Hair coloring process comprising the application of a (poly)carbodiimide compound, a silicone acrylic copolymer and a coloring agent

Abstract

The present invention relates to a hair coloring process comprising the application to the hair of at least one composition C comprising: - one or more (poly)carbodiimide compounds of the following formula (II): (II); - one or more silicone acrylic copolymers; - one or more coloring agent(s) chosen from pigments, direct dyes and mixtures thereof.

Description

Title of the invention: Hair coloring process comprising the application of a (poly)carbodiimide compound, a silicone acrylic copolymer and a coloring agent

[0001] The present invention relates to a method for coloring hair comprising the application to the hair of a composition C comprising a specific (poly)carbodiimide compound, a silicone acrylic copolymer and a coloring agent. Technical field

[0002] In the field of coloring hair keratin fibers, in particular human hair, it is already known to color hair keratin fibers by different techniques using direct dyes or pigments for non-permanent colorings or dye precursors for permanent colorings.

[0003] There are basically three types of hair coloring process:

[0004] a) so-called permanent coloring which has the function of bringing about a significant modification of the natural color and which uses oxidation dyes which penetrate into the hair fiber and form the dye by a process of oxidative condensation;

[0005] b) non-permanent, semi-permanent or direct coloring, which does not involve the oxidative condensation process and is resistant to 4 or 5 shampoos; consists of dyeing keratin fibers with dyeing compositions containing direct dyes;

[0006] c) temporary coloring which results in a change in the natural color of the hair which lasts from one shampoo to the next and which serves to enhance or correct a shade already obtained. It can also be likened to a “make-up” process.

[0007] For this latter type of coloring, it is known to use colored polymers formed by grafting one or more dyes of azoic, triphenyl-methane, azine, indoamine or anthraquinone nature onto a polymer chain. These colored polymers are not entirely satisfactory, particularly in terms of the homogeneity of the coloring obtained, its resistance, not to mention the problems linked to their manufacture and particularly to their reproducibility.

[0008] Another coloring method consists of using pigments. Indeed, the use of pigment on the surface of keratin fibers generally makes it possible to obtain visible colorings on dark hair since the pigment on the surface masks the natural color of the fiber. However, the colorings obtained by this coloring method have the disadvantage of having low resistance to shampoos as well as to external agents such as sebum, perspiration, brushing and / or friction.

[0009] Furthermore, temporary hair coloring compositions may also have usage qualities which are not entirely satisfactory, particularly in terms of brushing or combing through the hair.

[0010] There therefore remains a need to have a hair coloring process, which has the advantage of obtaining a homogeneous colored coating on the hair, while forming a coating that is resistant to shampoos and various attacks that the hair may be subjected to such as brushing and / or rubbing without damaging the hair.

[0011] Thus, the aim of the present invention is to develop a hair coloring process which has the advantage of obtaining a homogeneous and smooth colored coating on the hair, while forming a coating which is resistant to shampoos and various attacks which the hair may be subjected to such as brushing and / or rubbing without damaging the hair while improving the qualities of use such as brushing or combing. Statement of the invention

[0012] The present invention therefore relates to a process for coloring hair comprising the application to the hair of at least one composition C comprising:

[0013] - one or more (poly)carbodiimide compound(s) chosen from the compounds of following formula (II):

[0014]

[0015] in which:

[0016] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0017] - Ri and R2 independently represent a hydrocarbon radical optionally in interrupted by one or more heteroatom(s);

[0018] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w denotes a whole number ranging from 1 to 3;

[0019] - Li independently represents a divalent aliphatic hydrocarbon radical in C 1 - Cig, a C3-Ci5 cycloalkylene radical, a C3-Ci2 heterocycloalkylene group, or a C6-Ci4 arylene group, and mixtures thereof;

[0020] - E independently represents a group chosen from:

[0021] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-,

[0022] in which R3 and R4 independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s);

[0023] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, possibly interrupted by one or more heteroatom(s);

[0024] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s);

[0025] - one or more silicone acrylic copolymers; and

[0026] - one or more coloring agent(s) chosen from pigments, dyes direct, and their mixtures.

[0027] Thanks to the hair coloring process according to the invention, colored coatings are obtained on the hair making it possible to obtain a visible coloring on all types of hair in a way that remains after shampooing while preserving the physical qualities of the hair. Such a coating can be resistant to external aggressions that the hair may be subjected to, such as brushing and perspiration. In particular, it makes it possible to obtain a homogeneous deposit.

[0028] In addition, the composition according to the invention has good qualities of use, in particular in terms of brushing and combing.

[0029] By "remanent coloration after shampooing" is meant, within the meaning of the present invention, that the coloration obtained persists after shampooing, preferably after 3 shampoos, more preferably after 5 shampoos.

[0030] The expression “at least one” means one or more.

[0031] Unless otherwise indicated, the limits of a domain of values ​​are included in this domain, in particular in the expressions “between” and “ranging from ... to ...”.

[0032] The invention is not limited to the illustrated examples. The characteristics of the different examples may in particular be combined within variants not illustrated.

[0033] For the purposes of the present invention and, unless otherwise indicated,

[0034] - an “alkyl” radical denotes a saturated linear or branched radical containing by example of 1 to 20 carbon atoms;

[0035] - an “aminoalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an NH2 group;

[0036] - a “hydroxyalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an OH group;

[0037] - an “alkylene” radical denotes a divalent saturated C2-C4 hydrocarbon group, linear or branched, such as methylene, ethylene, or propylene;

[0038] - a “cycloalkyl” or “alicycloalkyl” radical denotes a hydrocarbon group mono- or bicyclic saturated cyclic, preferably monocyclic, comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 24 carbon atoms, in particular comprising from 3 to 20 carbon atoms, more particularly from 3 to 13 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, or norbomyl, in particular cyclopropyl, cyclopentyl or cyclohexyl. it being understood that the cycloalkyl radical may be substituted by one or more (Ci-C4)alkyl groups such as methyl, preferably the cycloalkyl radical is then an isobomyl group,

[0039] - a “cycloalkylene” radical denotes a divalent cycloalkyl group with “cy “cloalkyl” as defined above, preferably C3-C12;

[0040] - an “aryl” radical is an unsaturated and aromatic cyclic hydrocarbon radical, comprising from 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms, mono / bi / or tri / cyclic, fused or not, preferably the aryl group comprises 1 cycle with 6 carbon atoms such as phenyl, naphthlyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical may be substituted by one or more (Ci-C4)alkyl groups such as methyl, preferably tolyl, xylyl, or methylnaphthyl, preferably the aryl group represents phenyl;

[0041] - an “arylene” radical is a divalent aryl radical with “aryl” as defined above preferably arylene represents phenylene;

[0042] - a “heterocyclic” radical denotes a mono or poly hydrocarbon radical cyclic, saturated or unsaturated, non-aromatic or aromatic, comprising one or more heteroatoms, preferably from 1 to 5 atoms chosen from O, S or N, comprising from 3 to 20 links, preferably between 5 and 10 links such as imidazolyl, pyrrolyl and furanyl;

[0043] - a “heterocycloalkylene” radical is a divalent heterocyclic group with “heterocyclic” as defined above;

[0044] - an “aryloxy” radical denotes an aryl-oxy radical with “aryl” as defined above cededly;

[0045] - an “alkoxy” radical denotes an alkyl-oxy radical with “alkyl” as defined previously;

[0046] - an “acyloxy” radical denotes an ester radical RC(O)-O- with R an alkyl group as previously defined;

[0047] - a “reactive” group is a group capable of forming a bond covalent with another group, identical or different, by chemical reaction.

[0048] Unless otherwise indicated, when compounds are mentioned in the present application, their optical isomers, their geometric isomers, their tautomers, their salts, alone or in mixture, are also meant.

[0049] By "hair keratin fibers" is meant hair. In other words, the expressions "hair keratin fibers" and "hair" are equivalent in the remainder of the description.

[0050] For the purposes of the present invention, the term "hair" means the hair of the head. This term does not correspond to body hair, eyebrows, or eyelashes. Polycarbodiimide compound

[0051] As indicated previously, the composition C used in the context of the process according to the invention comprises one or more (poly)carbodiimide compound(s) chosen from the compounds of formula (II).

[0052] Composition C may comprise at least two distinct (poly)carbodiimide compounds as defined above, present as a mixture in the composition.

[0053] The term “hydrocarbon radical” means a saturated or unsaturated, linear or branched radical having from 1 to 300 carbon atoms, preferably from 1 to 250 carbon atoms, more preferably from 1 to 200 carbon atoms. Preferably, the hydrocarbon radical is a linear and saturated radical.

[0054] The hydrocarbon radical may comprise one or more cyclic groups.

[0055] The hydrocarbon radical may be interrupted by one or more heteroatom(s), in particular chosen from O, S or N and / or substituted by one or more cation(s), anion(s), or zwitterion(s) or cationic group(s) such as ammonium, anionic group(s) such as carboxylate, or zwitterionic group(s), and / or comprising a metal ion which may be incorporated in the form of a salt.

[0056] The term "heteroatom(s)" means an oxygen O, sulfur S or nitrogen N atom, as well as halogen atoms such as Cl, F, Br and I. If the heteroatom is included in the chain of the hydrocarbon radical, the heteroatom is preferably chosen from oxygen O, sulfur S or nitrogen N atoms.

[0057] Preferably, X1 and X2 independently represent an oxygen atom.

[0058] Preferably, R 1 and R 2 are independently selected from dialkylaminoalcohols, hydroxycarboxylic acid alkyl esters and (poly)alkylene glycol monoalkyl ethers, in which a hydroxy group has been removed, and mixtures thereof.

[0059] According to a preferred embodiment, R1 and R2 are independently chosen from the following groups (i) to (iv):

[0060] (i) the compound of formula (III) following:

[0061] R7-OC(O)-C(R8)(H)-(III),

[0062] in which R7 represents a C1-C3 alkyl group, and R8 represents a hydrogen atom or a C1-C3 alkyl group, preferably R7 is a methyl and R8 is a hydrogen atom or a methyl.

[0063] (ii) the compound of formula (IV) following:

[0064] R9-[O-CH2-C(H)(R10)]p-(IV),

[0065] wherein R9 represents a C1-C4 alkyl group, R10 represents a hydrogen atom or a C1-C4 alkyl group and p denotes an integer ranging from 1 to 3; preferably, R9 is methyl, ethyl or butyl and R10 is a hydrogen atom or methyl and p is equal to 1.

[0066] (iii) the compound of formula (V) following:

[0067] (Rn)2N-CH2-C(H)(R12)- (V),

[0068] in which Ru represents a C1-C4 alkyl group and R[2 represents a hydrogen atom or a C1-C4 alkyl group; preferably Ru is methyl, ethyl or butyl and R[2 is a hydrogen atom or methyl.

[0069] (iv) the compound of formula (VI) following:

[0070] R13-[O-CH2-C(H)(R14)]q- (VI),

[0071] in which R[3 represents a C1-C4 alkyl group or a phenyl, R[4 represents a hydrogen atom or a C1-C4 alkyl group and q denotes an integer ranging from 4 to 30; preferably Rn is a methyl, ethyl or butyl and Ru is a hydrogen atom or a methyl.

[0072] Preferably, R1 and R2 independently represent a compound of formula (VI) in which R13 represents a Cr-C4 alkyl group or a phenyl, preferably a Cr-C4 alkyl group, more preferably a methyl, R14 represents a hydrogen atom or a Cr-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.

[0073] According to an alternative embodiment, R 1 and R 2 are different and one of the radicals R 1 or R 2 represents a compound of formula (IV) as described above and the other radical R 1 or R 2 represents a compound of formula (VI) as described above.

