A hair coloring process comprising the application of a treatment with an alcohol and a composition comprising a specific (poly)carbodiimide compound and a coloring agent

Abstract

The present invention relates to a hair coloring process comprising: (i) a step of treating the hair with a composition T comprising at least one alcohol, then (ii) a step of applying to the hair at least one coloring composition C comprising: (1) at least one (poly)carbodiimide compound of formula (II); and (2) at least one coloring agent selected from pigments, direct dyes, and mixtures thereof.

Description

Title of the invention: Method for coloring hair comprising the application of a treatment with an alcohol and a composition comprising a specific (poly)carbodiimide compound and a coloring agent

[0001] The present invention relates to a method for coloring hair comprising the application of a treatment with a composition comprising at least one alcohol, then the application to the hair of a coloring composition C comprising a particular (poly)carbodiimide compound and a coloring agent. Technical field

[0002] In the field of coloring hair keratin fibers, it is already known to color hair keratin fibers using 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] Another coloring method consists of using pigments. Indeed, the use of pigments 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 rubbing. The colorings obtained can also be too selective, that is to say that the difference in coloring is too great along the same keratin fiber which is differently sensitized between its tip and its root.

[0008] There therefore remains a need for a hair coloring process which has the advantage of obtaining a homogeneous colored coating on the hair, even sensitized, damaged and / or weakened hair, while forming a coating that is resistant to shampoos and various aggressions that the hair may be subjected to such as brushing and / or rubbing, and which also has the advantage of leading to good dyeing properties, particularly in terms of selectivity.

[0009] Thus, the aim of the present invention is to develop a hair coloring process which has the advantage of obtaining a colored coating on the hair, even sensitized, damaged and / or weakened hair, while forming a coating which is resistant to shampooing and to various aggressions which the hair may be subjected to such as brushing and / or rubbing, and which also has the advantage of leading to good dyeing properties, in particular low selectivity. Statement of the invention

[0010] The present invention therefore relates to a hair coloring process comprising:

[0011] (i) a step of treating the hair with a composition T comprising at least minus one alcohol, then

[0012] (ii) a step consisting of applying to the hair at least one coloring composition C comprising:

[0013] (1) at least one (poly)carbodiimide compound chosen from the compounds of formula (II) following:

[0014] in which

[0015] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0016] - Ri and R2 independently represent a hydrocarbon radical optionally in interrupted by one or more heteroatom(s);

[0017] - 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;

[0018] - 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;

[0019] - E independently represents a group chosen from:

[0020] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-,

[0021] in which R3 and R4 independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s);

[0022] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, possibly interrupted by one or more heteroatom(s);

[0023] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s); and

[0024] (2) at least one coloring agent chosen from pigments, direct dyes and their mixtures.

[0025] Thanks to the hair coloring process according to the invention, colored coatings are obtained on the hair, even sensitized, damaged and / or weakened hair, making it possible to obtain a visible coloring on all types of hair, not very selective, that is to say homogeneous along the fiber, and resistant to shampooing. Such a coating can be resistant to external aggressions that the hair can undergo such as brushing and perspiration. The coloring process according to the invention makes it possible in particular to obtain a homogeneous coating.

[0026] The expression “at least one” means one or more.

[0027] 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 ...”.

[0028] The invention is not limited to the illustrated examples. The characteristics of the different examples may in particular be combined within non-illustrated variants.

[0029] For the purposes of the present invention and unless otherwise indicated,

[0030] - an “alkyl” radical denotes a saturated linear or branched radical containing by example of 1 to 20 carbon atoms;

[0031] - an “aminoalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an NH2 group;

[0032] - a “hydroxyalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an OH group;

[0033] - an “alkylene” radical denotes a divalent saturated C2-C4 hydrocarbon group, linear or branched, such as methylene, ethylene, or propylene;

[0034] - a “cycloalkyl” or “alicycloalkyl” radical denotes a hydrocarbon group saturated cyclic mono-, or polycyclic, preferably monocyclic, bicyclic or tricyclic, 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 norbornyl, 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 isobornyl group,

[0035] - a “cycloalkylene” radical denotes a divalent cycloalkyl group with “cy “cloalkyl” as defined above, preferably C3-C12;

[0036] - 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;

[0037] - an “arylene” radical is a divalent aryl radical with “aryl” as defined above preferably arylene represents phenylene;

[0038] - 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;

[0039] - a “heterocycloalkylene” radical is a divalent heterocyclic group with “heterocyclic” as defined above;

[0040] - an “aryloxy” radical denotes an aryl-oxy radical with “aryl” as defined above cededly;

[0041] - an “alkoxy” radical denotes an alkyloxy radical with “alkyl” as defined previously;

[0042] - an “acyloxy” radical denotes an ester radical RC(O)-O- with R an alkyl group as defined above;

[0043] - a “reactive” group is a group capable of forming a bond covalent with another group, identical or different, by chemical reaction.

[0044] 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.

