, the total amount of non-carboxylate anionic thickeners ranges from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, better still from 0.1% to 5% by weight, and even better still from 0.1% to 2% by weight, relative to the total weight of composition A.

[0104] Composition B As indicated above, the coloring method according to the invention uses composition B as defined above.

[0105] Associative Polymers Composition B according to the invention, used in the context of the coloring method according to the invention, comprises at least one associative polymer.

[0106] Associative polymers are different from the non-carboxylate anionic thickeners previously described.

[0107] Recall that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0108] Its chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0109] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon chain containing at least 10 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms, more preferentially 18 to 30 carbon atoms.

[0110] Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also refer to a hydrocarbon-based polymer (such as polybutadiene).

[0111] Associative polymers can be nonionic, anionic, cationic or amphoteric.

[0112] Preferably, the associative polymer is selected from anionic associative polymers.

[0113] Among the anionic associative polymers that may be mentioned are the following: (a) those comprising at least one hydrophilic unit and at least one fatty chain allyl ether unit, more particularly those in which the hydrophilic unit is formed from an anionic ethylenically unsaturated monomer, more particularly those formed from a vinyl carboxylic acid, most particularly those formed from acrylic acid or methacrylic acid, or a mixture thereof.

[0114] Among these anionic associative polymers, those particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and / or methacrylic acid, 5% to 60% by weight of lower alkyl (meth)acrylates, 2% to 50% by weight of fatty-chain allyl ethers and 0 to 1% by weight of a crosslinker (a well-known copolymerizable unsaturated polyethylenic monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylene bisacrylamide).

[0115] Among the latter polymers, the most preferred are crosslinked terpolymers of methacrylic acid, ethyl acrylate and polyethylene glycol (10EO) stearyl alcohol ether (Steareth-10), in particular the aqueous 30% emulsion of crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10 allyl ether (40 / 50 / 10) sold by Ciba under the names Salcare SC 80® and Salcare SC 90®. -(b) i) comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type and ii) at least one hydrophobic unit such as a (C10-C30) alkyl ester of unsaturated carboxylic acid type.

[0116] The unsaturated carboxylic acids useful in the present invention (C 10 ~C 30 ) Alkyl esters include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, and dodecyl acrylate and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

[0117] Anionic polymers of this type are described and prepared, for example, by US Pat. No. 3,915,921 and US Pat. No. 4,509,949.

[0118] Among this type of anionic associative polymer, 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C 10 ~C 30 alkyl acrylate (hydrophobic unit) and 0 to 6% by mass of a cross-linkable polymerizable monomer, or the above-mentioned, 98% to 96% by mass of acrylic acid (hydrophilic unit), 1% to 4% by mass of C 10 ~C 30 More particularly, one consisting of alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of a cross-linking polymerizable monomer will be used.

[0119] Among the above-mentioned polymers, those most particularly preferred according to the invention are Pemulen TR1®, Pemulen TR2®, Carbopol 1382®, and even more preferentially the product sold by Goodrich under the trade name Pemulen TR1® and the product sold by SEPPIC under the name Coatex SX®.

[0120] Mention may also be made of the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer sold under the name Acrylidone LM by the company ISP. -(c) Maleic anhydride / C 30 ~C 38α-olefin / alkyl maleate terpolymers, such as those sold under the trade name Performa V 1608® by Newphase Technologies (maleic anhydride / C 30 ~C 38 α-olefin / isopropyl maleate copolymer). (d) acrylic terpolymers, including: i) approximately 20% by mass to 70% by mass of an α,β-monoethylenically unsaturated carboxylic acid [A]; ii) about 20% to 80% by weight of an α,β-monoethylenically unsaturated non-surfactant monomer other than [A]; iii) about 0.5% to 60% by weight of a nonionic monourethane that is the reaction product of a surfactant having one hydroxyl group and a monoethylenically unsaturated monoisocyanate; For example, the terpolymer described in EP-A-0 173 109, more specifically in Example 3, namely an aqueous 25% dispersion of terpolymer of methacrylic acid / methyl acrylate / behenyl alcohol dimethyl-meta-isopropenyl benzyl isocyanate ethoxylate (40EO). - (e) Copolymers comprising as monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkylenated fatty alcohol.

[0121] Preferentially, these compounds also contain, as monomers, esters of α,β-monoethylenically unsaturated carboxylic acids and C1-C4 alcohols.

[0122] Examples of this type of compound include Aculyn 22®, sold by Roehm & Haas, which is a terpolymer of methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate, and Aculyn 88, also sold by Roehm & Haas.

[0123] Advantageously, the associative polymer is chosen from acrylic associative polymers, more preferentially carboxylic acrylic associative polymers.

[0124] Particularly preferably, the associative polymer different from the non-carboxylic acid anionic thickener is chosen from copolymers which contain among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid with an oxyalkylenated fatty alcohol.

[0125] Advantageously, the total amount of associative polymer ranges from 0.1% to 30%, preferably from 0.1% to 20%, more preferentially from 0.2% to 10%, better still from 0.2% to 5% and even more particularly from 0.2% to 2% by weight relative to the total weight of composition B.

[0126] Advantageously, the total amount of associative polymer ranges from 0.05% to 15% by weight, preferably from 0.05% to 10% by weight, more preferentially from 0.1% to 5% by weight and even more preferentially from 0.1% to 1% by weight relative to the total weight of composition C.

[0127] Compounds containing at least one carboxylic acid group Composition B according to the invention, used in the context of the coloring method according to the invention, comprises at least one compound, different from the associative polymer, containing at least one carboxylic acid group.

[0128] Preferably, the compound different from the associative polymer containing at least one carboxylic acid group is selected from silicone compounds, polyurethanes, acrylic polymers and mixtures thereof, all of which contain at least one carboxylic acid group.

[0129] Polyurethane and acrylic polymers: According to a preferred embodiment, composition B comprises one or more compounds, different from the associative polymer, containing at least one carboxylic acid group chosen from polyurethanes, acrylic polymers and mixtures thereof.

[0130] Preferably, the compound different from the associative polymer containing at least one carboxylic acid group is in the form of an aqueous dispersion of particles of a polymer chosen from polyurethanes, acrylic polymers and mixtures thereof.

[0131] Preferably, composition B comprises one or more compounds, different from the associative polymer, containing at least one carboxylic acid group in the form of an aqueous dispersion of particles of polyurethanes, acrylic polymers and mixtures thereof.

[0132] Thus, in this embodiment, the polymer used in the aqueous dispersion of polymer particles is different from the associative polymer.

[0133] The dispersion may be a simple dispersion of the cosmetic composition in an aqueous medium. A specific example of a dispersion is a latex.

[0134] The aqueous dispersion of polymer particles may be selected from aqueous dispersions of polyurethane particles.

[0135] More particularly, the polyurethanes present in the aqueous dispersions used in the present invention are: -the following formula (A): [ka] (In the formula, -R1 represents a divalent radical of a dihydroxylated compound; -R2 represents an aliphatic or cycloaliphatic polyisocyanate radical, -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) with a prepolymer of; -the following formula (B): H2N-R4-NH2(B) wherein R4 represents an alkylene or alkylene oxide group that is not substituted with one or more ionic or potentially ionic groups. with at least one chain extender according to the formula: Formula (C) below: H2N-R5-NH2(C) wherein R5 represents an alkylene group substituted with one or more ionic or potentially ionic groups. and at least one chain extender according to It is obtained by the reaction:

[0136] Among the dihydroxylated compounds that can be used according to the present invention, particular mention can be made of compounds containing two hydroxyl groups and having a number average molecular weight of about 700 to about 16,000, preferably about 750 to about 5,000. Examples of high molecular weight dihydroxylated compounds include polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadiene, polyhydroxylated polythioethers, and mixtures thereof. Preferably, the hydroxylated compound is selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0137] 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.

[0138] 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.

[0139] Preferably, R2 represents an organic diisocyanate. Examples of organic diisocyanates may be selected in particular from: tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)methane, isomers of toluene diisocyanate (TDI), such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, diphenylmethane 4,4'-diisocyanate and mixtures thereof with its diphenylmethane 2,4-diisocyanate isomer, optionally with diphenylmethane 2,2'-diisocyanate isomer, naphthalene 1,5-diisocyanate and mixtures thereof.

[0140] 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.

[0141] 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, alicyclic or aromatic groups. Preferably, they contain only aliphatic groups.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] The prepolymer is chain extended by using chain extenders belonging to two groups: The first group of chain extenders corresponds to compounds of general formula (B):

[0146] The chain extender of formula (B) is preferably an alkylene diamine, such as hydrazine, ethylene diamine, propylene diamine, 1,4-butylene diamine, piperazine; an alkylene oxide diamine, 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), hexane diamine, isophorone diamine, 4,4-methylenedi(cyclohexylamine), Tomah and mixtures thereof.

[0147] The second group of chain extenders corresponds to compounds of general formula (C). Compounds of this type preferably have an ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Compounds of this type can optionally contain two groups that react with isocyanate groups and one group that is ionic or capable of forming an ionic group.

[0148] The ionic or potentially ionic groups may preferably be selected from tertiary or quaternary ammonium groups or groups that can be converted into such groups, carboxyl groups, carboxylate groups, sulfonic acid groups and sulfonate groups. The conversion of at least a portion of the groups that can be converted into salts of tertiary or quaternary ammonium groups can be carried out before or during mixing with water.

[0149] 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.

[0150] The polyurethanes that can be used according to the invention can also optionally contain compounds (chain terminators) located at the respective chain ends that terminate the chains, such compounds being described in particular in US Pat. No. 7,445,770 and / or US Pat. No. 7,452,770.

[0151] 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.

[0152] 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 means that the polyurethane content (solids) of the aqueous dispersion is preferably from 20% to 60% by weight, more preferentially from 25% to 55% by weight, and better still from 30% to 50% by weight, relative to the total weight of the dispersion.

[0153] Also preferably, the glass transition temperature (Tg) of the aqueous dispersion of polyurethane particles is lower than or equal to -25°C, preferably lower than -35°C and more preferentially lower than -40°C.

[0154] The average diameter of the polyurethane particles can be up to about 1000 nm, for example, from about 50 nm to about 800 nm, and better still, from about 100 nm to about 500 nm. These particle sizes can be measured using a laser particle size distribution analyzer (e.g., Brookhaven BI90).

[0155] Non-limiting examples of aqueous polyurethane dispersions include those sold by Bayer under the name Baycusan®, 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).

[0156] Mention may also be made of aqueous polyurethane dispersions of isophthalic acid / adipic acid copolymer / hexylene glycol / neopentyl glycol / dimethylol acid / isophorone diisocyanate (INCI name: Polyurethane-1, for example Luviset® PUR from BASF), polyurethanes of polycarbonate, polyurethanes of aliphatic polyesters and aliphatic polyurethanes (for example the Neorez® series from DSM, such as Neorez® R989, Neorez® and R-2202).

[0157] 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.

[0158] Preferably, the compound different from the associative polymer containing at least one carboxylic acid group is in the form of an aqueous dispersion of particles of an acrylic polymer, more preferentially in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0159] For the purposes of the present invention, the term "polymer" means a compound corresponding to the repetition of one or more units, which are derived from compounds known as monomers, where this or these units are repeated at least twice, preferably at least three times.

[0160] 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 a keratinous material, either alone or in the presence of an auxiliary film-forming agent.

[0161] 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.

[0162] 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.

[0163] The (meth)acrylic acid esters (also known as (meth)acrylates) are advantageously alkyl (meth)acrylates, in particular C1-C 30 , preferably C1 to C 20 , or better C1 to C 10 Alkyl (meth)acrylates, aryl (meth)acrylates, especially C6-C 10 It is selected from aryl (meth)acrylates and hydroxyalkyl (meth)acrylates, in particular C2 to C6 hydroxyalkyl (meth)acrylates.

[0164] 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.

[0165] Among the hydroxyalkyl(meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0166] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0167] Particularly preferred (meth)acrylic acid esters are alkyl, preferably C1-C 30 , and more preferentially C1~C 20 , and even better C1 to C 10 and even more particularly C1 to C4 alkyl (meth)acrylates.

[0168] 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.

[0169] 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.

[0170] The acrylic polymer according to the invention may be a homopolymer or a copolymer, advantageously a copolymer, better still a copolymer of (meth)acrylic acid and a (meth)acrylic acid ester.

[0171] Preferably, the acrylic polymer according to the present invention comprises the following monomers: a) (meth)acrylic acid; and b) C1~C 30 , and more preferentially C1~C 20 , or better C1 to C 10 More particularly, it contains one or more units derived from a C1 to C4 alkyl (meth)acrylate.

[0172] Preferably, the aqueous dispersion of acrylic polymer particles is surfactant-free.