[0074] Preferably, in formula (IV), R9 is methyl, ethyl or butyl and R10 is hydrogen or methyl and p is 1.

[0075] Preferably, in formula (VI), Rn is methyl, ethyl or butyl and R[4 is hydrogen or methyl and q denotes an integer ranging from 4 to 30.

[0076] According to another alternative embodiment, R1 and R2 are identical and represent a compound of formula (VI) in which Rn represents a Cr-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferably a methyl, R[4 represents a hydrogen atom or a Cr-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.

[0077] Preferably, n denotes an integer ranging from 1 to 20, more preferably from 2 to 20.

[0078] Preferably, z denotes an integer ranging from 1 to 20, more preferably from 2 to 20.

[0079] Preferably, w is equal to 1.

[0080] Preferably, w is equal to 1, n+z denotes an integer ranging from 4 to 10.

[0081] Preferably, Li is chosen from a divalent C 1 -C 10 aliphatic hydrocarbon radical. -Ci8 such as methylene, ethylene, and propylene, a C3-Cn cycloalkylene radical such as cyclopentylene, cycloheptylene, and cyclohexylene, a C3-Ci2 heterocycloalkylene group such as imidazolene, pyrrolene, and furanylene, or a C6-Ci4 arylene group such as phenylene, and mixtures thereof.

[0082] For example, Li may be selected from a radical derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis-(8-isocyanateoctyl)-1,3-dioctylcyclobutane, 4,4'-dicylclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate and phenylene diisocyanate and mixtures thereof.

[0083] Preferably, Li is chosen from a C3-Ci5 cycloalkylene radical, or a C6-Ci4 arylene group and mixtures thereof, such as the compounds of formula (VII) below:

[0084] . ...x? \ ......... / v ..... . . î ; > ï ï ; !

[0085] Preferably, L1 is 4,4-dicyclohexylene methane corresponding to the formula (VIII) following:

[0086] (VIII). 17 L 1

[0087] According to another embodiment, when L1 is a C6-C14 arylene group, Li is not the m-tetramethylxylylene radical represented by the following formula (IX):

[0088] » (IX).

[0089] As indicated previously, E independently represents a group chosen from:

[0090] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0091] in which R3 and R4 independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s);

[0092] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, optionally interrupted by one or more heteroatom(s); and

[0093] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

[0094] Preferably, R3 and IC are independently chosen from a C6-CM arylene radical such as phenylene, a C3-Ci2 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C1-Ci8 alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatom(s) and mixtures thereof.

[0095] More preferably, R3 and IC are independently chosen from a linear or branched CrCi8 alkylene radical such as methylene, butylene, propylene, ethylene, optionally interrupted by one or more heteroatom(s).

[0096] Preferably, when R5 is not a covalent bond, R5 is chosen from a C6-Ci4 arylene radical such as phenylene, a C3-Ci2 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C1-Ci8 alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0097] Preferably, R6 is chosen from a C6-Ci4 arylene radical such as phenylene, a C3-C[2] cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C1Ci8 alkylene radical such as methylene and ethylene, even permanently interrupted by one or more heteroatom(s), and their mixtures.

[0098] Preferably, E represents a group -O-R3-O- in which R3 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1Ci8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0099] More preferably, E represents a group - -O-R3-O- in which R3 represents a linear or branched CrCi8 alkylene radical such as methylene, butylene, propylene, ethylene, optionally interrupted by one or more heteroatom(s).

[0100] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from alpha-methylstyryl-isocyanates of the following formula (X):

[0101] (X),

[0102] wherein R independently represents an alkyl group having from 1 to 24 carbon atoms, a cycloalkyl group having from 3 to 24 carbon atoms or an aryl group having from 6 to 24 carbon atoms, and,

[0103] n denotes an integer ranging from 2 to 100.

[0104] In this embodiment, the term “alkyl group” is as defined above.

[0105] In this embodiment, the term “cycloalkyl group” is as defined above.

[0106] In this embodiment, n can denote an integer ranging from 2 to 50, preferably from 3 to 30, more preferably from 5 to 10.

[0107] According to another particular embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI):

[0108] 0¾ (XI), CH GsssssR ™— R H-----

[0109] wherein R independently represents an alkyl group having from 1 to 24 carbon atoms, a cycloalkyl group having from 3 to 24 carbon atoms, or an aryl group having from 6 to 24 carbon atoms.

[0110] “Alkyl group”, “cycloalkyl group” and “aryl group” are as defined above.

[0111] According to a preferred embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0112] - Xi and X2 independently represent an oxygen atom;

[0113] - R1 and R2 are independently chosen from dialkylaminoalcohols, al- esters hydroxycarboxylic acid alkyl ethers and (poly)alkylene glycol monoalkyl ethers, in which a hydroxy group has been removed, and mixtures thereof, preferably (poly)alkylene glycol monoalkyl ethers, in which a hydroxy group has been removed, more preferably, the compound of formula (VI) as described above in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferably a methyl, RM represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30

[0114] - n and z, when present, denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0115] - Li, when present, is chosen from an aliphatic hydrocarbon radical divalent C1-C18, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group, or a C6-C14 arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical;

[0116] - A, when present, is chosen from an aliphatic hydrocarbon radical divalent C1-C18, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group, or a C6-C14 arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical;

[0117] - E, when present, independently represents a group chosen from:

[0118] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0119] in which R3 and R4 are independently chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

[0120] - when R5 is not a covalent bond, R5, when present, is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof; and

[0121] - R6, when present, is chosen from a C6-C14 arylene radical, a cy radical C3-C12 alkylene, a linear or branched C1-C18 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0122] Preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0123] - Xi and X2 independently represent an oxygen atom;

[0124] - R1 and R2 are independently chosen from dialkylaminoalcohols, al- esters hydroxycarboxylic acid alkyl ethers and (poly)alkylene glycol monoalkyl ethers, in which one hydroxy group has been removed, and mixtures thereof;

[0125] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0126] - Li is chosen from a divalent aliphatic hydrocarbon radical in CrCi8, a C3-Ci5 cycloalkylene radical, a C3-Ci2 heterocycloalkylene group, or a C6-Ci4 arylene group, and mixtures thereof;

[0127] - E independently represents a group chosen from:

[0128] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0129] in which R3 and R4 are independently chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1-Ci8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

[0130] - when R5 is not a covalent bond, R5 is chosen from an arylene radical in C6-Ci4, a C3-Ci2 cycloalkylene radical, a linear or branched C1-Ci8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof; and

[0131] -R6 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0132] More preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0133] - Xi and X2 independently represent an oxygen atom;

[0134] - R1 and R2 are independently monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed;

[0135] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0136] - Li is a C3-Ci5 cycloalkylene radical;

[0137] - E independently represents a group chosen from:

[0138] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0139] in which R3 and R4 are independently chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

[0140] - when R5 is not a covalent bond, R5 is chosen from an arylene radical in C6-Ci4, a C3-Ci2 cycloalkylene radical, a linear or branched C1-Ci8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof; and

[0141] - R6 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0142] Even more preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0143] - Xi and X2 independently represent an oxygen atom;

[0144] - R1 and R2, independently represent the compound of formula (VI) following:

[0145] R13-[O-CH2-C(H)(R14)]q- (VI),

[0146] in which R13 represents a Cr-C4 alkyl group or a phenyl, preferably a Cr-C4 alkyl group, more preferably a methyl, R14 represents a hydrogen atom or a Cr-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;

[0147] - n and z denote an integer ranging from 2 to 20, with n+z ranging from 4 to 10 and w is equal to 1;

[0148] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cyclo- heptylene, cyclohexylene and 4,4-dicyclohexylene methane; and

[0149] - E represents a group -O-R3-O- in which R3 is chosen from a radical C6-Ci4 arylene, a C3-Ci2 cycloalkylene radical, a linear or branched C1-Ci8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0150] Even more preferably, the (poly)carbodihnide compound is chosen from the compounds of formula (II) in which:

[0151] - Xi and X2 independently represent an oxygen atom;

[0152] - R1 and R2, independently represent the compound of formula (VI) following:

[0153] R13-[O-CH2-C(H)(R14)]q- (VI)

[0154] in which R13 represents a Cr-C4 alkyl group or a phenyl, preferably a Cr-C4 alkyl group, more preferably a methyl, R14 represents a hydrogen atom or a Cr-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;

[0155] - n and z denote an integer ranging from 2 to 20, with n+z ranging from 4 to 10 and w is equal to 1;

[0156] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cyclo- heptylene, cyclohexylene, 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and

[0157] - E represents a group -O-R3-O- in which R3 represents a radical linear or branched C1-C18 alkylene such as methylene, propylene, butylene ethylene, optionally interrupted by one or more heteroatom(s).

[0158] According to a preferred embodiment, the (poly)carbodihnide compound is a compound of the following formula (XII):

[0159]

[0160] in which L1 is 4,4-dicyclohexylene methane, n and z denote an integer ranging from 2 to 20, with n+z ranging from 4 to 10, E represents a group -O-R3-O- in which R3 represents a linear or branched CrCi8 alkylene radical such as methylene, propylene, butylene ethylene, optionally interrupted by one or more heteroatom(s), and r and s denote an integer ranging from 4 to 30.

[0161] Advantageously, the total amount of the (poly)carbodiimide compound(s) of formula (II) ranges from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, even more preferably from 0.5 to 8%, better still from 1 to 6% by weight relative to the total weight of composition C. Silicone acrylic copolymer

[0162] Composition C used in the context of the process according to the invention comprises one or more silicone acrylic copolymers.

[0163] Preferably, said silicone acrylic copolymer(s) comprise:

[0164] - at least one acrylic or methacrylic or crotonic unit; and

[0165] - at least one polydimethylsiloxane (PDMS) unit.

[0166] For the purposes of the present invention, the term "polydimethylsiloxanes" (also abbreviated as PDMS) is understood to mean, in accordance with general acceptance, any organosilicon polymer or oligomer with a linear structure, of variable molecular weight, obtained by polymerization and / or polycondensation of suitably functionalized silanes, and consisting essentially of a repetition of main units in which the silicon atoms are linked together by oxygen atoms (Si-O-Si siloxane bond), comprising methyl radicals directly linked via a carbon atom on said silicon atoms.

[0167] The PDMS chains which can be used to obtain the copolymer used according to the invention comprise at least one polymerizable radical group, preferably located on at least one of the ends of the chain, that is to say that the PDMS can have for example a polymerizable radical group on each of the two ends of the chain or have a polymerizable radical group on one end of the chain and a trimethylsilyl terminal group on the other end of the chain.

[0168] By polymerizable radical group is meant a radical capable of polymerizing with other polymerizable radical groups or monomers. Preferably, the poly-dimethylsiloxane unit comprises at least one polymerizable radical group.

[0169] Preferably, the polymerizable radical group comprises at least one vinyl group.

[0170] Preferably, the polydimethylsiloxane (PDMS) unit comprises at least one polymerizable radical group comprising a vinyl group, preferably at least two polymerizable radical groups comprising a vinyl group, preferably located on at least one of the ends of the chain.

[0171] As indicated previously, said silicone acrylic copolymer(s) preferably comprise at least one acrylic or methacrylic or crotonic unit, i.e. at least one unit comprising a carboxylic group.

[0172] The term “carboxylic group” means a COOH or COO functional group, the counterion of the COO group being able to be chosen from alkali metals, alkaline earth metals, quaternary ammoniums.

[0173] Preferably, said silicone acrylic copolymer(s) comprise:

[0174] - at least one acrylic or methacrylic or crotonic unit, and at least one unit acrylic ester or methacrylic ester or vinyl ester; and

[0175] - at least one polydimethylsiloxane (PDMS) unit.