[0045] By "keratin (capillary) fibers" is meant hair. In other words, the expressions "keratin (capillary) fibers" and "hair" are equivalent in the remainder of the description.

[0046] 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. Treatment with an alcohol

[0047] The method according to the invention comprises a step consisting of treating the hair with a composition T comprising at least one alcohol.

[0048] The alcohol(s) according to the invention may be volatile or non-volatile.

[0049] The alcohol(s) may be chosen from monoalcohols having from 1 to 10 carbon atoms and polyalcohols (polyols) having 2 to 32 carbon atoms.

[0050] By "monoalcohol" is meant any organic molecule which comprises a single free hydroxyl group. By "polyol", is meant, for the purposes of the present invention, any organic molecule comprising at least two free hydroxyl groups. Preferably, a polyol in accordance with the present invention is present in liquid form at room temperature.

[0051] The alcohol(s) may be chosen from monoalcohols having from 1 to 10 carbon atoms as indicated above. Among the monoalcohols which may be used in the composition according to the invention, mention may in particular be made of aliphatic or aromatic monoalcohols having from 1 to 10 carbon atoms, such as methanol, ethanol, isopropanol, propan-1-ol, butan-1-ol and its isomers, pentan-1-ol and its isomers, hexan-1-ol and its isomers, heptan-1-ol and its isomers, benzyl alcohol and their mixtures.

[0052] Preferably, the monoalcohol is chosen from monoalcohols having from 1 to 10 carbon atoms. More preferably, the monoalcohol is chosen from methanol, ethanol, isopropanol, propan-1-ol, butanol, benzyl alcohol and mixtures thereof. Better still, the monoalcohol is isopropanol.

[0053] The alcohol(s) may be chosen from polyols having from 2 to 32 carbon atoms. Among the polyols which may be used in the composition according to the invention, mention may be made of:

[0054] - glycerol and its derivatives, such as ethylhexylglycerin;

[0055] - polyglycerols, such as diglycerol;

[0056] - glycols having from 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, trimethylene glycol (1,3-propanediol), 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, pentylene glycol, 1,2-hexylenediol, hexylenetriol, hexamethylene glycol (hexan-1,6-diol), caprylyl glycol (1,2-octanediol), octamethylene glycol (1,8-octanediol), isoprene glycol;

[0057] - glycerol oligomers such as polyethylene glycol or polypropylene glycol;

[0058] - glycol ethers, such as diethylene glycol, dipropylene glycol, tri- propylene glycol;

[0059] - polyols comprising three or more hydroxyl functions, such as trimethyl- lolpropane, or pentaerythritol

[0060] - their mixtures.

[0061] The polyols advantageously suitable for the formulation of a composition according to the present invention are those having in particular from 2 to 32 carbon atoms, preferably 3 to 16 carbon atoms, in particular from 3 to 8 carbon atoms.

[0062] Advantageously, the polyol may be chosen from glycerol, C3-C6 glycols such as propylene glycol, butylene glycol, pentylene glycol, hexylene glycol and glycol ethers such as dipropylene glycol or diethylene glycol, and mixtures thereof.

[0063] Preferably, the polyol according to the invention is butylene glycol.

[0064] According to a preferred embodiment, the alcohol(s) are chosen from lower monoalcohols having from 1 to 10 carbon atoms, glycerol, polyglycerols, glycols having from 2 to 8 carbon atoms, glycerol oligomers such as polyethylene glycol or polypropylene glycol, glycol ethers, polyols comprising three or more hydroxyl functions, and mixtures thereof.

[0065] According to a preferred embodiment, the alcohol(s) are chosen from isopropanol, butylene glycol, and their mixture, preferably the alcohol is butylene glycol.

[0066] Composition T may comprise an organic solvent other than the alcohol described above, or water.

[0067] According to a particular embodiment of the invention, the water content can range from 0.01% to 80% by weight, preferably from 1% to 70% by weight, even more preferably from 2% to 60% by weight relative to the total weight of the composition T according to the invention.

[0068] According to a preferred embodiment, composition T does not comprise water.

[0069] Preferably, the alcohol(s) as defined above is (are) present in a content of 10% to 100% by weight, preferably 50% to 100% by weight, more preferably 80% to 100% by weight, even more preferably 90% to 100% by weight, better still equal to 100% by weight relative to the total weight of the composition T according to the invention. Polycarbodiimide compound

[0070] Composition C used in the context of the process according to the invention comprises at least one (poly)carbodiimide compound of particular formula (II) as indicated above. Before.

[0071] The composition may comprise at least two distinct (poly)carbodiimide compounds, present as a mixture in the composition.

[0072] The term “(poly)carbodiimide compound” means a compound comprising one or more carbodiimide groups, preferably at least two carbodiimide groups, more preferably at least three carbodiimide groups; in particular, the number of carbodiimide groups does not exceed 200, preferably 150, more preferably 100.

[0073] The term “carbodiimide group” means a divalent linear triatomic moiety of general formula -(N=C=N)-.