[0173] The term "surfactant" refers to any agent that can modify the surface tension between two surfaces.

[0174] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and ethyl acrylate, such as the compound sold by BASF under the trade name Luvimer MAE, or the compound sold by Lubrizol under the trade name Fixate Superhold Polymer, such as polyacrylate-2 crosspolymer, or the compound sold by Daito Kasei Kogyo under the trade name Daitosol 3000VP3, or the compound sold by Daito Kasei Kogyo under the trade name Daitosol 3000 SLPN-PE1, such as acrylate copolymer.

[0175] The acrylic polymer may optionally contain one or more additional monomers other than (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide monomers.

[0176] Additional monomers may include, for example, styrene monomers, particularly styrene and alpha-methylstyrene, preferably styrene.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] Preferably, composition B comprises at least one aqueous dispersion of acrylic polymer particles.

[0181] More preferentially, composition B comprises the following monomers: a) (meth)acrylic acid; and b) C1~C 30 , and more preferentially C1~C 20 , or better C1 to C 10 More particularly, it comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more units derived from C1-C4 alkyl (meth)acrylate.

[0182] 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 better still between 25% and 50% by weight, based on the weight of the dispersion.

[0183] The total amount of compounds containing at least one carboxylic acid group and different from the associative polymer present in composition B preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 55% by weight, better still from 5% to 50% by weight and even more preferentially from 10% to 45% by weight, relative to the total weight of composition B.

[0184] The total amount of compounds different from the associative polymer and containing at least one carboxylic acid group preferably ranges from 0.1% to 35% by weight, more preferentially from 0.5% to 30% by weight, better still from 1% to 25% by weight and even more preferentially from 3% to 25% by weight, relative to the total weight of composition C.

[0185] The total amount of aqueous dispersion of polymer particles other than the aforementioned associative polymer, chosen from polyurethanes, acrylic polymers, and mixtures thereof, preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 55% by weight, even more preferably from 5% to 50% by weight, and even more preferentially from 10% to 45% by weight, relative to the total weight of composition B.

[0186] According to a particular embodiment, the total amount of aqueous dispersion of acrylic polymer particles different from the associative polymer described above preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 55% by weight, better still from 5% to 50% by weight and even more preferentially from 10% to 45% by weight, relative to the total weight of composition B.

[0187] The total amount of aqueous dispersion of polymer particles different from the aforementioned associative polymer, chosen from polyurethanes, acrylic polymers, and mixtures thereof, preferably ranges from 0.1% to 35% by weight, more preferentially from 0.5% to 30% by weight, even more preferentially from 1% to 25% by weight, and even more preferentially from 3% to 25% by weight, relative to the total weight of composition C.

[0188] According to a particular embodiment, the total amount of aqueous dispersion of acrylic polymer particles different from the associative polymer described above preferably ranges from 0.1% to 35% by weight, more preferentially from 0.5% to 30% by weight, better still from 1% to 25% by weight and even more preferentially from 3% to 25% by weight, relative to the total weight of composition C.

[0189] Compounds containing at least one hydroxyl functional group Composition B according to the invention, used in the context of the coloring method according to the invention, comprises at least one compound containing at least one hydroxyl function.

[0190] Advantageously, said compound containing at least one hydroxyl function is aromatic or non-aromatic.

[0191] Preferably, the compounds containing at least one hydroxyl function are chosen from those having a molecular weight of less than 500 g / mol, more preferentially less than 300 g / mol and even better still less than 250 g / mol.

[0192] Preferably, said composition B comprises at least two compounds containing at least one hydroxyl functional group.

[0193] According to a particular embodiment, when said composition B comprises at least two compounds containing at least one hydroxyl functional group, at least one is an aromatic compound and at least one is a non-aromatic compound.

[0194] According to a particular embodiment, said composition B comprises at least three compounds containing at least one hydroxyl function.

[0195] Preferably, composition B comprises at least one compound, preferably at least two compounds, containing at least one hydroxyl functional group selected from phenoxyethanol, 1,2-hexanediol, 4-hydroxyacetophenone, ethanol, chlorphenesin, pentylene glycol and mixtures thereof.

[0196] According to a particular embodiment, composition B comprises at least three compounds, preferably at least four compounds, containing at least one hydroxyl function selected from phenoxyethanol, 1,2-hexanediol, 4-hydroxyacetophenone, ethanol, chlorphenesin, pentylene glycol, and mixtures thereof.

[0197] According to a particularly preferred embodiment, said compound containing at least one hydroxyl function is selected from a mixture of phenoxyethanol, 1,2-hexanediol, 4-hydroxyacetophenone, ethanol, chlorphenesin and pentylene glycol.

[0198] According to another embodiment, composition B comprises at least 1,2-hexanediol, preferably in a content ranging from 0.1% to 2% by weight, more preferentially from 0.5% to 1.5% by weight, relative to the total weight of composition B.

[0199] Advantageously, the total content of compounds containing at least one hydroxyl function is at least 2% by weight, preferably at least 3% by weight, more preferentially between 3% and 30% by weight, even more preferentially between 4% and 20% by weight, and even more preferentially between 5% and 15% by weight, relative to the total weight of composition B.

[0200] coloring agent Composition A and / or composition B according to the invention, used in the context of the coloring method according to the invention, comprises at least one colorant chosen from pigments, direct dyes, and mixtures thereof.

[0201] Preferably, composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof.

[0202] Advantageously, composition A and / or composition B according to the invention, used in the context of the coloring method according to the invention, comprise one or more pigments.

[0203] Preferably, composition B according to the invention comprises one or more pigments.

[0204] The term "pigment" refers to any pigment that colors keratinous materials and has a solubility in water at 25°C and atmospheric pressure (760 mmHg) of less than 0.05% by weight, preferably less than 0.01%.

[0205] Pigments that may be used are chosen in particular from organic and / or mineral pigments known in the art and in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.

[0206] These may be natural products of natural origin or non-natural products.

[0207] These pigments may be in the form of pigment powders or pastes. They may be coated or uncoated.

[0208] 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.

[0209] 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 encyclopaedia. 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.

[0210] 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.

[0211] The organic pigments may be chosen in particular from nitroso, nitro, azo, xanthene, pyrene, quinoline, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal complexes, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

[0212] 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.

[0213] Examples of pigment pastes with organic pigments include those sold by Hoechst under the following names: - Cosmenyl Yellow 10G: Pigment Yellow 3 (CI 11710); - Cosmenyl Yellow G: Pigment Yellow 1 (CI 11680); - Cosmenyl Orange GR: Pigment Orange 43 (CI 71105); - Cosmenyl Red R: Pigment Red 4 (CI 12085); - Cosmenyl Carmine FB: Pigment Red 5 (CI 12490); - Cosmenyl Violet RL: Pigment Violet 23 (CI 51319); - Cosmenyl Blue A2R; Pigment Blue 15.1 (CI 74160); - Cosmenyl Green GG: Pigment Green 7 (CI 74260); - Cosmenyl Black R: Pigment Black 7 (CI 77266).

[0214] The pigments according to the invention may 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 portion of the core.

[0215] 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 when used.

[0216] The mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.

[0217] Among the dyes, mention may be made of carminic acid, also known by 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 5 (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

[0218] An example of a lake is the product known by the following name: D&C Red 7 (CI 15 850:1).

[0219] Pigments can also be special effect pigments. The term "special effect pigments" refers to pigments that generally produce a colored appearance (characterized by a particular hue, a particular saturation, and a particular level of brightness) that is non-uniform and changes depending on the conditions of observation (light, temperature, angle of observation, etc.), thereby differing from colored pigments that exhibit standard uniform opaque, translucent, or transparent shades.

[0220] 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.

[0221] 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. As pearlescent pigments, mention may be made of 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.

[0222] Gold pearlescent agents, in particular those sold by BASF under the names Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); bronze pearlescent agents, in particular those sold by Merck under the names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super bronze (Cloisonne); orange pearlescent agents, in particular those sold by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion orange (Colorona) and Matte orange (17449) (Microna); brown pearlescent agents, in particular those sold by BASF under the names Nu-antique Copper copper-tinted pearlescent agents, in particular those sold by BASF under the name Copper 340A (Timica); red-tinted pearlescent agents, in particular those sold by Merck under the name Sienna fine (17386) (Colorona); yellow-tinted pearlescent agents, in particular those sold by BASF under the name Yellow (4502) (Chromalite); gold-tinted red pearlescent agents, in particular those sold by BASF under the name Sunstone G012 (Gemtone); pink-tinted pearlescent agents, in particular those sold by BASF under the name Tan opale G005 (Gemtone); gold-tinted black pearlescent agents, in particular those sold by BASF under the name Nu antique bronze 240 blue pearlescent agents, in particular those sold under the name AB (Timica); blue pearlescent agents, in particular those sold under the name Matte blue (17433) (Microna) by Merck; silvery white pearlescent agents, in particular those sold under the name Xirona Silver by Merck;Mention may also be made of gold-green to pink to orange-shifting pearlescent agents, in particular those sold under the name Indian summer (Xirona) by Merck; and mixtures thereof.

[0223] Further examples of pearlescent agents may include particles comprising a borosilicate substrate coated with titanium oxide.

[0224] Particles comprising a glass substrate coated with titanium oxide are sold in particular under the name Metashine MC1080RY by the company Toyal.

[0225] Finally, examples of pearlescent agents that may be mentioned include polyethylene terephthalate glitter flakes, in particular those sold under the name Silver 1P 0.004X0.004 (silver glitter flakes) by Meadowbrook Inventions, Inc. Multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate, and aluminum may also be envisaged.

[0226] 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 the physical and chemical properties and surface condition, are able to reflect incident light, and this reflection can, if appropriate, be strong enough to produce, when applied to the support to be made up, a bright spot visible to the naked eye on the surface of the composition or mixture, i.e. a brighter spot that appears to be noticeably brighter than its surroundings.

[0227] The reflective particles can be selected so as not to significantly alter the color effect of the colorant with which they are combined, more particularly to optimize this effect in terms of color rendering, which can more particularly have yellow, pink, red, bronze, orange, brown, gold and / or copper colors or shades.

[0228] These particles may have various morphologies, in particular in the form of platelets or spheres, in particular in the form of spheres.

[0229] Regardless of their morphology, the reflective particles may or may not have a multi-layer structure, and if multi-layered, may have at least one layer of a particularly reflective material, for example of uniform thickness.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] The reflective material may include a metal or a layer of metallic material.

[0234] Reflective particles are described in particular in documents JP 09-188830, JP 10-158450, JP 10-158541, JP 07-258460 and JP 05-017710.

[0235] As a further example of reflective particles comprising a mineral substrate coated with a metal layer, mention may also be made of particles comprising a borosilicate substrate coated with silver.

[0236] Silver-coated glass-based particles in platelet form are sold by Toyal under the name Microglass Metashine REFSX 2025 PS. Nickel / chromium / molybdenum alloy-coated glass-based particles are sold by the same company under the names Crystal Star GF 550 and GF 2525.

[0237] 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, wherein the substrate is 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.

[0238] Mention may be made, by way of example, of the aluminum, bronze or copper powders coated with SiO2 sold under the name Visionaire by the company Eckart.

[0239] Mention may also be made of pigments that are not bound to a substrate and exhibit interference effects, such as liquid crystals (Helicones HC from Wacker) or holographic luminescent flakes (Geometric Pigments or Spectra f / x from Spectratek). Special effect pigments also include fluorescent pigments (which are either substances that fluoresce in daylight or produce ultraviolet fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, such as those sold by Quantum Dots Corporation.

[0240] The variety of pigments that can be used in the present invention makes it possible to obtain a wide range of colors and also to obtain specific optical effects such as metallic or interference effects.

[0241] 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.

[0242] The pigment can be dispersed in the composition with a dispersant.

[0243] Dispersants serve to prevent the aggregation or flocculation of dispersed particles. They can be surfactants, oligomers, polymers, or mixtures of several of these, each containing one or more functional groups with a strong affinity for the surface of the particles to be dispersed. In particular, they can be physically or chemically 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, 12-hydroxystearic acid esters and esters of C8-C20 fatty acids and polyols such as glycerol or diglycerol are used, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g / mol, for example, the product sold by Avecia under the name Solsperse 21000, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold by Henkel under the trade name Dehymyls PGPH, or other polyhydroxystearates, such as the product sold by Uniqema under the trade name Arlacel P100, and mixtures thereof.

[0244] Other dispersants that may be used in the compositions of the present 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 trade designations DC2-5185 and DC2-5225 C.

[0245] The pigments that can be used in the composition can be surface-treated with an organic agent.