[0176] More preferably, the composition comprises one or more silicone acrylic copolymers comprising: - at least one crotonic unit and at least one unit chosen from an alkyl crotonate unit, the alkyl radical being a linear or branched, saturated radical containing from 1 to 20 carbon atoms; a vinyl acetate unit; a vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms; and mixtures thereof; and - at least one polydimethylsiloxane (PDMS) unit.

[0177] By crotonic unit is meant a unit derived from a crotonic acid monomer or one of its salts.

[0178] By alkyl crotonate unit is meant a unit derived from a crotonic acid ester monomer, having a linear or branched, saturated alkyl radical containing from 1 to 20 carbon atoms.

[0179] By vinyl alkyl ester unit is meant a unit derived from a vinyl ester monomer having a linear or branched, saturated alkyl radical containing from 2 to 20 carbon atoms.

[0180] By vinyl acetate unit is meant a unit derived from a vinyl acetate monomer.

[0181] According to a preferred embodiment, said silicone acrylic copolymer(s) comprise: - at least one crotonic unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms, and - at least one polydimethylsiloxane (PDMS) unit, preferably comprising at least one polymerizable radical group comprising a vinyl group.

[0182] According to a particularly preferred embodiment, said silicone acrylic copolymer(s) comprise: - at least one crotonic unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 6 to 16 carbon atoms, and

[0183] - at least one polydimethylsiloxane (PDMS) unit comprising at least one group polymerizable radical comprising a vinyl group.

[0184] More preferably, the composition comprises one or more silicone acrylic copolymers comprising: - at least one crotonic unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms; and - at least one polydimethylsiloxane (PDMS) unit comprising at least one polymerizable radical group comprising a vinyl group.

[0185] Even more preferably, the composition comprises one or more silicone acrylic copolymers comprising:

[0186] - at least one crotonic unit, at least one vinylacetate unit and at least one unit vinyl alkyl ester, the alkyl radical being a linear or branched, saturated radical containing from 6 to 16 carbon atoms; and

[0187] - at least one polydimethylsiloxane (PDMS) unit comprising at least one group polymerizable radical comprising a vinyl group.

[0188] Among the silicone acrylic copolymers that can be used in the context of the invention, mention may be made of the compound sold by the company Wacker Chemie AG under the trade name Belsil® PI 101, with the INCI name Crotonic Acid / Vinyl C8-12 Isoalkyl Esters / VA / Bis-Vinyldimethicone Crosspolymer.

[0189] Advantageously, the total quantity of silicone acrylic copolymer(s) ranges from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 15% by weight, better still from 2 to 10% by weight relative to the total weight of composition C. Coloring agent

[0190] Composition C used in the context of the process according to the invention comprises one or more coloring agent(s) chosen from pigments, direct dyes, and mixtures thereof.

[0191] Preferably, the composition C used in the context of the process according to the invention comprises one or more pigments.

[0192] By "pigment" is meant all pigments providing color to keratin materials. Their solubility in water at 25°C and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

[0193] The pigments which can be used are in particular chosen from organic and / or mineral pigments known in the art, in particular those which are described in the Kirk-Othmer encyclopedia of chemical technology and in the Ullmann encyclopedia of industrial chemistry.

[0194] They can be natural, of natural origin, or not.

[0195] These pigments can be in the form of powder or pigment paste. They can be coated or uncoated.

[0196] The pigments may for example be chosen from mineral pigments, organic pigments, lakes, special effect pigments such as mother-of-pearl or glitter, and mixtures thereof.

[0197] The pigment may be a mineral pigment. By mineral pigment is meant any pigment which meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Among the mineral pigments useful in the present invention, mention may be made of iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

[0198] The pigment may be an organic pigment. By "organic pigment" we mean any pigment that meets the definition in the Ullmann encyclopedia in the organic pigment chapter.

[0199] The organic pigment may in particular be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complex type compounds, isoindolinone, isoindoline, qui-nacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane, quinophthalone.

[0200] In particular, the white or colored organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments codified in the Color Index under the references Cl 42090, 69800, 69825, 74100, 74160, yellow pigments codified in the Color Index under the references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indolic, phenolic derivatives as described in patent FR 2 679 771.

[0201] As an example, we can also cite organic pigment pigment pastes such as the products sold by the company HOECHST under the name:

[0202] - COSMENYL YELLOW IOG: Pigment YELLOW 3 (Cl 11710);

[0203] - COSMENYL YELLOW G: Pigment YELLOW 1 (Cl 11680);

[0204] - ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);

[0205] - COSMENYL RED R: Pigment RED 4 (Cl 12085);

[0206] - CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);

[0207] - VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);

[0208] - COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);

[0209] - COSMENYL GREEN GG: Pigment GREEN 7 (Cl 74260);

[0210] - COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

[0211] The pigments in accordance with the invention may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments may be composed in particular of particles comprising an inorganic core, at least one binder ensuring the fixing of the organic pigments on the core, and at least one organic pigment at least partially covering the core.

[0212] The organic pigment may also be a lake. By lake is meant the dyes adsorbed on insoluble particles, the whole thus obtained remaining insoluble during use.

[0213] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

[0214] Among the colorants, mention may be made of carminic acid. Mention may also be made of the colorants known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).

[0215] As examples of lacquers, we can cite the product known under the following name: D & C Red 7 (CI 15 850:1).

[0216] The pigment may also be a special effect pigment. Special effect pigments are understood to mean pigments which generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) which is non-uniform and changes depending on the observation conditions (light, temperature, observation angles, etc.). They are thus opposed to colored pigments which provide a conventional uniform opaque, semi-transparent or transparent shade.

[0217] There are several types of special effect pigments, those with a low refractive index such as fluorescent or photochromic pigments, and those with a higher refractive index such as pearlescent pigments, interference pigments or glitter.

[0218] Examples of special effect pigments include pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxides, mica coated with iron oxide, mica coated with titanium and in particular ferric blue or chromium oxide, mica coated with titanium and an organic pigment as defined above, and pearlescent pigments based on bismuth oxychloride. Pearlescent pigments include Cellini pearlescent pigments marketed by BASF (Mica-TiO 2-lake), Prestige pearlescent pigments marketed by Eckart (Mica-TiO2), Prestige Bronze pearlescent pigments marketed by Eckart (Mica-Fe2O3) and Colorona pearlescent pigments marketed by Merck (Mica-TiO2-Fe2 O3).

[0219] Mention may also be made of gold-colored mother-of-pearls marketed in particular by BASF under the name Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); bronze mother-of-pearls marketed in particular by MERCK under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super bronze (Cloisonne); orange mother-of-pearls marketed in particular by BASF under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by MERCK under the name Passion orange (Colorona) and Matte orange (17449) (Microna); brown-tinted mother-of-pearl, notably marketed by BASF under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); copper-reflecting mother-of-pearl, notably marketed by BASF under the name Copper 340A (Timica);red-reflecting mother-of-pearl, notably marketed by the company MERCK under the name Sienna fine (17386) (Colorona); yellow-reflecting mother-of-pearl, notably marketed by the company BASF under the name; Yellow (4502) (Chromalite); red mother-of-pearl with a gold sheen, notably marketed by BASF under the name Sunstone G012 (Gemtone); pink mother-of-pearl, notably marketed by BASF under the name Tan opale G005 (Gemtone); black mother-of-pearl with a gold sheen, notably marketed by BASF under the name Nu antique bronze 240 AB (Timica), blue mother-of-pearl, notably marketed by MERCK under the name Matte blue (17433) (Microna), white mother-of-pearl with a silver sheen, notably marketed by MERCK under the name Xirona Silver and orangey pinkish-green gold mother-of-pearl, notably marketed by MERCK under the name Indian summer (Xirona) and mixtures thereof.

[0220] Still as an example of nacres, we can also cite particles comprising a borosilicate substrate coated with titanium oxide.

[0221] Particles with a glass substrate coated with titanium oxide are sold in particular under the name METASHINE MC1080RY by the company TOYAL.

[0222] Finally, as examples of nacres, mention may also be made of polyethylene terephthalate flakes, in particular those marketed by the company Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver flakes). Multilayer pigments based on synthetic substrates such as alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum may also be considered.

[0223] The special effect pigments may also be chosen from reflective particles, that is to say in particular particles whose size, structure, in particular the thickness of the layer(s) which constitute it and their physical and chemical nature, and surface condition, enable them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create on the surface of the composition or mixture, when the latter is applied to the support to be made up, highlights visible to the naked eye, that is to say brighter points which contrast with their environment by appearing to shine.

[0224] The reflective particles may be selected so as not to significantly alter the coloring effect generated by the coloring agents associated with them and more particularly so as to optimize this effect in terms of color rendering. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or reflection.

[0225] These particles can have various shapes, in particular being platelet-shaped or globular, in particular spherical.

[0226] The reflective particles, whatever their shape, may have a multi-layer structure or not and, in the case of a multi-layer structure, for example at least one layer of uniform thickness, in particular of a reflective material.

[0227] When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, in particular titanium or iron oxides obtained by synthesis.

[0228] When the reflective particles have a multi-layer structure, they may for example comprise a natural or synthetic substrate, in particular a synthetic substrate at least partially coated with at least one layer of a reflective material, in particular at least one metal or metallic material. The substrate may be single-material, multi-material, organic and / or inorganic.

[0229] More particularly, it can be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica and their mixtures, this list not being limiting.

[0230] The reflective material may comprise a layer of metal or a metallic material.

[0231] Reflective particles are described in particular in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0232] Still as an example of reflective particles comprising a mineral substrate coated with a layer of metal, mention may also be made of particles comprising a borosilicate substrate coated with silver.

[0233] Platelet-shaped particles with a silver-coated glass substrate are sold under the name MICROGLASS METASHINE REFSX 2025 PS by the company TOYAL. Particles with a nickel / chromium / molybdenum alloy-coated glass substrate are sold under the name CRYSTAL STAR GF 550, GF 2525 by the same company.

[0234] It is also possible to use particles comprising a metallic substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, titanium, said substrate being coated with at least one layer of at least one metallic oxide such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

[0235] Examples include aluminum, bronze or copper powders coated with SiO2 marketed under the name VISIONAIRE by the company ECKART.

[0236] Mention may also be made of interference effect pigments not fixed on a substrate such as liquid crystals (Helicones HC from Wacker), interference holographic flakes (Geometry Pigments or Spectra f / x from Spectratek). Special effect pigments also include fluorescent pigments, whether they are substances that fluoresce in daylight or that produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, marketed for example by the company Quantum Dots Corporation.

[0237] The variety of pigments that can be used in the present invention makes it possible to obtain a rich palette of colors, as well as particular optical effects such as metallic and interference effects.

[0238] The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 qm, preferably between 20 nm and 80 qm, and more preferably between 30 nm and 50 qm.

[0239] The pigments may be dispersed in the composition using a dispersing agent.

[0240] The dispersing agent serves to protect the dispersed particles against agglomeration or flocculation. This dispersing agent may be a surfactant, an oligomer, a polymer or a mixture of several of them, carrying one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they may attach physically or chemically to the surface of the pigments. These dispersants also have at least one functional group that is compatible or soluble in the continuous medium.In particular, esters of 12-hydroxystearic acid in particular and of C8 to C20 fatty acid and polyol such as glycerol, diglycerin, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750g / mol such as that sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel or polyhydroxystearic acid such as that sold under the reference Arlacel P100 by the company Uniqema and their mixtures are used.

[0241] As another dispersant that can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17 000 sold by the company Avecia, poly dimethylsiloxane / oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185, DC2-5225 C.

[0242] The pigments used in the composition may be surface-treated with an organic agent.