[0074] The (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) below: H' H

[0075] in which:

[0076] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0077] - Ri and R2 independently represent a hydrocarbon radical optionally in interrupted by one or more heteroatom(s);

[0078] - 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;

[0079] - Li independently represents a divalent aliphatic hydrocarbon radical in C 1 - C18, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group, or a C6-C14 arylene group, and mixtures thereof;

[0080] - E independently represents a group chosen from:

[0081] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-,

[0082] in which R3 and R4 independently represent a divalent hydrocarbon radical possibly interrupted by one or more heteroatom(s);

[0083] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, possibly interrupted by one or more heteroatom(s);

[0084] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

[0085] 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.

[0086] The hydrocarbon radical may comprise one or more cyclic groups.

[0087] 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.

[0088] 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.

[0089] Preferably, X1 and X2 independently represent an oxygen atom.

[0090] Preferably, R1 and R2 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.

[0091] According to a preferred embodiment, Ri and R2 are independently chosen from the following groups (i) to (iv):

[0092] (i) the compound of formula (III) following:

[0093] R7-OC(O)-C(R8)(H)-(III),

[0094] 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.

[0095] (ii) the compound of formula (IV) following:

[0096] R9-[0-CH2-C(H)(Rio)]p-(IV),

[0097] 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.

[0098] (iii) the compound of formula (V) following:

[0099] (Rn)2N-CH2-C(H)(R12)- (V),

[0100] wherein Rn represents a C1-C4 alkyl group and Rn represents a hydrogen atom or a C1-C4 alkyl group; preferably Ru is methyl, ethyl or butyl and Rn is a hydrogen atom or methyl.

[0101] (iv) the compound of formula (VI) following:

[0102] R13-[O-CH2-C(H)(R14)]q- (VI),

[0103] in which Rn represents a Cr-C4 alkyl group or a phenyl, RM represents a hydrogen atom or a Cr-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.

[0104] Preferably, R1 and R2 independently represent a compound of formula (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.

[0105] According to an alternative embodiment, Ri and R2 are different and one of the radicals Ri or R2 represents a compound of formula (IV) as described above and the other radical Ri or R2 represents a compound of formula (VI) as described above.

[0106] Preferably, in formula (IV), R9 is methyl, ethyl or butyl and Rio is hydrogen or methyl and p is 1.

[0107] 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.

[0108] 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 Cr-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.

[0109] Preferably, n denotes an integer ranging from 1 to 20, more preferably from 2 to 20.

[0110] Preferably, z denotes an integer ranging from 1 to 20, more preferably from 2 to 20.

[0111] Preferably, w is equal to 1.

[0112] Preferably, w is equal to 1, n+z denotes an integer ranging from 4 to 10.

[0113] Preferably, Li is chosen from a divalent C 1 -C 10 aliphatic hydrocarbon radical. -Ci8 such as methylene, ethylene, and propylene, a C3-Cb cycloalkylene radical such as cyclopentylene, cycloheptylene, and cyclohexylene, a C3-C[2 heterocycloalkylene group such as imidazolene, pyrrolene, and furanylene, or a C6-Ci4 arylene group such as phenylene, and mixtures thereof.

[0114] 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-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate and phenylene diisocyanate and mixtures thereof.

[0115] Preferably, Li is chosen from a C3-Ci5 cycloalkylene radical, or a C6-Ci4 arylene group and their mixtures, such as the compounds of formula (VII) below:

[0116] Preferably, L1 is 4,4-dicyclohexylene methane corresponding to the following formula (VIII):

[0117] 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): (IX).

[0118] As indicated previously, E independently represents a group chosen from:

[0119] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0120] in which R3 and R4 independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s);

[0121] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, possibly interrupted by one or more heteroatom(s); and

[0122] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

[0123] Preferably, R3 and R4 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 CrCi8 alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatom(s) and mixtures thereof.

[0124] More preferably, R3 and R4 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).

[0125] 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.

[0126] Preferably, R6 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.

[0127] 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.

[0128] 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).

[0129] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from alpha-methylstyryl-isocyanates of the following formula (X): (X),

[0130] 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,

[0131] n denotes an integer ranging from 2 to 100.

[0132] In this embodiment, the term “alkyl group” is as defined above.

[0133] In this embodiment, the term “cycloalkyl group” is as defined above.

[0134] In this embodiment, n can denote an integer ranging from 2 to 50, preferably from 3 to 30, more preferably from 5 to 10.

[0135] According to another particular embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI):

[0136] 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.

[0137] “Alkyl group”, “cycloalkyl group” and “aryl group” are as defined above.