[0246] Thus, pre-surface-treated pigments useful in the context of the present invention are pigments which have been subjected, in whole or in part, to a surface treatment of a chemical, electronic, electrochemical, mechanochemical or mechanical nature using organic agents, such as those described in Cosmetics and Toiletries, February 1990, Vol. 105, pp. 53-64, and which, after such treatment, are dispersed in the compositions of the present invention. These organic agents may 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 acid polymers, such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, such as silicones, in particular polydimethylsiloxane; organic fluorine compounds, such as perfluoroalkyl ethers; fluorosilicone compounds.

[0247] 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.

[0248] 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.

[0249] Preferably, the surface-treated pigment is coated with an organic layer.

[0250] The organic agent with which the pigment is treated may be deposited on the pigment by evaporating the solvent, by chemical reaction between molecules of the surface treatment agent, or by forming a covalent bond between the surface treatment agent and the pigment.

[0251] 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.

[0252] Preferably, an organic agent that is covalently bonded to the pigment will be used.

[0253] The surface treatment agent may represent 0.1% to 50% by weight, preferably 0.5% to 30% by weight, and even more preferentially 1% to 20% by weight of the total weight of the pigment to be surface treated.

[0254] Preferably, the surface treatment of the pigment is selected from the following treatments: PEG-silicone treatments, such as the AQ surface treatment sold by LCW; - methicone treatments, such as the SI surface treatment sold by LCW; dimethicone treatments, such as Covasil 3.05 surface treatment sold by LCW; - dimethicone / trimethylsiloxysilicate treatments, such as Covasil 4.05 surface treatment sold by LCW; magnesium myristate treatments, such as the MM surface treatment sold by LCW; aluminum dimyristate treatment agents, such as the MI surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - perfluoropolymethyl isopropyl ether treatments, such as the FHC surface treatment sold by LCW; isostearyl sebacate treatment agents, such as the HS surface treatment agent sold by Miyoshi Kasei Co., Ltd.; perfluoroalkylphosphate treatment agents, such as the PF surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - acrylate / dimethicone copolymer and perfluoroalkylphosphate treatment agent, such as the FSA surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - polymethylhydrogenosiloxane / perfluoroalkylphosphate treatment agents, such as the FSO1 surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - acrylate / dimethicone copolymer treatment agents, such as the ASC surface treatment agent sold by Daito Chemical Industry Co., Ltd.; isopropyl titanium triisostearate treatment agents, such as the ITT surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - acrylate copolymer treatment agents, such as the APD surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - Perfluoroalkylphosphate / isopropyl titanium triisostearate treatment agents, such as the PF+ITT surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.

[0255] 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.

[0256] The terms "submicron" or "submicron-rich" 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.

[0257] According to one embodiment, the dispersant and the pigment are present in an amount (dispersant:pigment) of 1:4 to 4:1, in particular 1.5:3.5 to 3.5:1, or even better 1.75:3 to 3:1, by weight ratio.

[0258] Thus, the dispersant may have a silicone backbone, such as a silicone polyether, and may be an aminosilicone type dispersant. Suitable dispersants include: aminosilicones, i.e. silicones containing one or more amino groups, such as those sold under the name BYK LPX 21879 by BYK, and those sold under the names GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1 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.

[0259] According to one particular embodiment, the dispersant is of the aminosilicone type and is cationic.

[0260] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments, or organic pigments.

[0261] 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.

[0262] direct dye Composition A and / or composition B used in the context of the method according to the invention may comprise one or more direct dyes. In particular, composition B may comprise one or more direct dyes.

[0263] The term "direct dyes" means natural and / or synthetic dyes other than oxidative dyes. These are dyes that will diffuse superficially onto the fiber.

[0264] These can be ionic or non-ionic, preferably cationic or non-ionic.

[0265] Examples of suitable direct dyes include azo direct dyes, either alone or in mixtures; (poly)methine dyes, such as cyanine, hemicyanine, and styryl; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes; and natural direct dyes.

[0266] The direct dyes are preferably cationic direct dyes, such as hydrazonocationic dyes of the following formulae (XIII) and (XIV) and (XV) and (XVI): Het + -N(Ra)-N=C(Rb)-Ar,Q- (XIII), Het + -C(Ra)=NN(Rb)-Ar,Q (XIV), Het + -N=N-Ar,Q- (XV), Ar + -N=N-Ar'',Q- (XVI) (In formulas (XIII) to (XVI), -Het+ represents a cationic heteroaryl group, such as imidazolium, indolium or pyridinium, preferentially having a cationic charge in the ring and preferentially optionally substituted with at least one (C1-C8) alkyl group, such as methyl; -Ar+ represents an aryl group such as phenyl or naphthyl bearing an exocyclic cationic charge, preferentially ammonium, in particular tri(C1-C8)alkylammonium such as trimethylammonium; -Ar preferentially represents one or more electron-donating groups, such as i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8)(alkyl)amino, in which the alkyl group is optionally substituted with a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) an aryl group, in particular phenyl, optionally substituted with an optionally substituted N—(C1-C8) alkyl-N-aryl(C1-C8) alkylamino, or alternatively, Ar represents a julolidine group; -Ar" represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, preferentially optionally substituted with one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups; - Ra and Rb may be identical or different and represent a hydrogen atom or a (C1-C8) alkyl group optionally substituted (preferentially by a hydroxyl group); Or else, Het + the substituents Ra together with the substituents of and / or Rb together with the substituents of Ar 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. Examples of the azocationic dyes include the following.

[0267] Mention may be made in particular of the azo and hydrazono direct dyes with an endocyclic cationic charge of the formulae (XIII) to (XVI) defined above, more particularly the cationic direct dyes with an endocyclic cationic charge described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954, preferentially the following direct dyes: [ka] (In formulas (XVII) and (XVIII), -R 1 represents a (C1-C4) alkyl group such as methyl; -R 2 and R 3 may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl; -R 4represents a hydrogen atom or an electron donating group, such as an optionally substituted (C1-C8) alkyl, an optionally substituted (C1-C8) alkoxy or a (di)(C1-C8)(alkyl)amino, wherein the alkyl group is optionally substituted with a hydroxyl group; in particular, R 4 is a hydrogen atom; -Z represents a CH group or a nitrogen atom, preferentially CH, -Q- is an anionic counterion as defined above, especially a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl).

[0268] 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.

[0269] The direct dye can be selected from anionic direct dyes. The anionic direct dye of the present invention is a dye generally referred to as an "acid" direct dye, due to its affinity for alkaline substances. The term "anionic direct dye" refers to a direct dye containing at least one COR or SOR substituent in its structure, where R represents a hydrogen atom or a cation or ammonium ion derived from a metal or amine. The anionic dye can be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethanoic acid dyes, indoamine acid dyes, anthraquinonic acid dyes, indigoid dyes, and natural acid dyes.

[0270] Acid dyes useful in the present invention include dyes of the following formulae (XIX), (XIX'), (XX), (XX'), (XXI), (XXI'), (XXII), (XXII'), (XXIII), (XXIV), (XXV) and (XXVI): a) diaryl anionic azo dyes of formula (XIX) or (XIX'): [ka] (In formulas (XIX) and (XIX'), -R7, R8, R9, R 10 , R'7, R'8, R'9 and R' 10 may be the same or different and are hydrogen atoms or the following: - alkyl; -alkoxy, alkylthio; -hydroxyl, mercapto; - nitro, nitroso; -R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be the same or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); -(O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); -(O)CO - -,M + (In the formula, M + is as defined above); -R"-S(O)2- (wherein R" represents a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group); -R'''-S(O)2-X'- (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: - optionally substituted heteroaryl; preferentially a benzothiazolyl group; -cycloalkyl; in particular cyclohexyl; -Ar-N=N- (where Ar is an optionally substituted aryl group; preferentially one or more alkyl, (O)S(O - )-,M + or phenyl optionally substituted by a phenylamino group; or - two adjacent groups R7 and R8 or R8 and R9 or R9 and R 10 together form a fused benzo group A'; R'7 and R'8 or R'8 and R'9 or R'9 and R' 10 together form a fused benzo group B'; A' and B' are i) nitro; ii) nitroso; iii) (O)S(O - )-,M + iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N-; and xi) optionally substituted aryl(alkyl)amino; + , R°, X, X′, X″ and Ar are as defined above; -W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent radical: i) -NR-, 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 Ra and Rb together with the carbon atom carrying them form a spirocycloalkyl; preferentially, W represents a sulfur atom, or Ra and Rb together form a cyclohexyl; Formulas (XIX) and (XIX') contain at least one sulfonate group (O)S(O) on one of the rings A, A', B, B' or C. - )-,M + or one carboxylate group (O)CO - -,M + ; it is understood that it preferentially comprises sodium sulfonate).

[0271] Examples of dyes of formula (XIX) are Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3, or Sunset Yellow; Examples of the dye of formula (XIX') include Acid Red 111, Acid Red 134, and Acid Yellow 38. b) Formulas (XX) and (XX'): [ka] (In formulas (XX) and (XX'), -R 11 , R 12 and R 13 may be the same or different and are hydrogen or a halogen atom, an alkyl group, or -(O)S(O - ), M + (In the formula, M +is as defined above); -R 14 represents a hydrogen atom, an alkyl group, or -C(O)O - ,M + group (in the formula, M + is as defined above); -R 15 represents a hydrogen atom; -R 16 represents an oxo group, in which case R' 16 does not exist, or instead, R 15 is R 16 together to form a double bond; -R 17 and R 18 may be the same or different and represent a hydrogen atom or one of the following: -(O)2S(O - )-,M + (In the formula, M + is as defined above); -Ar-OS(O)2-, where Ar represents an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups. represents a group selected from: -R 19 and R 20 together form either a double bond or an optionally substituted benzo group D'; -R' 16 , R' 19 and R' 20 may be the same or different and represent a hydrogen atom or an alkyl group or a hydroxyl group; -R 21 represents a hydrogen atom, an alkyl group, or an alkoxy group; - Ra and Rb may be identical or different and are as defined above, and preferentially Ra represents a hydrogen atom and Rb represents an aryl group; -Y represents either a hydroxyl group or an oxo group; - [ka] represents a single bond when Y is an oxo group; represents a double bond when Y is a hydroxyl group; Formulas (XX) and (XX') contain at least one sulfonate group (O)S(O) on one of the rings D or E. - )-,M + or one carboxylate group -C(O)O - ,M + ; which are understood to comprise preferentially sodium sulfonates).

[0272] Examples of dyes of formula (XX) include Acid Red 195, Acid Yellow 23, Acid Yellow 27, and Acid Yellow 76; examples of dyes of formula (XX') include Acid Yellow 17; c) Anthraquinone dyes of formula (XXI) and (XXI'): [ka] (In formulas (XXI) and (XXI'): -R 22 , R 23 , R 24 , R 25 , R 26 and R 27 may be the same or different and represent a hydrogen or halogen atom, or one of the following: - alkyl; -hydroxyl, mercapto; -alkoxy, alkylthio; -Alkyl and (O)S(O - ),M + optionally substituted aryloxy or arylthio, which are preferentially substituted by one or more groups selected from + is as defined above); -Alkyl and (O)2S(O-)-, M + (In the formula, M + is as defined above); -(di)(alkyl)amino; -(di)(hydroxyalkyl)amino; -(O)2S(O - )-,M + (In the formula, M + is as defined above) represents a group selected from: -Z' is a hydrogen atom or a group NR 28 R 29 (wherein R 28 and R 29 may be the same or different and are hydrogen atoms or the following: - alkyl; -Polyhydroxyalkyl, such as hydroxyethyl; one or more groups, in particular i) alkyl, such as methyl, n-dodecyl, n-butyl, etc.; ii) (O)S(O - )-, M + (In the formula, M + is as defined above; iii) aryl optionally substituted with R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above and preferentially R° represents an alkyl group); -cycloalkyl, in particular cyclohexyl; 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 + ; it is understood that it preferentially comprises sodium sulfonate).

[0273] Examples of dyes of formula (XXI) include Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2; and an example of a dye of formula (XXI') is Acid Black 48. d) Nitro dyes of formula (XXII) and (XXII'): [ka] (wherein in formula (XII) and (XII'): -R 30 , R 31 and R 32 may be the same or different and represent a hydrogen or halogen atom, or one of the following: - alkyl; -alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups; -hydroxyl, mercapto; - nitro, nitroso; -polyhaloalkyl; -R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X', and X'' are as defined above); -(O)2S(O - )-,M + (In the formula, M + is as defined above); -(O)CO - -,M + (In the formula, M + is as defined above); -(di)(alkyl)amino; -(di)(hydroxyalkyl)amino; - represents a group selected from heterocycloalkyl, such as piperidino, piperazino or morpholino; in particular R 30 , R 31 and R 32 represents a hydrogen atom; Rc and Rd may be the same or different and represent a hydrogen atom or an alkyl group; -W is as defined above; W especially represents 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] is a group consisting of one or more R 30 represents a benzo group optionally substituted with a group; Formulas (XXII) and (XXII') contain at least one sulfonate group (O)S(O - )-,M + or one carboxylate group -C(O)O - ,M + ; it is understood that it preferentially comprises sodium sulfonate).