[0243] Thus, the previously surface-treated pigments useful in the context of the invention are pigments which have undergone totally or partially a surface treatment of a chemical, electronic, electrochemical, mechanochemical or mechanical nature, with an organic agent such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, p. 53-64 before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethylmethacrylates; polymers and copolymers containing acrylate units; alkanoamines; silicone compounds, for example silicones, in particular polydimethylsiloxanes; fluorinated organic compounds, for example perfluoroalkyl ethers; fluoro-silicone compounds.

[0244] The surface-treated pigments useful in the composition may also have been treated with a mixture of these compounds and / or have undergone several surface treatments.

[0245] The surface-treated pigments useful in the context of the present invention can be prepared according to surface treatment techniques well known to those skilled in the art or found as such commercially.

[0246] Preferably, the surface-treated pigments are covered by an organic layer.

[0247] The organic agent with which the pigments are treated can be deposited on the pigments by solvent evaporation, chemical reaction between the molecules of the surfactant or creation of a covalent bond between the surfactant and the pigments.

[0248] The surface treatment can thus be carried out for example by chemical reaction of a surfactant with the surface of the pigments and creation of a covalent bond between the surfactant and the pigments or fillers. This method is described in particular in US patent 4,578,266.

[0249] Preferably, an organic agent covalently bound to the pigments will be used.

[0250] The surface treatment agent may represent from 0.1 to 50% by weight of the total weight of the surface-treated pigment, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 20% by weight of the total weight of the surface-treated pigment.

[0251] Preferably, the surface treatments of the pigments are chosen from the following treatments:

[0252] - a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW;

[0253] - a Methicone treatment such as the SI surface treatment marketed by LCW;

[0254] - a Dimethicone treatment like Covasil 3.05 com surface treatment marketed by LCW;

[0255] - a Dimethicone / Trimethylsiloxysilicate treatment as the surface treatment Covasil 4.05 marketed by LCW;

[0256] - a Magnesium Myristate treatment such as the MM com surface treatment marketed by LCW;

[0257] - an Aluminum Dimyristate treatment such as the MI com surface treatment Merchandised by Miyoshi;

[0258] - a Perfluoropolymethylisopropyl ether treatment as the surface treatment FHC marketed by LCW;

[0259] - an Isostearyl Sebacate treatment like the commercialized HS surface treatment by Miyoshi;

[0260] - a Perfluoroalkyl Phosphate treatment such as the PF surface treatment marketed by Daito;

[0261] - an acrylate / Dimethicone and Perfluoroalkyl Phosphate Copolymer treatment such as the FSA surface treatment marketed by Daito;

[0262] - a Polymethylhydrogen siloxane / Perfluoroalkyl Phosphate treatment such as the FS01 surface treatment marketed by Daito;

[0263] - an Acrylate / Dimethicone Copolymer treatment as the surface treatment ASC marketed by Daito;

[0264] - an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito;

[0265] - an Acrylate copolymer treatment such as the APD surface treatment com sold by Daito;

[0266] - a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito.

[0267] According to a particular embodiment of the invention, the dispersing agent is present with organic or inorganic pigments in particulate form of sub-micron size in composition B.

[0268] By "sub-micronic" or in English "sub-micronic" is meant pigments whose particle size has been micronized by micronization method and whose average particle size is less than one micrometer (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm.

[0269] According to one embodiment, the dispersing agent and the pigment(s) are present in an amount (dispersant: pigment), according to a weight ratio, of between 1:4 and 4:1, particularly between 1.5:3.5 and 3.5:1 or better between 1.75:3 and 3:1.

[0270] The dispersing agent(s) may therefore have a silicone backbone, such as silicone polyether and amino-silicone type dispersants. Suitable dispersing agents include:

[0271] - amino-silicones ie silicones comprising one or more amino groups such than those marketed under the names and references: BYK LPX 21879, by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, marketed by Genesee polymers,

[0272] - silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik,

[0273] - polydimethylsiloxane silicones (PDMS) with carboxylic groups such as X- 22162 and X-22370 by Shin-Etsu, silicone epoxy such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695, by Genesee Polymers, or Tego ® RC 1401, Tego ® RC 1403, Tego ® RC 1412, by Evonik.

[0274] According to a particular embodiment, the dispersing agent(s) are of the amino-silicone type and are cationic.

[0275] Preferably, the pigment(s) is(are) chosen from mineral, mixed mineral-organic or organic pigments.

[0276] In one variant of the invention, the pigment(s) are organic pigments, preferably organic pigments surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment(s) are mineral pigments.

[0277] Preferably, the pigment(s) are chosen from iron oxides, in particular red, brown or black. As an example of iron oxide, mention may be made of iron oxide sold by the company Sun Chemical under the name SunPuro® Red Iron Oxide.

[0278] Direct dye

[0279] Composition C used in the context of the process according to the invention may comprise one or more direct dye(s).

[0280] By "direct dye" we mean natural and / or synthetic dyes, different from oxidation dyes. These are dyes which will diffuse superficially on the fiber.

[0281] They can be ionic or non-ionic, preferably cationic or non-ionic.

[0282] Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or as mixtures.

[0283] The direct dyes are preferably cationic direct dyes. Mention may be made of the cationic hydrazono dyes of formulae (XIII) and (XIV), the cationic azo dyes (XV) and (XVI) below:

[0284] n'^VT? \ v rj (XIII), LJ Ret'-X(>a)-^=C(R^ v 7

[0285] Hét*-C(Ra)=NN(Rb)-Aî» Q (XIV),

[0286] Hét+-N=N-Ar: Q- ^XV)'

[0287]

[0288] formulas (XIII) to (XVI) in which:

[0289] - Het+ represents a cationic heteroaryl radical, preferably with a ca charge endocyclic cationic such as imidazolium, indolium, or pyridinium, optionally substituted preferentially by at least one (CrC8)alkyl group such as methyl;

[0290] - Ar+ represents an aryl radical, such as phenyl or naphthyl, with a cationic charge exocyclic preferentially ammonium particularly tri(Ci-C8)alkyl-ammonium such as trimethylammonium;

[0291] - Ar represents an aryl group, in particular phenyl, optionally substituted, preferentially by one or more electron-donating groups such as i) (Ci-C8)alkyl optionally substituted, ii) (Ci-C8)alkoxy optionally substituted, iii) (di)(Ci-C8)(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) N-(Ci-C8)alkyl-N-aryl(Ci-C8)alkylamino optionally substituted or Ar represents a julolidine group;

[0292] - Ar” represents an optionally substituted (hetero)aryl group such that phenyl or pyrazolyl optionally substituted, preferably by one or more (CrC8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (CrC8)alkoxy or phenyl groups;

[0293] - Ra and Rb, identical or different, representing a hydrogen atom or a (CrC8)alkyl group optionally substituted, preferably by a hydroxyl group;

[0294] or the substituent Ra with a substituent of Het+ and / or Rb with a substituent of Ar form together with the atoms which carry them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (CrC4)alkyl group optionally substituted by a hydroxyl group;

[0295] - Q- represents an organic or inorganic anionic counterion such as a halide or an alkyl sulfate.

[0296] In particular, mention may be made of the direct dyes with endocyclic azo and hydrazono cationic charge of formula (XIII) to (XVI) as defined above; more particularly, the direct cationic dyes with endocyclic cationic charge described in patent applications WO 95 / 15144, WO 95 / 01772 and EP-714954; preferably the following direct dyes:

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307] Formulas (XVII) and (XVIII) in which: - R1 represents a (Ci-C4)alkyl group such as methyl; - R2 and R3, identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group such as methyl; and - R4 represents a hydrogen atom or an electron-donating group such as (Ci-C8)alkyl optionally substituted, (Cr-C8)alkoxy optionally substituted, (di)(Cr-C8)(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group; particularly R4 is a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferably CH, - Q- is an anionic counterion as defined above, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl. In particular, the dyes of formula (XV) and (XVI) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives with Q' an anionic counterion as defined previously, particularly halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl. The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly called “acid” direct dyes for their affinity with alkaline substances. Anionic direct dyes means any direct dye comprising in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and acid natural dyes. As acid dyes useful in the invention, mention may be made of the dyes of formulae (XIX), (XIX'), (XX), (XX'), (XXI), (XXI'), (XXII), (XXII'), (XXIII), (XXIV), (XXV) and (XXVI) following:

[0308] a. diaryl anionic azo dyes of formula (XIX) or (XIX'):

[0311] formulas (XIX) and (XIX') in which:

[0312] - R7, R8, R9, Rio, R'7, R'8, R'9 and R'1O, identical or different, represent an atom of hydrogen or a group chosen from:

[0313] - alkyl;

[0314] - alkoxy, alkylthio;

[0315] - hydroxy, mercapto;

[0316] - nitro, nitroso;

[0317] - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing an atom hydrogen, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

[0318] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0319] - (O)CO—, M+ with M+ as defined previously;

[0320] - R”-S(O)2-, with R” representing a hydrogen atom, an alkyl group, a aryl, (di)(alkyl)amino, aryl(alkyl)amino group; preferably a phenylamino or phenyl group;

[0321] - R'”-S(O)2-X'- with R”' representing an alkyl, optionally aryl group substituted, X' as defined above;

[0322] - (di)(alkyl)amino;

[0323] - aryl(alkyl)amino optionally substituted by one or more selected groups among i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+ and iv) alkoxy with M+ as defined previously;

[0324] - optionally substituted heteroaryl; preferably a benzo- group thiazolyl;

[0325] - cycloalkyl, in particular cyclohexyl;

[0326] - Ar-N=N- with Ar representing an optionally substituted aryl group; pre preferably a phenyl optionally substituted by one or more alkyl, (O)2S(O-)-, M+ or phenylamino groups;

[0327] - or two contiguous groups R7 with R8 or R8 with R9 or R9 with R10 together form a fused benzo group A'; and R'7 with R'8 or R'8 with R'9 or R'9 with R'1O together form a fused benzo group B'; with A' and B' optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+; iv) hydroxy; 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; with M+, R°, X, X', X” and Ar as defined above;

[0328] - W represents a sigma o bond, an oxygen atom, a sulfur atom, or a radical divalent i) -NR- with R as defined above, or ii) methylene -C(Ra)(Rb)- with Ra and Rb identical or different, representing a hydrogen atom or an aryl group, or Ra and Rb together form with the carbon atom which carries them a cycloalkyl spiro; preferably W represents a sulfur atom or Ra and Rb together form a cyclohexyl;

[0329] it being understood that formulas (XIX) and (XIX') comprise at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical (O)CO—, M+ on one of the rings A, A', B, B' or C; preferably sodium sulfonate.