[0138] According to a preferred embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) or of formula (II) in which:

[0139] - Xi and X2 independently represent an oxygen atom;

[0140] - Ri and R2, are independently chosen from dialkylaminoalcohols, al- esters hydroxycarboxylic acid alkyls and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, more preferably, the compound of formula (VI) as described above in which Rn 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

[0141] - n and z, when present, denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0142] - 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;

[0143] - 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;

[0144] - E, when present, independently represents a group chosen from:

[0145] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0146] 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;

[0147] - 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

[0148] - R6, when present, is chosen from a C6-C14 arylene radical, a cy radical C3-Ci2 alkylene, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0149] Preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0150] - Xi and X2 independently represent an oxygen atom;

[0151] - Ri 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;

[0152] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0153] - 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;

[0154] - E independently represents a group chosen from:

[0155] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0156] 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;

[0157] - 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

[0158] - R6 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1-C18 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0159] More preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0160] - Xi and X2 independently represent an oxygen atom;

[0161] - Ri and R2, are independently monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed;

[0162] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0163] - Li is a C3-Ci5 cycloalkylene radical;

[0164] - E independently represents a group chosen from:

[0165] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0166] 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;

[0167] - 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

[0168] - 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.

[0169] Even more preferably, the (poly)carbodihnide compound is chosen from the compounds of formula (II) in which:

[0170] - Xi and X2 independently represent an oxygen atom;

[0171] - R1 and R2, independently represent the compound of formula (VI) following:

[0172] R13-[O-CH2-C(H)(R14)]q- (VI),

[0173] in which Rn 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;

[0174] - n and z denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10 and w is equal to 1;

[0175] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cyclo- heptylene, cyclohexylene and 4,4-dicyclohexylene methane; and

[0176] - 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 CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0177] Even more preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0178] - Xi and X2 independently represent an oxygen atom;

[0179] - R1 and R2, independently represent the compound of formula (VI) following:

[0180] R13-[O-CH2-C(H)(R14)]q- (VI)

[0181] in which R[3 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferably a methyl, R[4 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;

[0182] - n and z denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10 and w is equal to 1;

[0183] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cyclo- heptylene, cyclohexylene, 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and

[0184] - E represents a group -O-R3-O- in which R3 represents an alkylene radical linear or branched in CrCi8 such as methylene, propylene, butylene ethylene, possibly interrupted by one or more heteroatom(s).

[0185] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of the following formula (XII):

[0186] in which L1 is 4,4-dicyclohexylene methane, n and z denote an integer ranging from 1 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.

[0187] Advantageously, the total quantity 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. Coloring agent

[0188] Composition C used in the context of the process according to the invention comprises at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof.

[0189] Preferably, the composition C used in the context of the process according to the invention comprises one or more pigments.

[0190] Preferably, the composition C used in the context of the process according to the invention comprises at least one pigment.

[0191] 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%.

[0192] The pigments which can be used are in particular chosen from pigments organic and / or mineral materials known to the art, in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.

[0193] They can be natural, of natural origin, or not.

[0194] These pigments can be in the form of powder or pigment paste. They can be coated or uncoated.

[0195] 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.

[0196] The pigment may be a mineral pigment. By mineral pigment is meant any pigment that 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.

[0197] The pigment may be an organic pigment. By "organic pigment" is meant any pigment that meets the definition in the Ullmann encyclopedia in the organic pigment chapter.

[0198] 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.

[0199] In particular, the white or colored organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Color Index under the references Cl 11725, 45370, 71105, the 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 indole, phenolic derivatives as described in patent FR 2 679 771.

[0200] As an example, we can also cite organic pigment pigment pastes such as the products sold by the company HOECHST under the name:

[0201] - COSMENYL YELLOW IOG: Pigment YELLOW 3 (Cl 11710);

[0202] - COSMENYL YELLOW G: Pigment YELLOW 1 (Cl 11680);

[0203] - ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);

[0204] - COSMENYL RED R: Pigment RED 4 (Cl 12085);

[0205] - CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);

[0206] - VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);

[0207] - COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);

[0208] - COSMENYL GREEN GG: Pigment GREEN 7 (Cl 74260);

[0209] - COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

[0210] 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.

[0211] 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.

[0212] 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.

[0213] Among the colorants, we can cite carminic acid. Also included are dyes known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).

[0214] As examples of lacquers, we can cite the product known under the following name: D & C Red 7 (CI 15 850:1).

[0215] The pigment may also be a special effect pigment. Special effect pigments are understood to mean pigments that generally create a colored appearance (characterized by a certain shade, a certain vividness and a certain clarity) that is non-uniform and changes depending on the viewing conditions (light, temperature, viewing angles, etc.). They are thus opposed to colored pigments that provide a conventional uniform opaque, semi-transparent or transparent shade.

[0216] 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 nacres, interference pigments or glitter.

[0217] Examples of special effect pigments include pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, pearlescent pigments colored such as mica coated with titanium and iron oxides, mica coated with iron oxide, mica coated with titanium and in particular with ferric blue or chromium oxide, mica coated with titanium and an organic pigment as defined above as well as pearlescent pigments based on bismuth oxychloride. As pearlescent pigments, mention may be made of Cellini pearlescent pigments marketed by BASF (Mica-TiO 2-lake), Prestige marketed by Eckart (Mica-TiO2), Prestige Bronze marketed by Eckart (Mica-Fe2O3) Colorona marketed by Merck (Mica-TiO2-Fe2 O3).