[0274] Examples of dyes of formula (XXII) include Acid Brown 13 and Acid Orange 3; examples of dyes of formula (XXII') include Acid Yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4'-N,N-2''-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7; e) Triarylmethane dyes of formula (XXIII): [ka] (In formula (XXIII), -R 33 , R 34 , R 35 and R 36 may be identical or different and represent a hydrogen atom or a group selected from alkyl, optionally substituted aryl and optionally substituted arylalkyl; in particular alkyl groups and optionally (O) m S(O - )-, M + group (in the formula, M + and m represents a benzyl group substituted with (as defined above); -R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 may be the same or different and are hydrogen atoms or the following: - alkyl; -alkoxy, alkylthio; -(di)(alkyl)amino; -hydroxyl, mercapto; - nitro, nitroso; -R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be the same or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); -(O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); -(O)CO - -,M + (In the formula, M + is as defined above); or - two adjacent groups R 41 and R 42 or R 42 and R 43 or R 43 and R 44 together form a fused benzo group: I'; I' is i) nitro; ii) nitroso; iii) (O)S(O - )-,M + iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; and ix) R°-X'-C(X)-X''-, where M + , R°, X, X′, and X″ are as defined above); 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- ; understood to preferentially include sulfonates).

[0275] Examples of dyes of formula (XXIII) include Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid Green 3, Acid Green 5 and Acid Green 50. f) Xanthene dyes of formula (XXIV): [ka] (In formula (XXIV): -R 45 , R 46 , R 47 and R 48 may be the same or different and represent a hydrogen or halogen atom; -R 49 , R 50 , R 51 and R 52 may be the same or different and represent a hydrogen or halogen atom, or one of the following: - alkyl; -alkoxy, alkylthio; -hydroxyl, mercapto; - nitro, nitroso; -(O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); -(O)CO - -,M + (In the formula, M + is as defined above); represents a group selected from In particular, R 49 , R 50 , R 51 and R 52 represents a hydrogen or halogen atom; -G represents an oxygen or sulfur atom or an NRe group, where Re is as defined above; in particular, G represents an oxygen atom; -L is alkoxide O - , M + ; Thioalkoxide S - , M + or an NRf group (wherein Rf represents a hydrogen atom or an alkyl group, and M + is as defined above; M + is in particular sodium or potassium); -L' is an oxygen or sulfur atom or an ammonium group: N + RfRg (wherein Rf and Rg may be the same or different and represent a hydrogen atom or an optionally substituted alkyl or aryl group). L' represents, in particular, an oxygen atom or one or more alkyl or (O) m S(O - )-, M + Groups (wherein m and M + represents a phenylamino group optionally substituted with (as defined above); Q and Q', which may be the same or different, represent an oxygen or sulfur atom; in particular, Q and Q' represent an oxygen atom; -M + is as defined above).

[0276] Examples of dyes of formula (XXIV) include Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; and Acid Violet 9. g) Indole dyes of formula (XXV): [ka] (In formula (XXV): -R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 may be the same or different and are a hydrogen atom or one of the following: - alkyl; -alkoxy, alkylthio; -hydroxyl, mercapto; - nitro, nitroso; -R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be the same or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); -(O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); -(O)CO - -,M + (In the formula, M + is as defined above); represents a group selected from -G represents an oxygen or sulfur atom or an NRe group, where Re is as defined above; in particular, G represents an oxygen atom; - Ri and Rh may be the same or different and represent a hydrogen atom or an alkyl group; Formula (XXV) contains at least one sulfonate group (O)S(O - )-, M + or one carboxylate group -C(O)O - , M + ; it is understood that it preferentially comprises sodium sulfonate).

[0277] Examples of dyes of formula (XXV) include: Acid Blue 74; 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 64may 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 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 It is understood that formula (XXVI) contains at least one sulfonate group (O)2S(O-)-,M+, preferentially sodium sulfonate).

[0278] Examples of dyes of formula (XXVI) include Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0279] 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, orcein. Extracts or decoctions containing these natural dyes can also be used, in particular henna-based poultices or extracts.

[0280] Preferably, the direct dye is selected from anionic direct dyes.

[0281] The colorants may be present in a total content ranging from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, relative to the total weight of composition A and / or composition B, and preferably the colorants are chosen from pigments.

[0282] The pigments may be present in a total amount of 0.05% to 20% by weight, preferably 0.1% to 15% by weight, better still 5% to 15% by weight, relative to the total weight of composition A and / or composition B.

[0283] The direct dyes may be present in a total content ranging from 0.001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of composition A and / or composition B.

[0284] 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.

[0285] 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 better still from 0.5% to 10% by weight relative to the total weight of composition C.

[0286] The direct dyes may be present in a total content ranging from 0.001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of composition C.

[0287] silicone One and / or the other of compositions A and B may also contain at least one silicone.

[0288] Silicones are distinct from compounds that contain at least one carboxylic acid group.

[0289] Preferably, one and / or the other of compositions A and B comprises at least one silicone selected from non-aminosilicones, aminosilicones and mixtures thereof.

[0290] Silicone is a material that is resistant to atmospheric pressure (1.013 x 10 5 It may be solid or liquid and may be volatile or non-volatile.

[0291] The silicones that can be used may be soluble or insoluble in the compositions according to the invention and they may be in the form of oils, waxes, resins or gums, with silicone oils being preferred.

[0292] Silicones are particularly well-described in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press.

[0293] Preferably, one and / or the other of compositions A and B is at atmospheric pressure (1.013×10 5 The silicone composition contains one or more silicones that are liquid at temperatures below 100°C (Pa).

[0294] Volatile silicones can be selected from those having a boiling point between 60°C and 260°C (at atmospheric pressure), more particularly from: i) cyclic polydialkylsiloxanes containing 3 to 7, preferably 4 to 5, silicon atoms, such as: - Octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

[0295] refers to products sold by Union Carbide under the name Volatile Silicone 7207 or by Rhodia under the name Silbione 70045 V 2, and by Union Carbide under the name Volatile Silicone 7158 or by Rhodia under the name Silbione 70045 V 5; - cyclic copolymers of the dimethylsiloxane / methylalkylsiloxane type having the following chemical structure: [ka] Preferably, cyclomethylsiloxane.

[0296] Mention Volatile Silicone FZ 3109 sold by Union Carbide; - mixtures of cyclic silicones with silicon-based organic compounds, such as octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50 / 50) and octamethylcyclotetrasiloxane and 1,1'-oxy(2,2,2',2',3,3'-hexatrimethylsilyloxy)bisneopentane; ii) Generally, the viscosity at 25°C is 5 x 10 -6 m 2 / s or less, such as decamethyltetrasiloxane, containing 2 to 9 silicon atoms.

[0297] Other silicones belonging to this category are described in the article published in Cosmetics and Toiletries, Vol. 91, January 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics, and mention may be made of the product sold under the name SH 200 by Toray Silicone.

[0298] Among the non-volatile silicones, mention may be made of polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, either alone or in mixtures, as well as organopolysiloxanes (or organomodified polysiloxanes or alternatively organomodified silicones) that contain one or more organic functional groups, preferably selected from aryl groups, amine groups, alkoxy groups, and polyoxyethylene or polyoxypropylene groups, in their structure, generally bonded via hydrocarbon-based groups. Preferably, the non-volatile silicones are selected from optionally oxyethylenated and oxypropylenated polydimethyl / methylsiloxanes.

[0299] The organomodified silicone may be a polydiarylsiloxane, in particular a polydiphenylsiloxane and a polyalkylarylsiloxane modified with the organofunctional groups mentioned above, the latter being chosen in particular from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes.

[0300] Among the organically modified silicones, mention may be made of organopolysiloxanes, including: -Optionally C6~C 24 polyoxyethylene and / or polyoxypropylene groups containing alkyl groups; for example, dimethicone copolyols, in particular those sold under the name DC 1248 by Dow Corning or the oils Silwet® L722, L7500, L77 and L711 by Union Carbide; or (C12) alkylmethicone copolyols, in particular those sold under the name Q2-5200 by Dow Corning; substituted or unsubstituted amine groups, in particular C1-C4 aminoalkyl groups; examples include the products sold by Genesee under the names GP4 Silicone Fluid and GP7100 or by Dow Corning under the names Q2-8220, DC929 or DC939; thiol groups; for example, the products sold by Genesee under the names GP72A and GP71; alkoxylated groups, such as the product sold under the name Silicone Copolymer F-755 by SWS Silicones and the products sold under the name Abil Wax® 2428, 2434 and 2440 by Goldschmidt; - hydroxylated groups; for example, polyorganosiloxanes with hydroxyalkyl groups; acyloxyalkyl groups; for example, polyorganosiloxanes as described in US Pat. No. 4,957,732; anionic groups of the carboxylic acid type, such as those described in EP 186507 or anionic groups of the alkylcarboxylic acid type, such as the product X-22-3701E from Shin-Etsu Chemical Co., Ltd., or anionic groups of the 2-hydroxyalkylsulfonate or 2-hydroxyalkylthiosulfate type, such as the products sold under the names Abil® S201 and Abil® S255 by Goldschmidt; -hydroxyacylamino groups; for example, polyorganosiloxanes as described in EP-A-342834; for example, the product Q2-8413 from Dow Corning.

[0301] The silicone may also be chosen from polydialkylsiloxanes, among which mention is made mainly of polydimethylsiloxanes with trimethylsilyl end groups. Among these polydialkylsiloxanes, mention may be made of the following commercially available products: Silbione® or Mirasil® oils of the 47 and 70047 series sold by Rhodia, such as 70047 V 500000 oil; Mirasil® series oils sold by Rhodia; - Dow Corning 200 series oils, e.g., with a viscosity of 60,000 mm 2 DC200, viscosity in / s; - Viscasil® oils from General Electric and certain oils of the SF series from General Electric (SF 96, SF 18).

[0302] Mention may also be made of polydimethylsiloxanes with dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the 48 series oils from the company Rhodia.

[0303] Polydialkylsiloxanes in this category also include products sold by Goldschmidt under the names Abil Wax® 9800 and 9801, which are poly(C1-C20) dialkylsiloxanes.

[0304] More specific products that can be used in accordance with the present invention are mixtures such as: mixtures derived from polydimethylsiloxanes with hydroxyl chain ends, i.e. dimethiconol (CTFA), and from cyclic polydimethylsiloxanes, also known as cyclomethicone (CTFA), such as the product Q2-1401 sold by Dow Corning; mixtures made from polydimethylsiloxanes with hydroxyl groups at the chain ends, i.e. dimethiconol (CTFA) and from polydimethylsiloxanes also known as dimethicone (CTFA), such as Xiameter® PMX-1503 Fluid, a product sold by Dow Corning.

[0305] The polyalkylarylsiloxane is particularly preferred because it has a viscosity of 1×10 at 25°C. -5 ~5×10 -2 m 2 The siloxanes are selected from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes in the range of 1 / s.

[0306] Among these polyalkylarylsiloxanes, mention may be made of products sold under the following names: - Silbione® oils of the 70641 series from Rhodia; - Rhodorsil® 70633 and 763 series oils from Rhodia; -Dow Corning Oil Dow Corning 556 Cosmetic Grade Fluid; - PK series silicones from Bayer, for example product PK20; - PN and PH series silicones from Bayer, such as products PN1000 and PH1000; - Certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

[0307] Preferably, one and / or the other of compositions A and B comprises at least one aminosilicone. The term "aminosilicone" refers to any silicone containing at least one primary, secondary or tertiary amine or quaternary ammonium group.

[0308] The weight average molecular weight of these aminosilicones can be measured by gel permeation chromatography (GPC) at room temperature (25°C) in terms of polystyrene. A μ-styragel column is used. The eluent is THF, and the flow rate is 1 ml / min. 200 μl of a solution containing 0.5% by weight of silicone in THF is injected. Detection is performed by refractive index measurement and UV measurement.