[0330] A titre d’exemple de colorants de formule (XIX) on peut citer : 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 Yellow 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 ou sunset yellow;

[0331] et à titre d’exemple de colorants de formule (XIX’) on peut citer : Acid Red 111, Acid Red 134, Acid yellow 38 ;

[0332] b) les colorants azo anioniques pyrrazolone de formule (XX) et (XX’) :

[0335] formulas (XX) and (XX') in which:

[0336] - Rn, R12 and Rn, identical or different, represent a hydrogen atom, of halogen, an alkyl group or -(O)2S(O-), M+ with M+ as defined above;

[0337] - Rm represents a hydrogen atom, an alkyl group or a group - C(O)O-, M+ with M+ as defined previously;

[0338] - Rb represents a hydrogen atom;

[0339] - Ri6 represents an oxo group in which case R'i6 is absent, or else R[5 with R[6 together form a double bond;

[0340] - Rn and Ri8, identical or different, represent a hydrogen atom, or a group chosen from:

[0341] - (O)2S(O-)-, M+ with M+ as defined previously;

[0342] - Ar-OS(O)2- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted by one or more alkyl groups;

[0343] - R19 and R2q, together form either a double bond or a benzo D' group, possibly substituted;

[0344] - R' i6, R' 19 and R'2O, identical or different, represent a hydrogen atom or a alkyl or hydroxy group;

[0345] - R2i represents a hydrogen atom, an alkyl or alkoxy group;

[0346] - Ra and Rb, identical or different, are as defined previously, preferably Ra represents a hydrogen atom and Rb represents an aryl group;

[0347] - Y represents either a hydroxy group or an oxo group;

[0348] - * » - - represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group;

[0349] it being understood that formulas (XX) and (XX') comprise at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical -C(O)O-, M+ on one of rings D or E; preferably sodium sulfonate;

[0350] As examples of dyes of formula (XX) we can cite: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (XX') we can cite: Acid Yellow 17;

[0351] c) the anthraquinone dyes of formula (XXI) and (XXI'):

[0354] formulas (XXI) and (XXI') in which:

[0355] - R22, R23, R24, R25, R26 and R27, identical or different, represent an atom of hydrogen, halogen, or a group chosen from:

[0356] - alkyl;

[0357] - hydroxy, mercapto;

[0358] - alkoxy, alkylthio;

[0359] - optionally substituted aryloxy or arylthio, preferably substituted by one or several groups chosen from alkyl and (O)2S(O-)-, M+ with M+ as defined previously;

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368]

[0369]

[0370]

[0371]

[0372]

[0373] - aryl(alkyl)amino optionally substituted by one or more groups chosen from alkyl and (O)2S(O-)-, M+ with M+ as defined previously; - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino - (O)2S(O-)-, M+ with M+ as defined previously; - Z' represents a hydrogen atom or a group NR28R29 with R28 and R29, identical or different, representing a hydrogen atom or a group chosen from: - alkyl; - polyhydroxyalkyl such as hydroxyethyl; - aryl optionally substituted by one or more groups, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O-)-, M+ with M+ as defined above; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R°, X, X' and X” as defined above, preferably R° represents an alkyl group; - cycloalkyl, in particular cyclohexyl; - Z represents a group chosen from hydroxy and NR'28R'29 with R'28 and R'29, identical or different, representing the same atoms or groups as R28 and R29 as defined previously; it being understood that formulas (XXI) and (XXI') comprise at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical -C(O)O-, M+; preferably sodium sulfonate; 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 examples of dyes of formula (XXI') include: Acid Black 48; (d) nitrated dyes of formula (XXII), (XXII'): (XXII),

[0374] (XXII'),

[0375] formulas (XXII) and (XXII') in which:

[0376] - R3o, R3i and R32, identical or different, represent a hydrogen atom, of halogen, or a group chosen from:

[0377] - alkyl;

[0378] - alkoxy optionally substituted by one or more hydroxy groups, alkylthio optionally substituted by one or more hydroxy groups;

[0379] - hydroxy, mercapto;

[0380] - nitro, nitroso;

[0381] - polyhaloalkyl;

[0382] - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R°; X, X' and X” as defined previously;

[0383] - (O)2S(O-)-, M+ with M+ as defined previously;

[0384] - (O)CO—, M+ with M+ as defined previously;

[0385] - (di)(alkyl)amino;

[0386] - (di)(hydroxyalkyl)amino;

[0387] - heterocycloalkyl such as piperidino, piperazino or morpholino; particularly R 30, R3i and R32 represent a hydrogen atom;

[0388] - Rc and Rd, identical or different, represent a hydrogen atom or a alkyl group;

[0389] - W is as defined above; W particularly represents a group -NH-;

[0390] - ALK represents a linear or branched divalent alkylene group, C1-C6; particularly ALK represents a -CH2-CH2- group;

[0391] - n is 1 or 2;

[0392] - p represents an integer between 1 and 5 inclusive;

[0393] - q represents an integer between 1 and 4 inclusive;

[0394] - u is 0 or 1;

[0395] - when n is 1, J represents a nitro, or nitroso group; particularly nitro ;

[0396] - when n is 2, J represents an oxygen atom, a sulfur atom, or a divalent radical -S(0)m- with m representing an integer 1 or 2; preferably J represents a radical -S02- ;

[0397] - M' represents a hydrogen atom or a cationic counterion;

[0398] - ... present or absent represents a benzo group possibly

[0399]

[0400]

[0401]

[0402] substituted by one or more R30 groups as defined above, it being understood that formulas (XXII) and (XXII') comprise at least one sulfonate radical (O)2S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferably sodium sulfonate. Examples of dyes of formula (XXII) include: Acid Brown 13; Acid Orange 3; examples of dyes of formula (XXII') include: Acid Yellow 1, 2,4-dinitro-1-naphthol-7-sulfonic acid sodium salt, 2-piperidino 5-nitro benzene sulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid, 4-[3-hydroxyethylamino-3-nitrobenzene sulfonic acid; EXT D&C yellow 7; e) triarylmethane dyes of formula (XXIII): (XXIII),

[0403] formula (XXIII) in which:

[0404] - R33, R34, R35 and R36, identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted by a (O)mS(O-)-, M+ group with M+ and m as defined above;

[0405] - R37, R38, R39, R40, R41, R42, R43 and R44, identical or different, represent an atom of hydrogen or a group chosen from:

[0406] - alkyl;

[0407] - alkoxy, alkylthio;

[0408] - (di)(alkyl)amino;

[0409] - hydroxy, mercapto;

[0410] - nitro, nitroso;

[0411] - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X”- with R° representing an atony hydrogen, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

[0412] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0413] - (O)CO—, M+ with M+ as defined previously;

[0414] - or two contiguous groups Ru with R2 or R42 with R3 or R3 with R44 together form a fused benzo group: I'; with I' optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2 S(O-)-, M+; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X”-; with M+, R°, X, X', X” as defined above;

[0415] particularly R37 to Ro represent a hydrogen atom, and R4[ to R4, identical or different, represent a hydroxy group or (O)2S(O-)-, M+; and when R3 with R^ together form a benzo group, it is preferentially substituted by a (O)2S(O-)- group;

[0416] it being understood that at least one of the cycles G, H, I or I' comprises at least one sulfonate radical (O)2S(O-)- or one carboxylate radical -C(O)O-; preferably sulfonate.

[0417] As examples of dyes of formula (XXIII) we can cite: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50.

[0418] f) dyes derived from xanthene of formula (XXIV):

[0420] formula (XXIV) in which:

[0421] - R5, R46, R7 and R48, identical or different, represent a hydrogen atom or a halogen atom;

[0422] - R9, R50, R5i and R52, identical or different, represent a hydrogen atom, of halogen, or a group chosen from:

[0423] - alkyl;

[0424] - alkoxy, alkylthio;

[0425] - hydroxy, mercapto;

[0426] - nitro, nitroso;

[0427] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0428] - (O)CO—, M+ with M+ as defined previously;

[0429] particularly R49, R50, R5i and R52 represent a hydrogen or halogen atom

[0430] - G represents an oxygen atom, a sulfur atom or an NRe group with Re such that defined previously; particularly G represents an oxygen atom;

[0431] - L represents an alcoholate O-, M+; a thioalcoholate S-, M+ or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined previously; M+ is particularly sodium or potassium;

[0432] - L' represents an oxygen atom, sulfur or an ammonium group: N+RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an alkyl group, an optionally substituted aryl group; L' particularly represents an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (O)mS(O-)-, M+ with m and M+ as defined previously;

[0433] - Q and Q', identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;

[0434] - M+ is as defined previously.

[0435] As examples of dyes of formula (XXIV) we can cite: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[0436] g) dyes derived from indole of formula (XXV):

[0437] (XXV),

[0438] formula (XXV) in which:

[0439] - R53, R54, R55, R56, R57, R58, R59 and R60, identical or different, represent an atom of hydrogen or a group chosen from:

[0440] - alkyl;

[0441] - alkoxy, alkylthio;

[0442] - hydroxy, mercapto;

[0443] - nitro, nitroso;

[0444] - R°-C(X)-X'-, R°-X' -C(X)-, R°-X'-C(X)-X' ' - with R° representing an atony hydrogen, an alkyl or aryl group; X, X' and X”, identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

[0445] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0446] - (O)CO—, M+ with M+ as defined previously;

[0447] - G represents an oxygen atom, a sulfur atom or an NRe group with Re such that defined previously; particularly G represents an oxygen atom;

[0448] - Ri and Rh, identical or different, represent a hydrogen atom or a alkyl group;

[0449] it being understood that formula (XXIII) comprises at least one sulfonate radical (O)2S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferably sodium sulfonate.

[0450] As examples of dyes of formula (XXV) we can cite: Acid Blue 74;

[0451] h) quinoline-derived dyes of formula (XXVI): (XXVI),

[0453] formula (XXVI) in which:

[0454] - R6i represents a hydrogen atom, halogen or an alkyl group;

[0455] - R62, R63, and RM, identical or different, represent a hydrogen atom or a (O)2S(O-)-, M+ group with M+ representing a hydrogen atom or a cationic counterion;

[0456] or R6[ with R62, or R6[ with R64, together form a benzo group optionally substituted by one or more (O)2S(O-)-, M+ groups with M+ representing a hydrogen atom or a cationic counterion;

[0457] it being understood that formula (XXVI) comprises at least one sulfonate radical (O)2 S(O-)-, M+ preferably sodium sulfonate.

[0458] As examples of dyes of formula (XXVI) we can cite: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0459] 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, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin, orceins. Extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna may also be used.

[0460] Preferably, the direct dyes are chosen from anionic direct dyes.

[0461] The coloring agent(s) may be present in a total amount ranging from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight relative to the total weight of composition C, preferably the coloring agent(s) are chosen from pigments.

[0462] The pigment(s) may be present in a total amount ranging from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, better still from 0.5 to 10% by weight relative to the total weight of composition C.

[0463] The direct dye(s) may be present in a total amount ranging from 0.001 to 10% by weight of the total weight of the composition, preferably from 0.005 to 5% by weight relative to the total weight of composition C. Organic solvents

[0464] Composition C used in the context of the process according to the invention may comprise one or more organic solvents.

[0465] Preferably, the composition comprises ethanol.

[0466] The organic solvents may be present in a total amount ranging from 20 to 90% by weight, preferably ranging from 30 to 85% by weight, preferably ranging from 35 to 80% by weight relative to the total weight of composition C.

[0467] The composition C used in the context of the process according to the invention may be aqueous. The water content may range from 0.1 to 50% by weight, preferably from 1 to 50% by weight, more preferably from 10 to 50% by weight relative to the total weight of the composition C. Additives

[0468] Composition C used in the context of the process according to the invention may contain any adjuvant or additive usually used.

[0469] Among the additives that may be contained in the composition, mention may be made of reducing agents, thickening agents, softeners, anti-foaming agents, moisturizing agents, UV filters, peptizers, perfumes, anionic, cationic, non-ionic or amphoteric surfactants, proteins, vitamins, preservatives, oils, waxes and mixtures thereof.

[0470] Composition C used in the context of the process according to the invention may be in particular 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 multiple (W / O / W or polyol / O / W or O / W / O), in the form of a cream, mousse, stick, dispersion of vesicles in particular of ionic or non-ionic lipids, two-phase or multi-phase lotion.

[0471] A person skilled in the art will be able to choose the appropriate galenic form, as well as its method of preparation, on the basis of his general knowledge, taking into account on the one hand the nature of the constituents used, in particular their solubility in the support, and on the other hand the application envisaged for the composition. Application of composition D

[0472] The hair coloring process according to the invention may further comprise the application to the hair of a composition D comprising at least one silicone compound comprising at least one carboxylic group.