[0218] 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-tinted mother-of-pearl, notably marketed by MERCK under the name Sienna Fine (17386) (Colorona); yellow-tinted mother-of-pearl, notably marketed by BASF under the name Yellow (4502) (Chromalite); red-tinted mother-of-pearl with a gold tint, 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 pinkish-orange, golden-green mother-of-pearl notably marketed by MERCK under the name Indian Summer (Xirona) and their mixtures.;

[0219] Still as an example of nacres, we can also cite particles comprising a borosilicate substrate coated with titanium oxide.

[0220] Particles with a glass substrate coated with titanium oxide are notably sold under the name METASHINE MC1080RY by the company TOYAL.

[0221] Finally, as examples of mother-of-pearl, we can also cite poly glitter. ethylene terephthalate, including those marketed by Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver flakes). Multi-layer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate, and aluminum can also be considered.

[0222] 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 state, 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.

[0223] 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.

[0224] These particles can have various shapes, in particular being platelet-shaped or globular, in particular spherical.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] The reflective material may comprise a layer of metal or a metallic material.

[0230] Reflective particles are described in particular in documents JP- A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] Examples include aluminum, bronze or copper powders coated with SiO2 marketed under the name VISIONAIRE by the company ECKART.

[0235] 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.

[0236] 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.

[0237] 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.

[0238] The pigments may be dispersed in the composition using a dispersing agent.

[0239] 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 have, in addition, at least one functional group 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.

[0240] 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.

[0241] The pigments used in the composition may be surface-treated with an organic agent.

[0242] 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 which are 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 aluminum salts of fatty acids, for example aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethylmethacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, in particular polydimethylsiloxanes; fluorinated organic compounds, for example perfluoroalkyl ethers; fluorosilicon compounds.

[0243] 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.

[0244] 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.

[0245] Preferably, the surface-treated pigments are covered by an organic layer.

[0246] 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.

[0247] 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.

[0248] Preferably, an organic agent covalently bound to the pigments will be used.

[0249] 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.

[0250] Preferably, the surface treatments of the pigments are chosen from the following treatments:

[0251] - a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW;

[0252] - a Methicone treatment such as the SI surface treatment marketed by LCW;

[0253] - a Dimethicone treatment such as Covasil 3.05 com surface treatment marketed by LCW;

[0254] - a Dimethicone / Trimethylsiloxysilicate treatment as the surface treatment Covasil 4.05 marketed by LCW;

[0255] - a Magnesium Myristate treatment such as the MM com surface treatment marketed by LCW;

[0256] - an Aluminum Dimyristate treatment such as MI com surface treatment sold by Miyoshi;

[0257] - a Perfluoropolymethylisopropyl ether treatment as the surface treatment FHC marketed by LCW;

[0258] - an Isostearyl Sebacate treatment like the commercialized HS surface treatment by Miyoshi;

[0259] - a Perfluoroalkyl Phosphate treatment such as PF surface treatment marketed by Daito;

[0260] - an acrylate / Dimethicone and Perfluoroalkyl Phosphate Copolymer treatment such as the FSA surface treatment marketed by Daito;

[0261] - a Polymethylhydrogen siloxane / Perfluoroalkyl Phosphate treatment such as the FSO1 surface treatment marketed by Daito;

[0262] - an Acrylate / Dimethicone Copolymer treatment as the surface treatment ASC marketed by Daito;

[0263] - an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito;

[0264] - an Acrylate copolymer treatment such as APD surface treatment com sold by Daito;

[0265] - a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito.

[0266] 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.

[0267] 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.

[0268] 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.

[0269] The dispersing agent(s) may therefore have a silicone backbone, such as silicone polyether and amino-silicone dispersants. Suitable dispersing agents include:

[0270] - 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,

[0271] - silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik,

[0272] - 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.

[0273] According to a particular embodiment, the dispersing agent(s) are of amino-silicone type and are cationic.

[0274] Preferably, the pigment(s) is (are) chosen from mineral, mixed mineral-organic or organic pigments.

[0275] In a 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.

[0276] 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.

[0277] Direct dye

[0278] Composition C used in the context of the process according to the invention may comprise one or more direct dye(s).

[0279] By "direct dye" we mean natural and / or synthetic dyes, different from oxidation dyes. These are dyes which will diffuse superficially on the fiber.

[0280] They can be ionic or non-ionic, preferably cationic or non-ionic.

[0281] 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.

[0282] The direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazono cationic dyes of formulae (XIII) and (XIV), the azo cationic dyes (XV) and (XVI) below: Hér-N(Ra)-X=C(Rb)-Ar Q- (XIII)' (XIV), Hér-CCRa^N-NCRb)-^ Q HeV-NAN-Ai, Q- (XV), Ar-N=X-AL\ Q-

[0283] formulas (XIII) to (XVI) in which:

[0284] - 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;

[0285] - 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;

[0286] - Ar represents an aryl group, in particular phenyl, optionally substituted, preferentially by one or more electron-donating groups such as i) (CrC8 )alkyl optionally substituted, ii) (CrC8)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;

[0287] - 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;

[0288] - Ra and Rb, identical or different, representing a hydrogen atom or a (CrC8)alkyl group optionally substituted, preferably by a hydroxyl group;

[0289] 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 (C1-C4)alkyl group optionally substituted by a hydroxyl group;

[0290] - Q- represents an organic or inorganic anionic counterion such as a halide or an alkyl sulfate.