[0309] Preferably, the aminosilicones that can be used in connection with the present invention are selected from: a) Formula (A): [ka] (wherein x' and y' are integers that result in a mass average molecular weight (Mw) of approximately 5,000 to 500,000) Polysiloxanes corresponding to: b) Aminosilicones corresponding to formula (B): R'aG3-a-Si(OSiG2)n-(OSiGbR'2-b)mO-SiG3-a-R'a (B) (In the formula, -G may be identical or different and represent a hydrogen atom or a group from phenyl, OH, C1-C8 alkyl, such as methyl, or C1-C8 alkoxy, such as methoxy, -a may be identical or different and represents 0 or an integer from 1 to 3, in particular 0, -b represents 0 or 1, in particular 1, - m and n are numbers whose sum (n + m) is in the range of 1 to 2000, in particular 50 to 150, where n can represent a number from 0 to 1999, in particular 49 to 149, and m can represent a number from 1 to 2000, in particular 1 to 10; -R' may be the same or different and have the formula -CqH2qL, where q is a number ranging from 2 to 8, and L is one of the following groups: -N(R'')2; -N(R'')3A-; -NR''-QN(R'')2; and -NR''-Q-N(R'')3A-, where R'' may be the same or different and is hydrogen, phenyl, benzyl, or a monovalent saturated hydrocarbon-based group, such as C1-C 20 represents an alkyl group; Q represents a group of formula C r H 2r (r is an integer ranging from 2 to 6, preferably from 2 to 4), represents a linear or branched group; A- is an optionally quaternized amine group selected from cosmetically acceptable anions, in particular halide anions, such as fluoride, chloride, bromide or iodide).

[0310] Preferably, the aminosilicone is selected from aminosilicones of formula (B): Preferably, the aminosilicones of formula (B) are selected from aminosilicones corresponding to the following formulae (C), (D), (E), (F) and / or (G):

[0311] According to a first embodiment, the aminosilicone corresponding to formula (B) is of formula (C): [ka] wherein m and n are numbers such that the sum (n+m) ranges from 1 to 2000, in particular from 50 to 150; n optionally represents a number from 0 to 1999, in particular from 49 to 149; and m optionally represents a number from 1 to 2000, in particular from 1 to 10.

[0312] According to a second embodiment, the aminosilicone corresponding to formula (B) has the following formula (D): [ka] (In the formula, - m and n are numbers whose sum (n + m) is in the range of 1 to 1000, in particular in the range of 50 to 250, more particularly in the range of 100 to 200; n can represent a number from 0 to 999, in particular from 49 to 249, more particularly from 125 to 175, and m can represent a number from 1 to 1000, in particular from 1 to 10, more particularly from 1 to 5; R1, R2 and R3 may be identical or different and represent a hydroxyl or a C1-C4 alkoxy group, and at least one of the R1-R3 groups represents an alkoxy group. The silicones are selected from the group consisting of:

[0313] Preferably, the alkoxy group is a methoxy group.

[0314] The hydroxy / alkoxy molar ratio is preferably in the range of 0.2:1 to 0.4:1, preferably 0.25:1 to 0.35:1, more particularly 0.3:1.

[0315] The mass average molecular weight (Mw) of these silicones is preferably in the range of 2,000 to 1,000,000, more particularly in the range of 3,500 to 200,000.

[0316] According to a third embodiment, the aminosilicone corresponding to formula (B) has the following formula (E): [ka] (In the formula, - p and q are numbers whose sum (p + q) is in the range of 1 to 1000, in particular in the range of 50 to 350, more particularly in the range of 150 to 250; p can represent a number from 0 to 999, in particular from 49 to 349, more particularly from 159 to 239, and q can represent a number from 1 to 1000, in particular from 1 to 10, more particularly from 1 to 5; - R1 and R2 are different and represent hydroxyl or a C1-C4 alkoxy group, and at least one of the R1 or R2 groups represents an alkoxy group. The silicones are selected from the group consisting of:

[0317] Preferably, the alkoxy group is a methoxy group.

[0318] The hydroxy / alkoxy molar ratio is generally in the range of 1:0.8 to 1:1.1, preferably in the range of 1:0.9 to 1:1, and more particularly 1:0.95.

[0319] The mass average molecular weight (Mw) of the silicone is preferably in the range of 2,000 to 200,000, more particularly 5,000 to 100,000, and even more particularly 10,000 to 50,000.

[0320] Commercially available products containing silicones of structure (D) or (E) may contain in their composition one or more other aminosilicones having a structure different from formula (D) or (E).

[0321] A product containing aminosilicone of structure (D) is sold under the name Belsil® ADM 652 by Wacker.

[0322] Products containing aminosilicones of structure (E) are sold by Wacker under the names Fluid WR 1300® or Belsil® ADM LOG 1.

[0323] When these aminosilicones are used, a particularly advantageous embodiment consists in using them in the form of an oil-in-water emulsion. The oil-in-water emulsion may contain one or more surfactants. The surfactants may be of any nature, but are preferably cationic and / or nonionic. The number-average particle size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nanometers. Preferably, microemulsions are used, especially aminosilicones of formula (E), whose average particle size is in the range of 5 nm to 60 nm (inclusive), more particularly in the range of 10 nm to 50 nm (inclusive). Thus, in accordance with the present invention, aminosilicone microemulsions of formula (E) sold by Wacker under the names Finish CT 96 E (registered trademark) or SLM 28020 (registered trademark) can be used.

[0324] According to a fourth embodiment, the aminosilicone corresponding to formula (B) has the following formula (F): [ka] (In the formula, - m and n are numbers whose sum (n + m) is in the range of 1 to 2000, in particular 50 to 150, where n can represent a number from 0 to 1999, in particular 49 to 149, and m can represent a number from 1 to 2000, in particular 1 to 10; -A represents a linear or branched alkylene group containing 4 to 8 carbon atoms, preferably 4 carbon atoms. The group is preferably linear.

[0325] The weight average molecular weight (Mw) of these aminosilicones is preferably in the range of 2,000 to 1,000,000, more specifically 3,500 to 200,000.

[0326] A silicone corresponding to formula (B) is, for example, Xiameter MEM 8299 Emulsion from Dow Corning (INCI name: Amodimethicone and Trideceth-6 and Cetrimonium Chloride).

[0327] According to a fifth embodiment, the aminosilicone corresponding to formula (B) has the following formula (G): [ka] (In the formula, - m and n are numbers whose sum (n + m) is in the range of 1 to 2000, in particular 50 to 150, where n can represent a number from 0 to 1999, in particular 49 to 149, and m can represent a number from 1 to 2000, in particular 1 to 10; -A represents a linear or branched alkylene group containing 4 to 8 carbon atoms, preferably 4 carbon atoms. This group is preferably branched.

[0328] The weight average molecular weight (Mw) of these aminosilicones is preferably in the range of 500 to 1,000,000, and even more particularly 1,000 to 200,000.

[0329] A silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning; c) Formula (H): [ka] (In the formula, -R5 is a monovalent hydrocarbon group containing 1 to 18 carbon atoms, in particular C1-C 18 Alkyl or C2-C 18 represents an alkenyl group, for example methyl; -R6 is a divalent hydrocarbon group, particularly a C1-C 18 Alkylene group or divalent C1-C 18 For example, a C1-C8 alkyleneoxy group; -Q- is an anion, such as a halide ion, especially chloride, or an organic acid salt, especially acetate; -r represents a statistical mean value ranging from 2 to 20, especially from 2 to 8; -s represents a statistical mean value ranging from 20 to 200, especially 20 to 50) is an amino silicone corresponding to

[0330] Aminosilicones of this type are described in particular in US Pat. No. 4,185,087. -d) Formula (I): [ka] (In the formula, -R7 may be the same or different and are monovalent hydrocarbon-based groups containing 1 to 18 carbon atoms, in particular C1-C 18 Alkyl groups, C2-C 18 represents an alkenyl group or a ring containing 5 or 6 carbon atoms, for example methyl; -R6 is a divalent hydrocarbon group, particularly a C1-C 18 Alkylene group or divalent C1-C 18 For example, a C1-C8 alkyleneoxy group; -R8 may be the same or different and are each a hydrogen atom, a monovalent hydrocarbon group containing 1 to 18 carbon atoms, particularly C1 to C 18 Alkyl groups, C2-C 18 represents an alkenyl group or a -R6-NHCOR7 group; -X - is an anion, such as a halide ion, especially chloride, or an organic acid salt, especially acetate; -r represents a statistical mean value ranging from 2 to 200, especially 5 to 100) Quaternary ammonium silicone.

[0331] These silicones are described, for example, in patent application EP-A-0 530 974; e) Formula (J): [ka] (In the formula, R1, R2, R3 and R4 may be identical or different and represent a C1-C4 alkyl group or a phenyl group; -R5 represents a C1 to C4 alkyl group or a hydroxyl group; -n is an integer ranging from 1 to 5, -m is an integer ranging from 1 to 5, -x is selected so that the amine number is in the range of 0.01 to 1 meq / g) aminosilicone; f)(AB) n Multiblock polyoxyalkylenated aminosilicones of the type (A is a polysiloxane block and B is a polyoxyalkylene block containing at least one amine group).

[0332] The silicone preferably has the following general formula: [-(SiMeO) x SiMe2-RN(R'')-R'-O(C2H4O) a (C3H6O) b -R'-N(H)-R-] or [-(SiMe2O)xSiMe2-RN(R'')-R'-O(C2H4O) a (C3H6O) b -] (In the formula, -a is an integer greater than or equal to 1, preferably in the range of 5 to 200, more particularly 10 to 100; -b is an integer ranging from 0 to 200, preferably from 4 to 100, more particularly from 5 to 30; - x is an integer ranging from 1 to 10000, more particularly from 10 to 5000; -R'' is a hydrogen atom or methyl; -R may be the same or different and is a linear or branched divalent C-C alkyl group optionally containing one or more heteroatoms such as oxygen. 12represents a hydrocarbon-based group; preferably, R represents an ethylene group, a linear or branched propylene group, a linear or branched butylene group, or a CH2CH2CH2OCH2CH(OH)CH2- group; preferentially, R represents a CH2CH2CH2OCH2CH(OH)CH2- group; -R' may be the same or different and is a linear or branched divalent C-C alkyl group, optionally containing one or more heteroatoms such as oxygen. 12 represents a hydrocarbon-based group; preferably, R' represents an ethylene group, a linear or branched propylene group, a linear or branched butylene group or a CH2CH2CH2OCH2CH(OH)CH2- group; preferentially, R' represents -CH(CH3)-CH2- It is formed from repeating units represented by the following formula:

[0333] The siloxane blocks preferably represent from 50 mol % to 95 mol %, more particularly from 70 mol % to 85 mol %, relative to the total mass of silicones.

[0334] The amine content is preferably between 0.02 and 0.5 meq / g, more particularly between 0.05 and 0.2, in a solution containing 30% of the copolymer in dipropylene glycol.

[0335] The mass average molecular weight (Mw) of the silicone is preferably 5,000 to 1,000,000, and more specifically 10,000 to 200,000.

[0336] Mention may be made, inter alia, of the silicones sold by Momentive under the names Silsoft A-843 or Silsoft A+. g) and mixtures thereof.

[0337] Preferably, the aminosilicone of formula (B) is chosen from the aminosilicones corresponding to formula (E):

[0338] Preferably, the composition according to the invention comprises at least one aminosilicone with the INCI name Amodimethicone, preferably introduced in the form of an emulsion or microemulsion together with a surfactant.

[0339] Preferably, the composition according to the invention comprises at least one aminosilicone with the INCI name amodimethicone, as an emulsion or microemulsion, together with surfactants with the INCI names trideceth-5 and trideceth-10.

[0340] The silicones may be present in a total amount ranging from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight, and even more preferentially from 0.5% to 5% by weight, relative to the total weight of composition A and / or composition B.

[0341] The silicones may be present in a total amount ranging from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight and even more preferentially from 0.5% to 5% by weight relative to the total weight of composition C.

[0342] The silicones may be present in a total amount ranging from 0.01% to 20%, preferably from 0.05% to 15%, more preferentially from 0.1% to 10% and even more preferentially from 0.5% to 5% by weight relative to the total weight of composition C.

[0343] organic solvents One and / or the other of compositions A and B used in the context of the method according to the invention may comprise one or more organic solvents different from the compound containing at least one hydroxyl function described above.

[0344] Composition A and / or Composition B according to the invention are preferably aqueous. The water content may range from 20% to 99% by weight, preferably from 50% to 98% by weight, and more preferentially from 60% to 95% by weight, relative to the total weight of Composition A and / or Composition B.

[0345] additives One and / or the other of compositions A and B used in the context of the method according to the invention may contain any adjuvant or additive normally used.

[0346] Among the additives that may be used are reducing agents, emollients, antifoaming agents, moisturizing agents, UV screening agents, peptidizing agents, solubilizing agents, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than those mentioned above, oils, waxes, and mixtures thereof.

[0347] One and / or the other of compositions A and B may in particular be in the form of a suspension, dispersion, gel, 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.

[0348] 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.

[0349] Optional Application of Composition D The method for coloring keratinous fibers according to the invention may also comprise a step of applying to the hair keratinous fibers a composition D comprising at least one silicone compound containing at least one carboxyl group.