[0473] Preferably, the silicone compound comprising at least one carboxylic group is a silicone compound different from the silicone acrylic copolymer as described previously.

[0474] The term “carboxylic group” means a COOH or COO functional group, the counterion of the COO group being able to be chosen from alkali metals, alkaline earth metals, quaternary ammoniums.

[0475] The silicones that can be used can be soluble or insoluble in composition D; they can be in the form of oil, wax, resin or gum; silicone oils and gums are preferred.

[0476] Silicones are notably described in detail in the work of Walter NOLL "Chemistry and Technology of Silicones" (1968), Academie Press.

[0477] Preferably, the silicone compound(s) comprising at least one carboxylic group are chosen from the organosiloxanes of the following formula (XXVII):

[0478] (XXVII)

[0479] in which: - RI independently represent an alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms; a hydroxy group; an alkoxy group having from 1 to 20 carbon atoms or an aryl group having from 6 to 12 carbon atoms; - R2 independently represents a group R4-C00M with R4 representing a linear or branched alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from the sulfur atom, the nitrogen atom, the oxygen atom and their mixtures, and M representing a hydrogen atom; an alkali or alkaline-earth metal or a quaternary ammonium NR'3, with R' identical or different, representing H or alkyl having from 1 to 4 carbon atoms; a pyrrolidone radical comprising a carboxylic group COOH or a group Ra-(ORb)x-COOM with Ra representing a linear or branched alkylene group, having from 1 to 4 carbon atoms, Rb representing an alkyl group having from 1 to 4 carbon atoms, x being an integer ranging from 1 to 200;and M representing a hydrogen atom, an alkali or alkaline earth metal or a quaternary ammonium NR'3, with R', identical or different, representing H or an alkyl having from 1 to 4 carbon atoms; ; - R3 independently represent an alkyl group having from 1 to 20 carbon atoms; a hydroxy group; an R4-COOM group with R4 representing a linear or branched alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from the sulfur atom, the nitrogen atom, the oxygen atom and their mixtures, and M representing a hydrogen atom; an alkali or alkaline-earth metal or a quaternary ammonium NR'3, with R' identical or different, representing H or alkyl having from 1 to 4 carbon atoms; an alkoxy group having from 1 to 20 carbon atoms; an aryl group having from 6 to 12 carbon atoms or a group Ra-(ORb)x -COOM with Ra representing a linear or branched alkylene group having from 1 to 4 carbon atoms, Rb representing an alkyl group having from 1 to 4 carbon atoms, x being an integer ranging from 1 to 200;and M representing a hydrogen atom, an alkali or alkaline earth metal or a quaternary ammonium NR'3, with R', identical or different, representing H or an alkyl having from 1 to 4 carbon atoms; ; - n denotes an integer ranging from 1 to 1000; - p designated an integer ranging from 0 to 1000; it being understood that at least one of the radicals R2 and / or R3 comprises a carboxylic group COOH or COOM with M representing an alkali or alkaline-earth metal or a quaternary ammonium NR'3, with R', identical or different, representing H or an alkyl having from 1 to 4 carbon atoms.

[0480] In particular, the silicone compound(s) comprising at least one carboxylic group may be chosen from the organosiloxanes of the following formula (XXVIII):

[0481] (XXVIII), R1 ^OOC— R4—Si™ R1 R1 ~R4 — ÇQOM RI

[0482] in which: - RI independently represents a linear or branched alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, even better from 1 to 6 carbon atoms; preferably methyl; - R4 independently represents a linear or branched alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from the sulfur atom, the nitrogen atom, the oxygen atom and their mixtures; or a divalent group Ra-(ORb)x- with Ra representing a linear or branched alkylene group, having from 1 to 4 carbon atoms, Rb representing an alkylene group having from 1 to 4 carbon atoms, and x being an integer ranging from 1 to 200; - M independently represents a hydrogen atom, an alkali metal or an alkaline- earthy or a quaternary ammonium NR'3, with R' identical or different, re having H or an alkyl having from 1 to 4 carbon atoms; - n denotes an integer ranging from 1 to 1000;

[0483]

[0484] - organosiloxanes of the following formula (XXIX):

[0485] in which: - RI independently represents an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably a methyl - R4 represents a linear or branched, saturated or unsaturated alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from the sulfur atom, the nitrogen atom, the oxygen atom and mixtures thereof; or a divalent group Ra-(ORb)x- with Ra representing a linear or branched alkylene group having from 1 to 4 carbon atoms, Rb representing an alkylene group having from 1 to 4 carbon atoms, and x being an integer ranging from 1 to 200; - M represents a hydrogen atom; an alkali or alkaline-earth metal or a quaternary ammonium NR'3, with R' identical or different, representing H or a alkyl having from 1 to 4 carbon atoms; - p denotes an integer ranging from 1 to 1000; - n denotes an integer ranging from 1 to 1000;

[0486] - organosiloxanes of the following formula (XXX):

[0487]

[0488] in which: - RI independently represents an alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, even better from 1 to 6 carbon atoms; preferably methyl; - R4 represents a linear or branched alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from the sulfur atom, the nitrogen atom, the oxygen atom and their mixtures; or a divalent group Ra-(ORb)x- with Ra representing a linear or branched alkylene group, having from 1 to 4 carbon atoms, R b representing an alkylene group having from 1 to 4 carbon atoms, and x being an integer ranging from 1 to 200; - R3 represents an alkyl group having from 1 to 20 carbon atoms; an alkoxy group having from 1 to 20 carbon atoms or an aryl group having from 6 to 12 carbon atoms; - M independently represents a hydrogen atom, an alkali or alkaline earth metal or a quaternary ammonium NR'3, with R', identical or different, representing H or an alkyl having from 1 to 4 carbon atoms; - n denotes an integer ranging from 1 to 1000;

[0489] - organosiloxanes of the following formula (XXXI):

[0490]

[0491]

[0492]

[0493]

[0494] in which: - R8 represents an alkyl group having from 1 to 6 carbon atoms, preferably a methyl; - m denotes an integer ranging from 1 to 1000; - n denotes an integer ranging from 1 to 1000. -and their mixtures. Among the organosiloxanes of formula (XXVIII), we can cite polydimethylsiloxane (PDMS) with carboxy terminal function such as the compounds sold by the company Momentive under the trade name SILFORM INX (INCI name: Bis-Carboxydecyl dimethicone). Among the organosiloxanes of formula (XXIX), mention may be made of polydimethylsiloxane (PDMS) with a carboxy pendant function such as the compounds sold by the company Shin Etsu under the trade name X-22-3701E.

[0495]

[0496]

[0497]

[0498] Among the organosiloxanes of formula (XXX), mention may be made of polydimethylsiloxane (PDMS) with a carboxy terminal function such as the compounds sold by the company Shin Etsu under the trade name X-22-3710. Among the organosiloxanes of formula (XXXI), we can cite the compounds sold by the company Grant Industries under the trade name Grandsil SiW-PCA-10 (INCI name: Dimethicone (and) PCA Dimethicone (and) Butylene Glycol (and) Decyl Glucoside). Silicone compounds comprising a carboxylic group may, for example, correspond to the compounds described in patent application EPI86507 in the name of Chisso Corporation introduced here by reference. Preferably, the silicone compound(s) comprising at least one carboxylic group are chosen from organopolysiloxanes of formula (XXVIII), organo- monopolysiloxane of formula (XXIX) and mixtures thereof.

[0499] More preferably, the silicone compound(s) comprising at least one carboxylic group are chosen from the organopolysiloxanes of the following formula (XXVIII):

[0500] (XXVIII) ri r ri “ ri MOOC — R 4 — If «--OR— S s------O -— St —— R4 —C 00 M M RI '— — jj

[0501] in which:

[0502] - RI independently represents an alkyl group, linear or branched, having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, even better from 1 to 6 carbon atoms; preferably methyl; - R4 independently represents a linear or branched alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from the sulfur atom, the nitrogen atom, the oxygen atom and their mixtures; or a divalent group Ra-(ORb)x- with Ra representing a linear or branched alkylene group, having from 1 to 4 carbon atoms, Rb representing an alkylene group having from 1 to 4 carbon atoms, and x being an integer ranging from 1 to 200; - M independently represents a hydrogen atom, an alkali or alkaline earth metal or a quaternary ammonium NR'3, with R', identical or different, representing H or an alkyl having from 1 to 4 carbon atoms; - n denotes an integer ranging from 1 to 1000.

[0503] Advantageously, the total quantity of silicone compound(s) comprising at least one carboxylic group ranges from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.5 to 10% by weight, better still from 1 to 5% by weight relative to the total weight of composition D. Oils

[0504] Composition D may comprise one or more oil(s).

[0505] Preferably, composition D comprises one or more oil(s). More preferably, composition D comprises one or more oil(s) chosen from alkanes.

[0506] By “oil” is meant a fatty substance which is liquid at room temperature (25°C) and at atmospheric pressure (760 mm Hg or 1.013 105 Pa).

[0507] The oil may be volatile or non-volatile.

[0508] By "volatile oil" is meant an oil capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. Volatile oil is a volatile cosmetic oil, liquid at room temperature. More precisely, a volatile oil has an evaporation rate of between 0.01 and 200 mg / cm2 / min, inclusive (see protocol for measuring the evaporation rate indicated in the text below).

[0509] By "non-volatile oil" is meant an oil remaining on the skin or keratin fiber at room temperature and atmospheric pressure. More precisely, a non-volatile oil has an evaporation rate strictly less than 0.01 mg / cm2 / min (see protocol for measuring the evaporation rate indicated in the text below).

[0510] Preferably, the composition comprises one or more oil(s) chosen from C6-C16 alkanes and / or their mixtures.

[0511] As regards C6-Ci6 alkanes, these can be linear, branched, possibly cyclic.

[0512] Mention may in particular be made of branched C8-Ci6 alkanes such as C8-Ci6 isoalkanes (also called isoparaffins), isododecane, isodecane, isohexadecane and for example the oils sold under the trade names Isopars or Permetyls, and their mixtures.

[0513] Mention may also be made of linear alkanes, preferably of plant origin, comprising from 7 to 15 carbon atoms, in particular from 9 to 14 carbon atoms, and more particularly from 11 to 13 carbon atoms.

[0514] As an example of a linear alkane suitable for the invention, mention may be made of n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14), -pentadecane (C15), and mixtures thereof, and in particular the mixture of n-undecane (C11) and n-tridecane (C13) described in example 1 of application WO2008 / 155059 from Cognis.

[0515] Mention may also be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97, as well as their mixtures.

[0516] As examples of alkanes suitable for the invention, mention may be made of the alkanes described in patent applications WO 2007 / 068371 and WO2008 / 155059. These alkanes are obtained from fatty alcohols, themselves obtained from copra or palm oil.

[0517] According to a particular embodiment, the composition comprises isododecane. Such a compound is, for example, isododecane sold under the reference ISO-DODECANE by INEOS.

[0518] Preferably, composition D comprises one or more oil(s) chosen from C8-C16 alkanes, more preferably among isododecane, isohexadecane, tetradecane and / or their mixtures.

[0519] More preferably, composition D comprises isododecane.

[0520] Composition D may comprise one or more oils present in a total amount of between 30% and 99% by weight, preferably between 50% and 99% by weight, better still between 70% and 99% by weight relative to the total weight of composition D.

[0521] Composition D may comprise at least one coloring agent chosen from pigments, direct dyes, and their mixtures as described above. Protocol

[0522] Composition C and possible composition D described above can be used on dry or damp hair, as well as on all types of hair, light or dark, natural or colored, permed, bleached or straightened.