[0291] 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:

[0292] Formulas (XVII) and (XVIII) in which:

[0293] - R1 represents a (Ci-C4)alkyl group such as methyl;

[0294] - R2 and R3, identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group such as methyl; and

[0295] - R4 represents a hydrogen atom or an electron-donating group such that (Ci - C8)alkyl optionally substituted, (CrC8)alkoxy optionally substituted, (di)(Ci-C8)(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group; particularly R4 is a hydrogen atom,

[0296] - Z represents a CH group or a nitrogen atom, preferably CH,

[0297] - Q- is an anionic counterion as defined above particularly ha- lignide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0298] 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.

[0299] 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. By anionic direct dyes is meant 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.

[0300] 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:

[0301] a) diaryl anionic azo dyes of formula (XIX) or (XIX'):

[0302] formulas (XIX) and (XIX') in which:

[0303] - 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:

[0304] - alkyl;

[0305] - alkoxy, alkylthio;

[0306] - hydroxy, mercapto;

[0307] - nitro, nitroso;

[0308] - 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;

[0309] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0310] - (O)CO—, M+ with M+ as defined previously;

[0311] - 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;

[0312] - R'”-S(O)2-X'- with R”' representing an alkyl, optionally aryl group substituted, X' as defined above;

[0313] - (di)(alkyl)amino;

[0314] - 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 above;

[0315] - optionally substituted heteroaryl; preferably a benzo- group thiazolyl;

[0316] - cycloalkyl, in particular cyclohexyl;

[0317] - 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;

[0318] - 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'ç 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;

[0319] - W represents a sigma o bond, an oxygen atom, a sulfur atom, or a radical

[0320]

[0321]

[0322]

[0323] 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 spiro cycloalkyl; preferably W represents a sulfur atom or Ra and Rb together form a cyclohexyl; 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. 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; et à titre d’exemple de colorants de formule (XIX’) on peut citer : Acid Red 111, Acid Red 134, Acid yellow 38 ; b) les colorants azo anioniques pyrrazolone de formule (XX) et (XX’) :

[0324]

[0325] formulas (XX) and (XX') in which: - Ru, 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;

[0326] - Ru represents a hydrogen atom, an alkyl group or a group - C(O)O-, M+ with M+ as defined previously;

[0327] - Rn represents a hydrogen atom;

[0328] - Ri6 represents an oxo group in which case R'i6 is absent, or else R[5 with R[6 together form a double bond;

[0329] - Rn and Ri8, identical or different, represent a hydrogen atom, or a group chosen from:

[0330] - (O)2S(O-)-, M+ with M+ as defined previously;

[0331] - Ar-OS(O)2- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted by one or more alkyl groups;

[0332] - R19 and R2q, together form either a double bond or a benzo D' group, possibly substituted;

[0333] - R' 16, R' 19 and R'2O, identical or different, represent a hydrogen atom or a alkyl or hydroxy group;

[0334] - R2i represents a hydrogen atom, an alkyl or alkoxy group;

[0335] - Ra and Rb, identical or different, are as defined previously, preferably Ra represents a hydrogen atom and Rb represents an aryl group;

[0336] - Y represents either a hydroxy group or an oxo group;

[0337] - ~ • represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group;

[0338] 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;

[0339] 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;

[0340] c) the anthraquinone dyes of formula (XXI) and (XXI'):

[0341] formulas (XXI) and (XXI') in which:

[0342] - R22, R23, R24, R25, R26 and R27, identical or different, represent an atom of hydrogen, halogen, or a group chosen from:

[0343] - alkyl;

[0344] - hydroxy, mercapto;

[0345] - alkoxy, alkylthio;

[0346] - 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;

[0347] - aryl(alkyl)amino optionally substituted by one or more selected groups among alkyl and (O)2S(O-)-, M+ with M+ as defined previously;

[0348] - (di)(alkyl)amino;

[0349] - (di)(hydroxyalkyl)amino

[0350] - (O)2S(O-)-, M+ with M+ as defined previously;

[0351] - Z' represents a hydrogen atom or a group NR28R29 with R28 and R29, identical or different, represent a hydrogen atom or a group chosen from:

[0352] - alkyl;

[0353] - polyhydroxyalkyl such as hydroxyethyl;

[0354] - 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;

[0355] - cycloalkyl, in particular cyclohexyl;

[0356] - Z represents a group chosen from hydroxy and NR'28R'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined previously;

[0357] 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+; preferentially sodium sulfonate;