[0350] Silicone compounds with carboxylic functional groups 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.

[0351] The silicones that can be used may be soluble or insoluble in composition D and may be in the form of oils, waxes, resins or gums, with silicone oils and gums being preferred.

[0352] Silicones are particularly well-described in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press.

[0353] Preferably, the silicone compound containing at least one carboxyl group has the following formula (XXVII): [ka] (In the formula, -R1 independently represents an alkyl group containing 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; a hydroxyl group; an alkoxy group containing 1 to 20 carbon atoms; or an aryl group containing 6 to 12 carbon atoms; -R2 independently represent a group R4-COOM (R4 represents a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof, and M represents a hydrogen atom); an alkali metal or alkaline earth metal or quaternary ammonium NR'3 (R' may be the same or different and represent H or an alkyl group containing 1 to 4 carbon atoms); a carboxyl group COOH or a pyrrolidine group containing a group Ra-(ORb)x-COOM (where Ra represents a linear or branched alkylene group containing 1 to 4 carbon atoms, Rb represents an alkyl group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; M represents a hydrogen atom, an alkali metal or alkaline earth metal or quaternary ammonium NR'3, and R' may be the same or different and represent H or an alkyl group containing 1 to 4 carbon atoms); -R3 independently represents an alkyl group containing 1 to 20 carbon atoms; a hydroxyl group; an R4-COOM group (R4 represents a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted with at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof, and M represents a hydrogen atom); an alkali metal or alkaline earth metal or quaternary ammonium NR'3 (R' may be the same or different and represents H or an alkyl group containing 1 to 4 carbon atoms); an alkoxy group containing 1 to 20 carbon atoms; an aryl group containing 6 to 12 carbon atoms or R a -(OR b ) x -COOM group (in the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, and R b represents an alkyl group having 1 to 4 carbon atoms, x is an integer ranging from 1 to 200; M represents a hydrogen atom, an alkali metal or alkaline earth metal, or a quaternary ammonium NR'3 (wherein R' may be the same or different and represents H or an alkyl group having 1 to 4 carbon atoms); -n represents an integer ranging from 1 to 1000; -p represents an integer in the range of 0 to 1000; At least one of the R2 and / or R3 groups is selected from organosiloxanes containing a carboxyl group COOH or COOM, where M is understood to represent an alkali metal or alkaline earth metal or quaternary ammonium NR'3, where R' may be the same or different and represent H or alkyl containing 1 to 4 carbon atoms.

[0354] In particular, the silicone compound containing at least one carboxyl group has the following formula (XXVIII): [ka] (In the formula, -R1 independently represent a linear or branched alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and better still from 1 to 6 carbon atoms, preferentially methyl; -R4 is independently a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms, and mixtures thereof; or a divalent group R a -(OR b ) x -(In the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, R b represents an alkylene group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; -M independently represents a hydrogen atom, an alkali metal or alkaline earth metal, or a quaternary ammonium NR'3, where R' may be the same or different and represents H or an alkyl containing 1 to 4 carbon atoms; -n represents an integer ranging from 1 to 1000; of the following formula (XXIX): [ka] (In the formula, -R1 independently represent an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferentially methyl; -R4 is a linear or branched, saturated or unsaturated alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof; or a divalent group R a -(OR b ) x -(In the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, R b represents an alkylene group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; -M represents a hydrogen atom, an alkali metal or alkaline earth metal, or a quaternary ammonium NR'3, where R' may be the same or different and represents H or an alkyl containing 1 to 4 carbon atoms; -p represents an integer ranging from 1 to 1000; -n represents an integer ranging from 1 to 1000; -the following formula (XXX): [ka] (In the formula, -R1 independently represent an alkyl group containing 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms and better still 1 to 6 carbon atoms, preferentially methyl; -R4 is a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof; or a divalent group R a -(OR b ) x -(In the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, R b represents an alkylene group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; -R3 represents an alkyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms, or an aryl group containing 6 to 12 carbon atoms; -M independently represents a hydrogen atom, an alkali metal or alkaline earth metal, or a quaternary ammonium NR'3, where R' may be the same or different and represents H or an alkyl containing 1 to 4 carbon atoms; -n represents an integer ranging from 1 to 1000; of the following formula (XXXI): [ka] (In the formula, -R8 represents an alkyl group containing 1 to 6 carbon atoms, preferably methyl; -m represents an integer ranging from 1 to 1000; -n represents an integer ranging from 1 to 1000; - and mixtures thereof You can choose from:

[0355] Among the organosiloxanes of formula (XXVIII), mention may be made of polydimethylsiloxanes (PDMS) having carboxyl end groups, such as the compound sold by the company Momentive under the trade name Silform INX (INCI name: Biscarboxydecyldimethicone).

[0356] Among the organosiloxanes of formula (XXIX), mention may be made of polydimethylsiloxanes (PDMS) having pendant carboxyl groups, such as the compound sold by Shin-Etsu under the trade name X-22-3701E.

[0357] Among the organosiloxanes of formula (XXX), mention may be made of polydimethylsiloxanes (PDMS) having carboxyl end groups, such as the compound sold by Shin-Etsu Chemical Co., Ltd. under the trade name X-22-3710.

[0358] Among the organosiloxanes of formula (XXXI), mention may be made of the compound sold by Grant Industries under the trade name Grandsil SiW-PCA-10 (INCI name: dimethicone and PCA dimethicone and butylene glycol and decyl glucoside).

[0359] The silicone compounds containing carboxyl groups may correspond, for example, to the compounds described in EP 186507 in the name of Chisso Corporation, which is incorporated herein by reference.

[0360] Preferably, the silicone compound containing at least one carboxyl group is selected from organosiloxanes of formula (XXVIII), organopolysiloxanes of formula (XXIX), and mixtures thereof.

[0361] More preferentially, the silicone compound containing at least one carboxyl group has the following formula (XXIXa): [ka] (In the formula, -R4 represents a linear or branched, saturated or unsaturated alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof, or 8 to 12 carbon atoms; -p represents an integer ranging from 1 to 1000; -n represents an integer in the range of 1 to 1000) The organosiloxanes are selected from the following:

[0362] The total amount of silicone compounds containing at least one carboxyl group present in composition D preferably ranges from 0.01% to 20% by weight, more preferentially from 0.1% to 15% by weight, and better still from 0.5% to 10% by weight, relative to the total weight of composition D.

[0363] oil Composition D may also include one or more oils.

[0364] Preferably, composition D comprises one or more oils. More preferentially, composition D comprises one or more oils chosen from alkanes.

[0365] The term "oil" refers to oil at room temperature (25°C) and atmospheric pressure (760 mmHg, i.e., 1.013 x 10 5 "Liquid" refers to a fatty substance that is liquid at temperatures below 100°C (Pa).

[0366] The oil may be volatile or non-volatile.

[0367] The term "volatile oil" refers to an oil that can evaporate in less than one hour upon contact with the skin at room temperature and atmospheric pressure. Volatile oils are cosmetic volatile oils that are liquid at room temperature. More specifically, the evaporation rate of volatile oils is between 0.01 and 200 mg / cm. 2 / min (boundary values ​​included) (see procedure for measuring evaporation rate later in the text).

[0368] The term "non-volatile oil" refers to an oil that remains on the skin or keratinous fibers at room temperature and atmospheric pressure. More specifically, the evaporation rate of a non-volatile oil is exactly 0.01 mg / cm 2 / min (see procedure for measuring evaporation rate later in the text).

[0369] Preferably, the composition contains C6 to C 16 It comprises one or more oils selected from alkanes and / or mixtures thereof.

[0370] C6~C 16 With respect to alkanes, these may be straight-chain or branched, and optionally cyclic.

[0371] In particular, branches C8 to C 16 Alkanes, e.g., C8-C 16 Reference is made to isoalkanes (also known as isoparaffins), isododecane, isodecane or isohexadecane, for example the oils sold under the trade names Isopar or Permethyl, and mixtures thereof.

[0372] Reference is also made to linear alkanes, preferably of vegetable origin, containing 7 to 15 carbon atoms, in particular 9 to 14 carbon atoms, more particularly 11 to 13 carbon atoms.

[0373] Examples of linear alkanes suitable for use in the present invention include n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14) and n-pentadecane (C15) and mixtures thereof, in particular the mixture of n-undecane (C11) and n-tridecane (C13) described in Example 1 of Cognis patent application WO 2008 / 155059.

[0374] Mention may also be made of n-dodecane (C12) and n-tetradecane (C14), sold under the trade designations Parafol 12-97 and Parafol 14-97, respectively, by Sasol, as well as mixtures thereof.

[0375] Examples of alkanes suitable for use in the present invention include those described in patent applications WO 2007 / 068371 and WO 2008 / 155059. These alkanes are obtained from fatty alcohols, which themselves are obtained from coconut kernel oil or palm oil.

[0376] According to a particular embodiment, the composition comprises isododecane. A compound of this type is, for example, isododecane sold by Ineos under the trade designation Isododecane.

[0377] Preferably, composition D is C8 to C 16 It comprises one or more oils chosen from alkanes, more preferentially from isododecane, isohexadecane, tetradecane and / or mixtures thereof.

[0378] More preferentially, composition D comprises isododecane.

[0379] Composition D may comprise one or more oils present in a total amount of from 30% to 99% by weight, preferably from 50% to 99% by weight, and better still from 70% to 99% by weight relative to the total weight of composition D.

[0380] Composition D may contain at least one colorant selected from the pigments, direct dyes and mixtures thereof previously described.

[0381] protocol As indicated above, compositions A and B may be applied to keratinous fibers, such as hair, sequentially, in any order, or simultaneously.

[0382] According to one variant of the invention, compositions A and B are applied sequentially to hair keratinous fibers, such as hair, in any order, i.e. composition A may be applied to hair keratinous fibers before composition B, or vice versa.

[0383] According to a particular embodiment, the present invention provides a method for coloring keratinous fibers, such as hair, comprising: i) applying composition A or composition B to said hair keratinous fibers, Composition A comprises at least one (poly)carbodiimide compound as described above; Composition B is at least one associative polymer as described above; at least one compound different from the associative polymer, containing at least one carboxylic acid group as described above, and - comprising at least one compound, preferably at least two compounds, containing at least one hydroxyl functional group; Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof; - one and / or the other of compositions A and B optionally also comprises at least one silicone as defined above; ii) applying composition B to said hair keratinous fibers if composition A has been applied during step i), or composition A if composition B has been applied during step i).

[0384] Preferably, the present invention relates to a method for coloring keratinous fibers such as hair, comprising: i) applying composition A or composition B to said hair keratinous fibers, Composition A comprises at least one (poly)carbodiimide compound as described above; Composition B is at least one associative polymer as described above; at least one compound different from the associative polymer, containing at least one carboxylic acid group as described above, and - comprising at least one compound, preferably at least two compounds, containing at least one hydroxyl functional group; Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof; - one and / or the other of compositions A and B optionally also comprises at least one silicone as defined above; ii) optionally, leaving the composition A or composition B on the fiber for 1 minute to 30 minutes, preferably 1 to 20 minutes, and then iii) optionally washing, rinsing, dewatering or drying the fibers, preferably drying, then iv) application of composition B to said hair keratinous fibers if composition A has been applied during step i), or composition A if composition B has been applied during step i), then v) optionally washing, rinsing, dewatering or drying the fibers, preferably drying, then vi) applying to the hair keratin fibers a composition D comprising at least one silicone compound containing at least one carboxyl group as described above, and then vii) optionally leaving said composition D on the fibers for 1 minute to 30 minutes, preferably 1 to 20 minutes, then viii) optionally, washing, rinsing, dewatering or drying said fibers.

[0385] According to another variant of the invention, compositions A and B are preferably applied simultaneously.

[0386] According to this embodiment, compositions A and B can be mixed immediately at the time of use to obtain composition C, which is then applied to keratinous fibers such as hair.

[0387] The above-described composition C and optional composition D can be used on wet or dry hair keratin fibers and on any type of fiber, whether light or dark, natural or colored, permanently waved, bleached or straightened.

[0388] According to a preferred embodiment, composition C and composition D are applied simultaneously to the hair keratin fibres.

[0389] According to another preferred embodiment, composition D is applied to the hair keratinous fibers after composition C has been applied to the hair keratinous fibers.

[0390] According to another preferred embodiment, composition D is applied to the hair keratinous fibers before applying composition C to the hair keratinous fibers.

[0391] Preferably, composition D is applied to the hair keratinous fibers after composition C has been applied to the hair keratinous fibers.

[0392] According to a particular embodiment of the invention, the hair keratinous fibers are washed before applying composition C and optional composition D.

[0393] Preferably, a washing, rinsing, dewatering or drying step is carried out after applying composition C to the hair keratinous fibers and before applying composition D to the keratinous fibers.