[0523] According to a preferred embodiment, composition C and optional composition D are applied simultaneously to the keratin fibers.

[0524] According to another preferred embodiment, the optional composition D is applied to the hair after the application of composition C to the hair.

[0525] According to another preferred embodiment, the optional composition D is applied to the hair before the application of composition C to the hair.

[0526] More preferably, the optional composition D is applied to the hair after the application of composition C to the hair.

[0527] According to a particular embodiment of the invention, the hair is washed before applying composition C and optionally composition D.

[0528] Preferably, a washing, rinsing, wringing or drying step is carried out after the application of composition C to the hair and optionally before the application of composition D to the hair.

[0529] More preferably, a drying step is carried out after the application of composition C to the hair and optionally before the application of possible composition D to the hair.

[0530] Application to the hair can be carried out by any conventional means, in particular by means of a comb, a brush, a brush, a sponge or with the fingers.

[0531] The application of composition C and / or composition C followed by optional composition D to the hair is generally carried out at room temperature (between 15 and 25°C).

[0532] After applying composition C to the hair, one can wait between 1 minute and 6 hours, in particular between 1 minute and 2 hours, more particularly between 1 minute and 1 hour, more preferably between 1 minute and 30 minutes, before for example the application of composition D to the hair or for example a washing, rinsing, wringing or drying step.

[0533] Preferably, there is no exposure time after the application of composition C to the hair and before the application of the possible composition D to the hair.

[0534] After applying composition C and / or composition C followed by optional composition D, the hair may be left to dry or dried, for example at a temperature greater than or equal to 30°C.

[0535] The method according to the invention can thus comprise a step of applying heat to the keratin fibers using a heating tool.

[0536] The heat application step of the method of the invention can be implemented using a helmet, a hair dryer, a straightening or curling iron, a climazon, etc.

[0537] Preferably, the heat application step of the method of the invention is carried out using a hair dryer.

[0538] When the method of the invention implements a step of applying heat to the hair, the step of applying heat to the hair takes place after the application of composition C and composition D to the hair.

[0539] During the step of applying heat to the hair, a mechanical action on the strands can be exerted such as combing, brushing, or passing the fingers through.

[0540] When the step of applying heat to the hair is carried out using a helmet or a hair dryer, the temperature is preferably between 30 and 110°C, preferably between 50 and 90°C.

[0541] When the step of applying heat to the hair is carried out using a hair straightener, the temperature is preferably between 110 and 220°C, preferably between 140 and 200°C.

[0542] In a particular variant, the method of the invention implements a step (cl) of applying heat using a helmet, a hair dryer or a climazon, preferably a hair dryer and a step (c2) of applying heat using a straightening or curling iron, preferably a straightening iron.

[0543] Step (cl) can be carried out before step (c2).

[0544] During step (cl), also called the drying step, the hair may be dried, for example at a temperature greater than or equal to 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.

[0545] Preferably, if the hair is dried, it is dried, in addition to a heat supply, with a flow of air. This flow of air during drying makes it possible to improve the individualization of the sheathing.

[0546] During drying, a mechanical action on the strands can be exerted such as combing, brushing, passing the fingers.

[0547] During step (c2), the passage of the straightening or curling iron, preferably the straightening iron, can be carried out at a temperature ranging from 110 to 220°C, preferably between 140 and 200°C.

[0548] After the heating step, a shaping step can be carried out with, for example, a hair straightener, the temperature for the shaping step is between 110 and 220°C, preferably between 140 and 200°C.

[0549] Preferably, the invention is a hair coloring process comprising:

[0550] i) the application to the hair of at least one composition C comprising: - one or more (poly)carbodiimide compound(s) as described above,

[0551] - one or more silicone acrylic copolymers as described above; and - one or more coloring agent(s) chosen from pigments, direct dyes, and their mixtures; then

[0552] ii) optionally a time for leaving said composition C on the hair of 1 minute to 30 minutes, preferably of 1 to 20 minutes; then

[0553] iii) optionally a step of washing, rinsing, wringing or drying the hair, preferably a drying step, then

[0554] iv) optionally the application to the hair of a composition D comprising at least one silicone compound comprising at least one carboxylic group as described previously; then v) optionally a time for leaving said composition D on the hair of 1 minute to 30 minutes, preferably 1 to 20 minutes; then vi) optionally a step of washing, rinsing, wringing or drying the hair.

[0555] Advantageously, the coloring process comprises step iv) of applying to the hair a composition D comprising at least one silicone compound comprising at least one carboxylic group as described previously.

[0556] Preferably, the step of applying composition C to the hair is repeated several times.

[0557] According to a preferred embodiment, the coloring process according to the invention is a hair coloring process consisting of mixing extemporaneously at the time of use at least two compositions A and B to obtain a composition C and applying composition C to the hair, with: - composition A comprising one or more (poly)carbodiimide compound(s) as described previously; - composition B comprising one or more silicone acrylic copolymers as described previously,

[0558] composition A and / or composition B comprising at least one coloring agent chosen from pigments, direct dyes, and their mixtures.

[0559] Advantageously, the coloring process further comprises the application to the hair of at least one composition D comprising at least one silicone compound comprising at least one carboxylic group as described previously, said composition D being applied to the hair before and / or after the application of composition C to the hair.

[0560] According to this embodiment, compositions A and B are preferably mixed less than 15 minutes before application to the hair, more preferably less than 10 minutes before application, better still less than 5 minutes before application.

[0561] The weight ratio between composition A and composition B preferably ranges from 0.1 to 10, preferably from 0.2 to 5, better still from 0.5 to 2, or even from 0.6 to 1.5. In a particular embodiment, the weight ratio between composition A and composition B is equal to 1.

[0562] According to a particular embodiment, the hair coloring process according to the invention is a hair coloring process consisting of mixing extemporaneously at the time of use at least two compositions A and B to obtain a composition C, and applying composition C to the hair, with: - composition A comprising one or more (poly)carbodihnide compound(s) as described above; and - composition B comprising one or more silicone acrylic copolymers as described previously,

[0563] composition A or composition B comprising at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof; and - the application to the hair of at least one composition D comprising at least one silicone compound comprising at least one carboxylic group as described previously, said composition D being applied to the hair before and / or after the application of composition C to the hair.

[0564] The total amount of the (poly)carbodihnide compound(s) of formula (II) preferably ranges from 0.01 to 40% by weight, more preferably from 0.1 to 30% by weight, better still from 0.5 to 20% by weight, even more preferably from 1 to 12% by weight relative to the total weight of composition A.

[0565] The total amount of the silicone acrylic copolymer(s) preferably ranges from 2 to 60% by weight, more preferably from 5 to 40% by weight, better still from 5 to 20% by weight relative to the total weight of composition B. Multi-compartment device (kit)

[0566] The present invention also relates to a device for coloring hair comprising one or more compartments containing: - in a first compartment, a composition C comprising: a) one or more (poly)carbodiimide compound(s) as described above, b) one or more silicone acrylic copolymers as described above, and c) at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof, and - optionally in a second compartment, a composition D comprising at least one silicone compound comprising at least one carboxylic group as described previously.

[0567] The present invention also relates to a device for coloring hair comprising several compartments containing: - in a first compartment, a composition A comprising: a) one or more (poly)carbodiimide compound(s) as described above,

[0568] - in a second compartment, a composition B comprising: b) one or more silicone acrylic copolymers as described above,

[0569] composition A and / or composition B comprising: (c) at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof, and - optionally in a third compartment, a composition D comprising at least one silicone compound comprising at least one carboxylic group as described previously.

[0570] The present invention will now be described more specifically by way of examples, which are in no way limiting of the scope of the invention. However, the examples make it possible to support specific characteristics, variations, and preferred embodiments of the invention. EXAMPLES

[0571] The (poly)carbodiimide(s) of the invention are accessible by the synthesis methods known to those skilled in the art from commercial products or reagents that can be synthesized according to chemical reactions also known to those skilled in the art. Examples include the work Sciences of Synthesis - Houben - Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D-70469 Stuttgart, or the American patent US 4,284,730 or the Canadian application CA 2,509,861.

[0572] More particularly, the process for preparing the (poly)carbodiimides of the invention uses, during a first step, a diisocyanate reagent (1): O=C=N-LrN=C=O (1), formula (1) in which Li is as defined above, which reacts in the presence of a carboimidation catalyst (2) such as those described in US 4,284,730, in particular phosphorus catalysts particularly chosen from phospholene oxides and phospholene sulfoxides, diaza and oxazaphospholanes, preferably under at inert atmosphere (nitrogen or Argon), and in particular in a polar, preferably aprotic, solvent such as THF, glyme, diglyme, 1,4-dioxane, and DMF, at a temperature between room temperature and solvent reflux, preferably around 140°C; to yield the carbodiimide diisocyanate compound (3): O=C=N-L1-(N=C=N-L1)nN=C=O (3), formula (3) in which Li and n are as defined above. Halogenated benzoyl such as benzoyl chloride may be added to deactivate the catalyst.

[0573] To obtain “symmetrical” (poly)carbodiimides, during the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq) of nucleophilic reagent Ri-XrH, then 0.5 eq. of HEH reagent with Rb Xi and E as defined previously, to lead to the “symmetrical” compound according to the invention (4): [R1-X1-C(O)-NH-L1-(N=C=N-L1)n-NH-C(O)]2-E (4), formula (4) in which Rb Xb Lh n, and E are as defined previously. According to a variant to obtain compound (4) from (3) it is possible to first add 0.5 eq. of HEH reagent, then 1 eq. of Ri-XrH reagent.

[0574] To obtain “dissymmetric” (poly)carbodiimides, during the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq) of nucleophilic reagent Ri-XrH then 1 eq. of HEH reagent with Rb Xi and E as defined previously, to lead to compound (5): R1-X1-C(O)-NH-L1-(N=C=N-L1)n-NH-C(O)-EH (5), formula (5) in which Rb Xb Lh n, and E are as defined previously.

[0575] According to a variant to obtain compound (5) from (3) it is possible to first add 1 eq. of reagent Ri-XrH, then 0.5 eq. of reagent HEH.

[0576] In a third step, compound (5) reacts with 1 eq. of compound (6) R2-X2-C(O)-NH-Li-(N=C=N-Li)zN=C=O (6), said compound (6) is prepared beforehand from compound (3'): O=C=N-L1-(N=C=N-L1)ZN=C=O (3'),

[0577] formula (3') in which Li and z are as defined previously which reacts with 1 eq of nucleophilic reagent R2-X2-H with Lb R2, X2, and z as defined previously, to lead to 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),

[0578] Formula (7) in which Rb Xb Lb R2, X2, n, z and E are as defined previously.

[0579] It is also possible to react 1 molar equivalent of compound O=C=N-Li -(N=C=N-Li)zN=C=O (3') with 1 / w molar equivalent of HEH, then 1 eq. of nucleophilic reagent R2-X2-H to lead to compound (8): H-[EC(O)-NH-L1-(N=C=N-L1)z]w-NH-C(O)-X2-R2(8),

[0580] formula (8) in which Lb R2, X2, z and E are as defined previously, and w is an integer between 1 and 3, more preferably w = 1.

[0581] This last compound (8) can then react with 1 eq of compound (4'): Ri-Xi-C(O)-NH-Li-(N=C=N-Li)nN=C=O (4'), (said compound (4') can be synthesized by reaction of 0.5 eq. of nucleophilic reagent Ri-XrH with 1 equivalent of compound (3)), to yield the (poly)carbodiimide of the invention (9): 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), formula (9) in which Lb Rb Xb R2, X2, n, z, w, and E are as defined previously.