[0358] As examples of dyes of formula (XXI) we can cite: 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 as examples of dyes of formula (XXI') we can cite: Acid Black 48;

[0359] d) nitrated dyes of formula (XXII), (XXII'):

[0360] formulas (XXII) and (XXII') in which:

[0361] - R3o, R3i and R32, identical or different, represent a hydrogen atom, of halogen, or a group chosen from:

[0362] - alkyl;

[0363] - alkoxy optionally substituted by one or more hydroxy groups, alkylthio optionally substituted by one or more hydroxy groups;

[0364] - hydroxy, mercapto;

[0365] - nitro, nitroso;

[0366] - polyhaloalkyl;

[0367] - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X' ' - with R°; X, X' and X” as defined previously;

[0368] - (O)2S(O-)-, M+ with M+ as defined previously;

[0369] - (O)CO—, M+ with M+ as defined previously;

[0370] - (di)(alkyl)amino;

[0371] - (di)(hydroxyalkyl)amino;

[0372] - heterocycloalkyl such as piperidino, piperazino or morpholino; particularly R 30, R31 and R32 represent a hydrogen atom;

[0373] - Rc and Rd, identical or different, represent a hydrogen atom or a alkyl group;

[0374] - W is as defined above; W particularly represents a group -NH-;

[0375] - ALK represents a linear or branched divalent alkylene group, C1-C6; particularly ALK represents a -CH2-CH2- group;

[0376] - n is 1 or 2;

[0377] - p represents an integer between 1 and 5 inclusive;

[0378] - q represents an integer between 1 and 4 inclusive;

[0379] - u is 0 or 1;

[0380] - when n is 1, J represents a nitro, or nitroso group; particularly nitro ;

[0381] - 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 -SO2-;

[0382] - M' represents a hydrogen atom or a cationic counterion;

[0383] - .... .... present or absent represents a benzo group optionally substituted by one or more R30 groups as defined above,

[0384] it being understood that formulas (XXII) and (XXII') comprise at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical -C(O)O-, M+; preferentially sodium sulfonate.

[0385] As examples of dyes of formula (XXII) we can cite: Acid Brown 13; Acid Orange 3; as examples of dyes of formula (XXII') we can cite: Acid Yellow 1, Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 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;

[0386] e) triarylmethane dyes of formula (XXIII): (XXIII),

[0387] formula (XXIII) in which:

[0388] - 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 previously;

[0389] - R37, R38, R39, R4o, R41, R42, R43 and R44, identical or different, represent an atom of hydrogen or a group chosen from:

[0390] - alkyl;

[0391] - alkoxy, alkylthio;

[0392] - (di)(alkyl)amino;

[0393] - hydroxy, mercapto;

[0394] - nitro, nitroso;

[0395] - 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;

[0396] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0397] - (O)CO—, M+ with M+ as defined previously;

[0398] - or two contiguous groups R41 with R42 or R42 with R43 or R43 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;

[0399] particularly R37 to R40 represent a hydrogen atom, and R4[ to R44, identical or different, represent a hydroxy group or (O)2S(O-)-, M+; and when R43 with R44 together form a benzo group, it is preferentially substituted by a group (O)2S(O-)-;

[0400] 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-; preferentially sulfonate.

[0401] 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.

[0402] f) dyes derived from xanthene of formula (XXIV):

[0403] formula (XXIV) in which:

[0404] - R45, R46, R47 and R48, identical or different, represent a hydrogen atom or a halogen atom;

[0405] - R49. R5o, R51 and R52, identical or different, represent a hydrogen atom, of halogen, or a group chosen from:

[0406] - alkyl;

[0407] - alkoxy, alkylthio;

[0408] - hydroxy, mercapto;

[0409] - nitro, nitroso;

[0410] - (O)2S(O-)-, M+ with M+ representing a hydrogen atom or a counterion ca tionic;

[0411] - (O)CO—, M+ with M+ as defined previously;

[0412] particularly R49, R50, R51 and R52 represent a hydrogen or halogen atom

[0413] - G represents an oxygen atom, a sulfur atom or an NRe group with Re such that defined previously; particularly G represents an oxygen atom;

[0414] - 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;

[0415] - 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;

[0416] - Q and Q', identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;

[0417] - M+ is as defined previously.

[0418] 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;

[0419] g) dyes derived from indole of formula (XXV): (XXV),

[0420] formula (XXV) in which:

[0421] - R53, R54, R55, R56, R57, R58, R59 and R60, identical or different, represent an atom of hydrogen or a group chosen from:

[0422] - alkyl;

[0423] - alkoxy, alkylthio;

[0424] - hydroxy, mercapto;

[0425] - nitro, nitroso;

[0426] - 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;

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

[0430] - Ri and Rh, identical or different, represent a hydrogen atom or a alkyl group;

[0431] it being understood that formula (XXIII) comprises at least one sulfonate radical (O)2S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferentially sodium sulfonate.