[0394] More preferentially, a drying step is carried out after applying composition C to the hair keratinous fibers and before applying composition D to the hair keratinous fibers.

[0395] Application to the fibers can be carried out via any standard means, in particular with a comb, a fine-toothed brush, a wide-toothed brush, a sponge or the fingers.

[0396] The application of composition C and optional composition D to hair keratinous fibers is generally carried out at room temperature (15 to 25° C.).

[0397] After application of composition C to the hair keratinous 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 applying composition D to the hair keratinous fibers or before, for example, a washing, rinsing, dewatering or drying step.

[0398] Preferably, after composition C has been applied to the hair keratinous fibers, no standing time is allowed before composition D is applied to the hair keratinous fibers.

[0399] After applying composition C and optional composition D, the fibers may be allowed to dry naturally or may be dried at a temperature of, for example, 30° C. or higher.

[0400] Thus, the method according to the invention may comprise the step of applying heat to the hair keratin fibres using a heating appliance.

[0401] The heat application step of the method of the present invention can be carried out using a hood, a hair dryer, a straightener, a Climazon, or the like.

[0402] Preferably, the step of applying heat of the method of the present invention is carried out using a hair dryer.

[0403] When the method of the present invention includes a step of applying heat to the hair keratinous fibers, the step of applying heat to the hair keratinous fibers is carried out after applying composition C and / or optional composition D to the hair keratinous fibers.

[0404] During the step of applying heat to the hair keratin fibers, the hair strands can be subjected to mechanical action such as combing, brushing or hand combing.

[0405] If the step of applying heat to the hair keratin fibers is carried out using a hood dryer or a hair dryer, the temperature is preferably between 30°C and 110°C, preferentially between 50°C and 90°C.

[0406] If the step of applying heat to the hair keratin fibers is carried out using a straightening iron, the temperature is preferably between 110°C and 220°C, preferably between 140°C and 200°C.

[0407] In a particular variant, the method of the present invention comprises a step (b1) of applying heat using a hood dryer, a hair dryer or a crimson, preferably a hair dryer, and a step (b2) of applying heat using a straightening iron or curling iron, preferably a straightening iron.

[0408] Step (b1) can be carried out before step (b2).

[0409] During the implementation of step (b1), also referred to as drying step, the 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.

[0410] Preferably, when the fibers are dried, in addition to the supply of heat, they are dried using an air current, which makes it possible to improve the separation of the covering of the hair strands.

[0411] During drying, the hair strands can be subjected to mechanical action such as combing, brushing or hand combing.

[0412] The temperature at which the straightening iron or curling iron is slid in the drying step (b2) may preferably be in the range of 110°C to 220°C, more preferably 140°C to 200°C.

[0413] After the drying step is completed, a shaping step can be carried out using, for example, a straightening iron; the temperature in the shaping step is 110 to 220°C, preferably 140 to 200°C.

[0414] Preferably, the present invention relates to a method for coloring keratinous fibers, such as hair, comprising mixing composition A and composition B to obtain composition C, followed by: i) applying composition C to said hair keratin fibers: Composition A comprises at least one (poly)carbodiimide compound as described above; Composition B is at least one associative polymer as described above; at least one compound different from the associative polymer, containing at least one carboxylic acid group as described above, and - comprising at least one compound, preferably at least two compounds, containing at least one hydroxyl functional group; Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof; - one and / or the other of compositions A and B optionally also comprises at least one silicone as described above.

[0415] More preferentially, the present invention relates to a method for coloring keratinous fibers, such as hair, comprising mixing composition A and composition B to obtain composition C, and then: i) applying composition C to said hair keratin fibers: Composition A comprises at least one (poly)carbodiimide compound as described above; Composition B is at least one associative polymer as described above; at least one compound different from the associative polymer, containing at least one carboxylic acid group as described above, and - comprising at least one compound, preferably at least two compounds, containing at least one hydroxyl functional group; - comprising at least one colorant selected from pigments, direct dyes and mixtures thereof; - one and / or the other of compositions A and B optionally also comprises at least one silicone as defined above; ii) optionally, leaving the composition C on the fibers for 1 minute to 30 minutes, preferably 1 to 20 minutes, and then iii) optionally washing, rinsing, dewatering or drying the fibers, then iv) applying to the hair keratin fibers a composition D comprising at least one silicone compound containing at least one carboxyl group as described above, then v) optionally, leaving the composition D on the fibers for 1 minute to 30 minutes, preferably 1 to 20 minutes, then vi) optionally, washing, rinsing, dewatering or drying said fibers.

[0416] Preferably, the step of applying composition C to the hair keratinous fibers is repeated several times.

[0417] According to a preferred embodiment, the method for coloring hair keratin fibers, such as hair, is a method for coloring hair keratin fibers, which comprises extemporaneously mixing at least two compositions A and B at the time of use to obtain composition C, and applying composition C to the hair keratin fibers, composition A comprises at least one (poly)carbodiimide compound as defined above; - composition B comprises at least one associative polymer as described above, at least one compound different from the associative polymer as described above containing at least one carboxylic acid group, preferably at least one compound chosen from silicone compounds, polyurethanes, acrylic polymers and mixtures thereof containing at least one carboxylic acid group, at least one compound, preferably at least two compounds, containing at least one hydroxyl functional group, and at least one colorant chosen from pigments, direct dyes and mixtures thereof.

[0418] Composition A and / or Composition B optionally comprise at least one silicone as defined above.

[0419] Preferably, compositions A and B are mixed less than 15 minutes before application to the hair keratinous fibers, more preferentially less than 10 minutes before application, and better still less than 5 minutes before application.

[0420] The weight ratio of composition A to composition B is preferably in the range of 0.1 to 10, preferentially 0.2 to 5, better still 0.5 to 2, and even more preferably 0.6 to 1.5. In a particular embodiment, the weight ratio of composition A to composition B is equal to 1.

[0421] According to a specific embodiment, the method for coloring hair keratin fibers, such as hair, is a method for coloring hair keratin fibers, which method comprises extemporaneously mixing at least two compositions A and B at the time of use to obtain composition C, and applying composition C to the hair keratin fibers, composition A comprises at least one (poly)carbodiimide compound as defined above; composition B comprises at least one associative polymer as described above, at least one compound different from the associative polymer as described above containing at least one carboxylic acid group, preferably at least one compound chosen from silicone compounds, polyurethanes, acrylic polymers and mixtures thereof, containing at least one carboxylic acid group, at least one compound, preferably at least two compounds, containing at least one hydroxyl functional group, and at least one colorant chosen from pigments, direct dyes and mixtures thereof; Composition A and / or Composition B optionally comprise at least one silicone as defined above; and The method is characterized in that the aforementioned composition D is applied to the hair keratinous fibers before and / or after applying the composition C to the hair keratinous fibers.

[0422] The present invention also provides an apparatus for coloring keratinous fibers, such as hair, comprising: in a first compartment (E1), a composition A according to the invention as defined above; in a second compartment (E2), composition B according to the invention as defined above; - optionally also relates to a device comprising two compartments, the third compartment (E3) containing composition D as defined above.

[0423] The 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]

[0424] 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, such as those described 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.

[0425] More specifically, the process for preparing the (poly)carbodiimide of the present invention comprises, in a first step, reacting a diisocyanate reagent (1): O=C=N-L1-N=C=O (1) (wherein L1 is as defined above) in the presence of a carbodiimidization catalyst (2) such as those described in U.S. Pat. No. 4,284,730, particularly a phosphorus-based catalyst, particularly one selected from phospholene oxides and phospholene sulfoxides, diaza- and oxaza-phosphoranes, preferably in an inert atmosphere (nitrogen or argon), particularly preferably in an aprotic polar solvent such as THF, glyme, diglyme, 1,4-dioxane or DMF, at a temperature between room temperature and the reflux temperature of the solvent, preferably about 140° C., to produce a carbodiimide diisocyanate compound (3): O=C=N-L1-(N=C=N-L1) n -N=C=O (3) (wherein L1 and n are as defined above) to obtain a benzoyl halide such as benzoyl chloride, which may be added to deactivate the catalyst.

[0426] 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) (wherein R1, X1, L1, n and E are as defined above) is obtained. According to one variant for obtaining (4) from compound (3), it is possible to add 0.5 eq. of the reagent HEH, followed by 1 eq. of the reagent R1-X1-H.

[0427] 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) (wherein R1, X1, L1, n and E are as defined above) is obtained.

[0428] 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.

[0429] 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'), (wherein L1 and z are as defined above) was reacted with 1 eq. of a nucleophilic reagent R2-X2-H (wherein L1, R2, X2 and z are as defined above) to give the asymmetric compound (7): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EC(O)-NH-L1-(N=C=N-L1) z -NH-C(O)-X2-R2(7) (wherein R1, X1, L1, R2, X2, n, z and E are as defined above) is obtained.

[0430] 1 molar equivalent of the compound O=C=N-L1-(N=C=N-L1) z -N=C=O (3') is reacted with 1 / w molar equivalent of HEH, and then with 1 eq. of a nucleophile R2-X2-H to give compound (8): H-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NH-C(O)-X2-R2(8) (wherein L1, R2, X2, z and E are as defined above, and w is an integer of 1 to 3; more preferentially, w=1) can also be obtained.

[0431] The final compound (8) is then reacted with 1 eq. of compound (4'): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -N=C=O (4') (the compound (4') can be synthesized by reacting 0.5 eq. of a nucleophilic reagent R1-X1-H with 1 eq. of the compound (3)), to obtain the (poly)carbodiimide (9) of the present invention: R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NH-C(O)-X2-R2(9) (In formula (9), L1, R1, X1, R2, X2, n, z, w and E are as defined above.)

[0432] 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.

[0433] 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.

[0434] 2200-2300 cm by infrared spectroscopy -1 The reaction medium is heated under nitrogen at 140°C for 4 hours, and then cooled to 120°C, while the reaction is monitored by the absorption of isocyanate groups.

[0435] 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.

[0436] 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.

[0437] Example 2: Compositions A1, B1 and B2 described below were prepared: amounts are expressed as g / 100 g of starting material obtained.

[0438] [Table 1]

[0439] [Table 2]

[0440] Compositions A1, B1 and B2 are therefore compositions used in the context of the method according to the invention and are therefore considered to be compositions according to the invention.

[0441] a. Stability evaluation The appearance of the compositions is observed at TO after they have been prepared.

[0442] Composition A1 is in the form of a smooth, fluid gel.

[0443] Compositions B1 and B2 are in the form of a flowing, viscous, colored gel.

[0444] The compositions are then stored for 2 months at 45° C. and atmospheric pressure. The stability of each composition is then assessed by visual observation.

[0445] The stability of compositions A1, B1 and B2 is acceptable.

[0446] b. Antibacterial performance evaluation In the context of this evaluation, two tests are performed: an "orientation" test and a "confirmation" test.

[0447] Measurement method: The effectiveness of the preservatives according to the invention is evaluated by a challenge test which makes it possible to determine the level of antimicrobial protection of the composition.

[0448] This consists of artificially contaminating a test product with various microorganisms (bacteria, yeasts and molds) and monitoring the number of viable bacteria over time.

[0449] For this reason, a cleanliness control must be performed before the start of the test, making it possible to ensure that the product to be tested in the challenge test is not contaminated or meets the acceptance criteria. Multiple contaminations are therefore avoided for the correct progression of the challenge test.

[0450] A well-protected product must allow decontamination of introduced microorganisms, with this decontamination being more or less rapid as a function of the microbial strain, type of product, conditioning article, etc.

[0451] The product is dispensed into as many pill bottles as there are microorganisms to be tested for. The calibrated microbial suspension is 10 per gram of product. 6 A bacterial content is introduced into each of these bottles (each microbial suspension is counted to determine the exact content inoculated into the product).

[0452] The contaminated product is stored at 32.5°C ± 2.5°C for 24 hours, or 48 hours in the case of moulds.

[0453] The protective effectiveness of the formulation is tested against a limited but selected spectrum of microorganisms among species likely to contaminate the product both during its manufacture and during its use.

[0454] The microbial spectrum combines the various microorganisms used to perform the challenge test, including a Gram-positive bacterium (Enterococcus faecalis), a yeast (Candida albicans), and a mold (Aspergillus niger) for the orientation test and four bacteria (Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Enterococcus faecalis), a yeast (Candida albicans), and a mold (Aspergillus niger) for the confirmatory test.

[0455] Part 1 of the test: Orientation This is a screening test to direct the remaining tests and identify formulations that provide insufficient protection in the short term.

[0456] After 7 days of contact between the product and the bacteria, samples are taken for the purpose of enumerating the microorganisms remaining in the product.