[0582] The (poly)carbodiimide compounds as well as all reaction intermediates and reagents can be purified with conventional methods known to those skilled in the art, such as extraction with water and water-immiscible organic solvent, precipitation, centrifugation, filtration, and / or chromatography.

[0583] Example 1: Process for the synthesis of the compound (poly)carbodiimide

[0584] In a 500 mL three-necked flask equipped with a thermometer, a stirrer and a reflux tube, 50 g of dicyclohexylmethane 4,4'-diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-l-phenyl-lH-phosphole 1-oxide were introduced with stirring.

[0585] The reaction medium was heated to 140°C under nitrogen for 4 hours, monitoring the reaction by infrared spectroscopy through the absorption of the isocyanate functions between 2200 and 2300 cm1, then cooled to 120°C.

[0586] 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. The temperature of 120°C is maintained until the isocyanate functions have completely disappeared, monitored by infrared spectroscopy at 2200-2300 cm1, then cooled to room temperature.

[0587] After cooling to room temperature, the reaction medium is poured dropwise with vigorous stirring into a 500 mL glass beaker containing 85 g of distilled water to yield the desired product in the form of a translucent yellow liquid. Example 2

[0588] Compositions A1, A2, B1 and B2 as described below were prepared: the quantities are expressed in g of raw material as is / 100g, unless otherwise stated.

[0589] [Tables 1] Composition Al A2 Poly c arbodiimide< 24 24 Red iron oxide (CI 77491) 12 - Ethanol Qsp 100 Qsp 100

[0590] (1) synthesized according to the synthesis method described in example 1 (at 40% material active in water),

[0591] [Tables2] Compositions B1 B2 Crotonic Acid / Vinyl C8-12 Isoalkyl Esters / VA / Bis-Vinyldimethicone Crosspolymer (2) - 24 Red Iron Oxide (CI 77491) - 12 Ethanol Qsp 100 Qsp 100

[0592] (2) sold by Wacker Chemie AG under the trade name Belsil® PI 101 (50% active ingredient in ethanol)

[0593] Two mixtures are then made. Composition Al is mixed with composition B1, and composition A2 is mixed with composition B2 at a mass ratio of 50 / 50 for each of the mixtures to obtain two compositions Cl and C2.

[0594] Then, composition D as described below was prepared: the quantities are expressed in g of raw material as is / 100g.

[0595] [Tables3] Compositions D Organopolysiloxane with carboxylic group (3) 2 Isododecane qsp 100

[0596] (3) Silform INX sold by Momentive Performance Materials

[0597] Each of the compositions C1 and C2 is applied to strands of 90% white natural hair, at a rate of 0.8g of composition per gram of strand. The strands of hair are then untangled and dried with a hairdryer, then combed.

[0598] Then, composition D is applied to the locks of hair treated with compositions C1 and C2, respectively, at a rate of 0.5g of composition per gram of lock.

[0599] The locks of hair are then left at room temperature and humidity for 24 hours.

[0600] Thus, the hair treated with compositions C1 then D is treated by a comparative process, and the hair treated with compositions C2 then D is treated by the process according to the invention.

[0601] The locks of hair thus colored are then subjected to a test of several repeated shampoos in order to evaluate the tenacity (the persistence) of the coloring obtained from the shampoos, according to the shampoo protocol described below. Shampoo protocol:

[0602] The colored hair strands are combed, moistened under water at 35°C before being passed between the fingers 5 times for 5 seconds. The hair strands are then wrung out between two fingers.

[0603] A standard shampoo (Garnier Ultra Doux) is applied evenly to the colored strands at a rate of 0.4g of standard shampoo per gram of strands, gently kneading the strands of hair lengthwise (6 passes) for 15 seconds, from root to tip.

[0604] The strands of hair are then placed in a watch glass and left to rest for 1 minute.

[0605] Then, the hair strands are rinsed with water by passing the strand between the fingers (15 passes). The hair strands are then wrung out between two fingers before the next shampoo.

[0606] Once the tests of several shampoos are carried out, the strands of hair are combed and dried with a hairdryer. Results

[0607] The color persistence of the strands was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, specular component included).

[0608] In this L*a*b* system, L* represents the color intensity, a* indicates the green / red color axis and b* the blue / yellow color axis.

[0609] The persistence of the color is evaluated by the color difference AE between the colored strands before shampooing, then after having undergone 5 shampoos according to the protocol described above. The lower the AE value, the more the color persists after shampooing.

[0610] The value of AE is calculated according to the following equation:

[0611] to S ~ yiV L + (a* - *)* + ST - 3 S

[0612] In this equation, L*a*b* represent the values ​​measured after coloring the hair and after having undergone shampooing, and Lo*ao*bo* represent the values ​​measured after coloring the hair but before shampooing.

[0613] [Tables4] Processes Number of shampoos L* a* b* AE Cl + D (comparative) 0 33.2 21.2 15.1 - 5 64.2 1.2 16.7 36.9 C2 + D (invention) 0 34.9 27.9 21.5 - 5 36.0 28.1 21.6 1.1

[0614] Hair treated with the process according to the invention and washed with five shampoos has a lower AE value than that of hair treated with the comparative process.

[0615] Thus, the colored coating obtained with the process according to the invention has improved persistence to shampooing.

Claims

Claims

1. A method of coloring hair comprising the application to the hair of at least one composition C comprising: - one or more (poly)carbodiimide compounds of the following formula (II): (II), in which: - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group; - R1 and R2 independently represent a hydrocarbon radical optionally interrupted by one or more heteroatom(s); - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w denotes an integer ranging from 1 to 3; - Li independently represents a divalent C1-C18 aliphatic hydrocarbon radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group, or a C6-C14 arylene group, and mixtures thereof; - E independently represents a group chosen from: - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-, in which R3 and R4 independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s); - R5 independently represents a covalent bond or a divalent saturated hydrocarbon radical, optionally interrupted by one or more heteroatom(s); - R6 independently represents a hydrogen atom, or a hydrocarbon radical optionally interrupted by one or more heteroatom(s); - one or more silicone acrylic copolymers; - one or more coloring agent(s) chosen from pigments, direct dyes and their mixtures.

2. Process according to claim 1, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) in which: - X1 and X2 independently represent an oxygen atom; - R1 and R2 are independently chosen from dialkylaminoalcohols, hydroxycarboxylic acid alkyl esters and (poly)alkylene glycol monoalkyl ethers, in which a hydroxy group has been removed, and mixtures thereof; - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1; - L1 is chosen from a divalent C1-C18 aliphatic hydrocarbon radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group, or a C6-C14 arylene group, and mixtures thereof; - E independently represents a group chosen from: - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;in which R3 and R4 are independently selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof; - when R5 is not a covalent bond, R5 is selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof; and - R6 is selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof.;

3. Process according to claim 1 or 2, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) in which: - Xi and X2 independently represent an oxygen atom; - R1 and R2 are independently monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed; - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1; - Li is a C3-Ci5 cycloalkylene radical; - E independently represents a group chosen from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; in which R3 and R4 are independently chosen from a C6-C14 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched C1C18 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof; - when R5 is not a covalent bond, R5 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1-Ci8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof; and - R6 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1-Ci8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

4. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) in which: - Xi and X2 independently represent an oxygen atom; - R1 and R2, independently represent the compound of formula (VI) following: R13-[O-CH2-C(H)(R14)]q- (VI), in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferably a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30; - n and z denote an integer ranging from 2 to 20, with n+z ranging from 4 to 10 and w equal to 1; - Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, and - E represents a group -O-R3-O- in which R3 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1-Ci8 alkylene radical, optionally in- interrupted by one or more heteroatom(s), and mixtures thereof.

5. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) in which: - X1 and X2 independently represent an oxygen atom; - R1 and R2 independently represent the compound of the following formula (VI): R13-[O-CH2-C(H)(R14)]q- (VI), in which Rn represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferably a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30; - n and z denote an integer ranging from 2 to 20, with n+z ranging from 4 to 10, and w is equal to 1; - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane;and - E represents a group - -O-R3-O- in which R3 represents a linear or branched C1-C18 alkylene radical such as methylene, propylene, butylene, ethylene, optionally interrupted by one or more heteroatom(s).;

6. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (XII) below: (XII), in which Li is 4,4-dicyclohexylene methane, n and z denote an integer ranging from 2 to 20, with n+z ranging from 4 to 10, E represents a group - -O-R3-O- in which R3 represents a linear or branched C1-C18 alkylene radical such as methylene, propylene, butylene ethylene, optionally interrupted by one or more heteroatom(s), and r and s denote an integer ranging from 4 to 30.

7. Process according to any one of the preceding claims, characterized in that the total quantity of the (poly)carbodiimide compound(s) ranges from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, even more preferably from 0.5 to 8%, better still from 1 to 6% by weight relative to the total weight of composition C.

8. Method according to any one of the preceding claims, characterized in that the silicone acrylic copolymer(s) comprise: - at least one acrylic or methacrylic or crotonic unit; - at least one polydimethylsiloxane unit.

9. Method according to any one of the preceding claims, characterized in that the silicone acrylic copolymer(s) comprise: - at least one crotonic unit and at least one unit chosen from a alkyl crotonate unit, the alkyl radical being a linear or branched, saturated radical containing from 1 to 20 carbon atoms; a vinyl acetate unit; a vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms; and mixtures thereof; and - at least one polydimethylsiloxane unit.

10. Process according to any one of the preceding claims, characterized in that the silicone acrylic copolymer(s) comprise: - at least one crotonic unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, the alkyl radical being a linear or branched, saturated radical containing from 2 to 18 carbon atoms, preferably from 6 to 16 carbon atoms; and - at least one polydimethylsiloxane unit comprising at least one polymerizable radical group comprising a vinyl group.

11. Process according to any one of the preceding claims, characterized in that the total quantity of silicone acrylic copolymer(s) ranges from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 15% by weight, better still from 2 to 10% by weight relative to the total weight of composition C.

12. Method according to any one of the preceding claims, characterized in that the total quantity of coloring agent(s) ranges from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight relative to the total weight of composition C, preferably the coloring agent(s) are chosen from pigments.

13. Process according to any one of the preceding claims, characterized in that the total quantity of pigments ranges from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, better still from 0.5 to 10% by weight relative to the total weight of composition C.

14. Method according to any one of the preceding claims, characterized in that it further comprises a step of applying to the hair a composition D comprising at least one silicone compound comprising at least one carboxylic group.

15. Process according to claim 14, characterized in that the total quantity of silicone compound(s) comprising at least one carboxylic group ranges from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.5 to 10% by weight, better still from 1 to 5% by weight relative to the total weight of composition D.

16. Method according to claim 14 or 15, characterized in that composition D further comprises one or more oil(s), preferably chosen from C8-C16 alkanes, more preferably from isododecane, isohexadecane, tetradecane and / or their mixtures.

17. Method according to any one of claims 1 to 13, characterized in that it consists in extemporaneously mixing at the time of use at least two compositions A and B to obtain a composition C and in applying composition C to the hair, with: - composition A comprising one or more (poly)carbodiimide compound(s) as defined in any one of claims 1 to 6; - composition B comprising one or more silicone acrylic copolymers as defined in any one of claims 1 and 8 to 10, composition A and / or composition B comprising at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof.

18. Device for coloring hair comprising several compartments containing: - in a first compartment, a composition A comprising: a) one or more (poly)carbodiimide compound(s) as defined in any one of claims 1 to 6; - in a second compartment, a composition B comprising: b) one or more silicone acrylic copolymers as defined in any one of claims 1 and 8 to 10, composition A and / or composition B comprising: c) at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof, and - optionally in a third compartment, a composition D comprising at least one silicone compound comprising at least one carboxylic group as defined in claim 14 or 15.