[0457] Detection limit by this method: 250cfu / g

[0458] Therefore, the most favorable result is less than 250 bacteria / g (no microbial colonies on the dish).

[0459] Part 2 of the exam: Verification Except in special cases, only formulations retained at the end of the orientation test may undergo the validation step.

[0460] For orientation, after 7 days of contact between the product and the bacteria, a first sampling is performed to count the microorganisms remaining in the product.

[0461] The main difference between the validation and orientation steps is that two other sample collections are performed to monitor changes in antimicrobial protection over time: a sample taken on day 14 and another on day 28.

[0462] The dilutions made for the enumeration are plated in Petri dishes.

[0463] The bacteria remaining in the product are counted.

[0464] Example: 4.3x10 5 Bacteria / g

[0465] Detection limit by this method: 200cfu / g

[0466] Therefore, the most favorable result is less than 200 bacteria / g (no microbial colonies on the Petri dish).

[0467] To confirm the stability of antimicrobial protection over time, the test is repeated on the formulation after accelerated aging at 45°C for 2 months.

[0468] The results are collated in the following table:

[0469] [Table 3]

[0470] The coloring method according to the invention therefore uses compositions that have good stability over time and good protection against microorganisms and therefore good storage over time.

[0471] Example 3: Compositions A1, B1 and B2 described above in Example 2 were prepared.

[0472] Two mixtures are then made.

[0473] Composition A1 is mixed with composition B1 in a 50 / 50 ratio to obtain composition C1.

[0474] Composition A1 is mixed with composition B2 in a 50 / 50 ratio to obtain composition C2.

[0475] Compositions C1 and C2 are therefore compositions according to the invention.

[0476] The following composition D was then prepared: Amounts are expressed as g / 100g of starting material obtained.

[0477] [Table 4]

[0478] protocol: Compositions C1 and C2 are each applied to dry natural hair tresses containing 90% white hair at a rate of 0.8 g of composition per gram of tress.

[0479] The hair tresses are then dried using a hair dryer and then combed.

[0480] Composition D is then applied to the tresses of hair that have been treated with compositions C1 and C2 and dried, at a rate of 0.5 g of composition per gram of tress.

[0481] The tresses are then dried using a hair dryer and then combed.The tresses are then stored at room temperature and ambient humidity for 24 hours.

[0482] Next, in order to evaluate the durability (persistence) of the color obtained on the hair strands thus colored, the hair strands are subjected to a test in which the hair strands are repeatedly shampooed according to the shampooing procedure described below.

[0483] Shampoo Wash Protocol: The colored locks are combed, dampened with water at 35° C., and then hand combed five times for five seconds. The locks are then squeezed between two fingers and dried.

[0484] A standard shampoo (Garnier Ultra Doux) is applied evenly to the colored hair tresses at a ratio of 0.4 g of standard shampoo per gram of tress and gently massaged along the length of the tress from root to tip for 15 seconds (6 times).

[0485] The tress is then placed on a watch glass and allowed to stand for 1 minute.

[0486] The tress is then rinsed with water while passing it through the fingers (15 times) and then squeezed dry between two fingers before the next shampoo wash.

[0487] After the test, which involves several shampoo washes, the hair tresses are combed and dried with a hair dryer.

[0488] 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).

[0489] 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.

[0490] The durability of the color is evaluated by the color difference ΔE between the colored hair strand before shampooing and after shampooing five times according to the procedure described above. The lower the ΔE value, the better the color durability after shampooing.

[0491] The ΔE value is calculated according to the following formula:

number

[0492] In this formula, L*a*b* represents the value measured after coloring the hair and washing with shampoo, and L0*a0*b0* represents the value measured after coloring the hair and before washing with shampoo.

[0493] [Table 5]

[0494] The hair tresses treated with each of the compositions (C1 and C2) + D and washed with five shampoo washes have low ΔE values, and therefore the colored coating of the hair keratin fibers obtained with the compositions (C1 and C2) + D shows good durability against shampoo washes.

[0495] Furthermore, a smooth and uniform coating of color on the hair is observed.

[0496] Example 4: Compositions A2, B3 and B4 described below were prepared: amounts are expressed as g / 100g of starting material obtained.

[0497] [Table 6]

[0498] [Table 7]

[0499] Compositions A2 and B3 are therefore compositions used in the context of the method according to the invention. These compositions are therefore considered to be compositions according to the invention. Composition B4 is a comparative composition.

[0500] The appearance of the compositions is observed at TO after they have been prepared.

[0501] Composition A2 is in the form of a smooth, fluid gel.

[0502] Composition B3 is in the form of a flowable viscous gel.

[0503] Composition B4 is in the form of a very thick gel.

[0504] The compositions are then stored for 10 days at 55° C. and atmospheric pressure. The stability of each composition is then assessed by visual observation.

[0505] It can be seen that composition B4 was in the form of a very brittle dry gel containing many particles.

[0506] Therefore, the stability of composition B4 is insufficient and unacceptable.

[0507] On the other hand, the stability of composition B3 is acceptable, and the stability of composition A2 is also acceptable.

[0508] Example 5: Compositions A2 and B3 described above in Example 4 were prepared.

[0509] Composition A2 is mixed with composition B3 in a 50 / 50 weight ratio to obtain hair coloring composition C3.

[0510] Composition C3 is therefore a composition according to the invention.

[0511] Composition D described above in Example 3 is then used.

[0512] protocol: Composition C3 is applied to dry natural hair tresses containing 90% white hair at a rate of 0.5 g of composition per gram of tress.

[0513] The hair tresses are then dried using a hair dryer and then combed.

[0514] Composition D is then applied to the same tresses of hair that have been treated with composition C3 and dried, at a rate of 0.5 g of composition per gram of tress.

[0515] The tresses are then left at room temperature for 24 hours.

[0516] Next, in order to evaluate the durability (persistence) of the color obtained on the hair strands thus colored, the hair strands are subjected to a test in which the hair strands are repeatedly shampooed according to the shampooing procedure described below.

[0517] Shampoo Wash Protocol: The colored locks are combed, dampened with water at 35° C., and then hand combed five times for five seconds. The locks are then squeezed between two fingers and dried.

[0518] A standard shampoo (Garnier Ultra Doux) is applied evenly to the colored hair tresses at a ratio of 0.4 g of standard shampoo per gram of tress and gently massaged along the length of the tress from root to tip for 15 seconds (6 times).

[0519] The tress is then placed on a watch glass and allowed to stand for 1 minute.

[0520] The tress is then rinsed with water while passing it through the fingers (15 times) and then squeezed dry between two fingers before the next shampoo wash.

[0521] After the test, which involves several shampoo washes, the hair tresses are combed and dried with a hair dryer.

[0522] result:

[0523] [Table 8]

[0524] The hair tresses treated with composition C3+D and washed with 5 shampoo washes have low ΔE values, and therefore the colored coating obtained with composition C3+D shows good durability to shampoo washes.

[0525] Furthermore, a smooth and uniform coating of color on the hair is observed.

Claims

1. 1. A method for coloring hair keratinous fibers, comprising applying composition A and composition B to said hair keratinous fibers, The composition A contains at least one (poly)carbodiimide compound, The composition B is at least one associative polymer; at least one compound different from said associative polymer, containing at least one carboxylic acid group, and - comprises at least one compound containing at least one hydroxyl functional group; Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof; and A method wherein said composition A and said composition B are applied simultaneously or sequentially to said hair keratinous fibers.

2. The (poly)carbodiimide compound is a compound of the following formula (I): 【Chemical 1】 (In the formula, -X １ and X ２ independently represent an oxygen atom O, a sulfur atom S, or an NH group; -R １ and R ２ are independently selected from hydrocarbon groups optionally interrupted by one or more heteroatoms, alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, and azacyclopropane groups, and one or more and hydrocarbon radicals optionally interrupted by 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, 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 is a compound of the following formula (II): 【Chemistry 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 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 - (In the formula, -R ３ and R ４ independently represent a divalent hydrocarbon group optionally interrupted by one or more heteroatoms; -R ５ independently represent a covalent bond or a divalent saturated hydrocarbon group optionally interrupted by one or more heteroatoms; -R ６ independently represent a hydrogen atom or a hydrocarbon group optionally interrupted by one or more heteroatoms. represents a group selected from 2. The method of claim 1, wherein the compound is selected from the group consisting of:

4. The (poly)carbodiimide compound is selected from compounds of formula (II): -X １ and X ２ independently represent an oxygen atom; -R １ and R ２ are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, from which the hydroxyl groups have been removed, and mixtures thereof; - n and z represent integers ranging from 1 to 20, where n + z ≥ 2 and w is equal to 1; -L1 is C １ ~C １８ a divalent aliphatic hydrocarbon group of 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 - (In the formula, R3 and R4 are independently a C group optionally interrupted by one or more heteroatoms; ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups and mixtures thereof; -R ５ is not a covalent bond, R ５ is optionally interrupted by one or more heteroatoms, ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups and mixtures thereof; and -R ６ is optionally interrupted by one or more heteroatoms, ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ 4. The method of claim 3, wherein the aryl group represents a group selected from the group consisting of alkylene groups and mixtures thereof.

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

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

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

8. The (poly)carbodiimide compound is a compound of the following formula (XII): 【Chemistry 4】 (In the formula, L １ is 4,4-dicyclohexylenemethane, n and z represent integers ranging from 1 to 20, where n+z ranges from 4 to 10, and E is -O-R ３ -O- group (in the formula, R ３ is a linear or branched C optionally interrupted by one or more heteroatoms １ ~C １８ an alkylene group), and r and s represent integers ranging from 4 to 30.

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

9. The method according to any one of claims 1 to 8, characterized in that the total amount of the (poly)carbodiimide compounds is in the range of 0.01% by mass to 40% by mass relative to the total mass of composition A.

10. 10. The method according to any one of claims 1 to 9, characterized in that the associative polymer is chosen from anionic associative polymers.

11. 11. The method according to claim 1, wherein the total amount of associative polymer ranges from 0.1% to 30% by weight relative to the total weight of composition B.

12. 12. The method according to any one of claims 1 to 11, characterized in that the compound different from the associative polymer containing at least one carboxylic acid group is selected from silicone compounds, polyurethanes, acrylic polymers and mixtures thereof, all of which contain at least one carboxylic acid group.

13. 13. The method of claim 12, wherein the compound different from the associative polymer containing at least one carboxylic acid group is in the form of an aqueous dispersion of particles of a polymer chosen from polyurethanes, acrylic polymers and mixtures thereof.

14. The acrylic polymer may comprise the following monomers: a) (meth)acrylic acid; and b) C １ ~C ３０ Alkyl (meth)acrylate 14. The method of claim 13, comprising one or more units derived from

15. 15. The method according to any one of claims 1 to 14, characterized in that the total amount of said compounds, different from the associative polymer, containing at least one carboxylic acid group ranges from 0.2% to 60% by weight relative to the total weight of composition B.

16. 16. The method according to any one of claims 1 to 15, characterized in that composition B comprises at least one compound containing at least one hydroxyl function selected from phenoxyethanol, 1,2-hexanediol, 4-hydroxyacetophenone, ethanol, chlorphenesin, pentylene glycol and mixtures thereof.

17. 17. The method according to claim 1, wherein the total content of said compounds containing at least one hydroxyl function is at least 2% by weight, relative to the total weight of composition B.

18. 18. The method according to claim 1, wherein the content of the colorant is in the range of 0.001% by weight to 20% by weight relative to the total weight of composition A and / or composition B.

19. 19. The method according to claim 1, wherein the pigment content is in the range of 0.05% by weight to 20% by weight, relative to the total weight of composition A and / or composition B.

20. 20. The method according to any one of claims 1 to 19, characterized in that one and / or the other of compositions A and B also comprises at least one silicone.

21. 21. The method of claim 20, wherein the silicone is present in a total amount ranging from 0.01% to 20% by weight relative to the total weight of composition A and / or composition B.

22. 22. The method according to any one of claims 1 to 21, characterized in that it also comprises a step of applying to the hair keratin fibres a composition D comprising at least one silicone compound containing at least one carboxyl group.

23. 23. The method according to claim 22, characterized in that the total amount of the silicone compounds containing at least one carboxyl group present in composition D ranges from 0.01% to 20% by weight relative to the total weight of composition D.

24. 24. The method according to claim 22 or 23, characterized in that composition D also comprises one or more oils.

25. 1. An apparatus for coloring hair keratin fibers, comprising: - in a first compartment (E1), a composition A as defined in any one of claims 1 to 9 and 18 to 21; - in a second compartment (E2), a composition B as defined in any one of claims 1 and 10 to 21; optionally in a third compartment (E3), composition D as defined in any one of claims 22 to 24; 10. The device according to claim 1, wherein the at least two compartments comprise:

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