[0432] As examples of dyes of formula (XXV) we can cite: Acid Blue 74;

[0433] h) quinoline-derived dyes of formula (XXVI):

[0434] formula (XXVI) in which:

[0435] - R6i represents a hydrogen atom, halogen or an alkyl group;

[0436] - 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;

[0437] 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;

[0438] it being understood that formula (XXVI) comprises at least one sulfonate radical (O)2 S(O-)-, M+ preferably sodium sulfonate.

[0439] As examples of dyes of formula (XXVI) we can cite: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0440] 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.

[0441] Preferably, the direct dyes are chosen from anionic direct dyes.

[0442] 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.

[0443] 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.

[0444] The direct dye(s) may be present in a total amount ranging from 0.001 at 10% by weight, preferably from 0.005 to 5% by weight relative to the total weight of composition C. Non-carboxylic anionic thickening agent

[0445] Composition C used in the context of the process according to the invention may further comprise at least one non-carboxylic anionic thickening agent.

[0446] For the purposes of the present invention, the term “non-carboxylic agent” means an agent which does not comprise a carboxylic acid (-COOH) or carboxylate (-COO) function.

[0447] For the purposes of the present invention, the term “thickening agent” means a compound which increases the viscosity of a composition into which it is introduced at a concentration of 0.05% by weight relative to the total weight of the composition, by at least 20 cps, preferably by at least 50 cps, at room temperature (25°C), at atmospheric pressure and at a shear rate of 1 s 1 (the viscosity can be measured using a cone / plate viscometer, Haake R600 Rheometer or the like).

[0448] Preferably, the non-carboxylic anionic thickening agent(s) are chosen from non-carboxylic anionic polymers, more preferably from anionic polymers with sulfonic group(s).

[0449] For the purposes of the invention, the term “anionic polymer” means a polymer comprising one or more anionic or anionizable groups and not comprising a cationic or cationizable group.

[0450] Advantageously, the non-carboxylic anionic thickening agent(s) are chosen from anionic polymers comprising at least one ethylenically unsaturated monomer with a sulfonic group, in free or partially or totally neutralized form.

[0451] These polymers may be crosslinked or non-crosslinked. They are preferably crosslinked.

[0452] These polymers may be associative or not, preferably non-associative.

[0453] It is recalled that “associative polymers” are polymers capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

[0454] Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0455] By “hydrophobic group” is meant a radical or polymer with a hydrocarbon chain, saturated or not, linear or branched, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms.

[0456] Preferably, the hydrocarbon group originates from a monofunctional compound. For example, the hydrophobic group may originate from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It may also designate a hydrocarbon polymer such as, for example, polybutadiene.

[0457] The ethylenically unsaturated monomers with a sulfonic group are chosen in particular from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci-C22)alkylsulfonic acids, N-(CrC22)alkyl(meth)acrylamido-(Ci-C22)alkylsulfonic acids such as undecyl-acrylamido-methane-sulfonic acid as well as their partially or totally neutralized forms.

[0458] More preferably, (meth)acrylamido(Ci-C22) alkylsulfonic acids will be used, such as, for example, acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, as well as their partially or totally neutralized forms.

[0459] More particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or totally neutralized forms will be used.

[0460] Among the copolymers of 2-acrylamido-2-methylpropane sulfonic acid, mention may be made of crosslinked copolymers of 2-acrylamido-2-methylpropane sulfonic acid and partially or totally neutralized acrylamide, and mention may be made in particular of the product described in example 1 of document EP 503 853 and reference may be made to this document with regard to these polymers.

[0461] Mention may also be made of copolymers of 2-acrylamido-2-methylpropane sulfonic acid or its salts and hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT 10 by the company SEPPIC (INCI name: hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer).

[0462] The associative AMPS polymers may in particular be chosen from random associative AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine, and such as those described in patent application WO 00 / 31154 (forming an integral part of the content of the description). These polymers may also contain other ethylenically unsaturated hydrophilic monomers chosen for example from (meth)acrylic acid derivatives, such as their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, or mixtures of these compounds.

[0463] The preferred polymers of this family are chosen from associative copolymers of AMPS and at least one hydrophobic monomer with ethylenic unsaturation.

[0464] These same copolymers may also contain one or more ethyl monomers. lenically unsaturated compounds not containing a fatty chain such as (meth)acrylic acid derivatives, in particular their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, or mixtures of these compounds.

[0465] These copolymers are described in particular in patent application EP-A-750899, patent US 5089578 and in the following publications by Yotaro Morishima:

[0466] - “Self-assembly amphiphilic polyelectrolytes and their nanostructures - Chinese Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336. » ;

[0467] - “Miscelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, Vol. 33, No. 10 (2000), 3694-3704”;

[0468] - “Solution properties of micelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte: known effects on rheological behavior - Langmuir, Vol. 16, No. 12, (2000) 5324-5332”;

[0469] - “Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers - Polym. Preprint, Div. Polym. Chem., 40(2), (1999), 220-221”.

[0470] Among these polymers, we can cite:

[0471] - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C8-Ci6)alkyl(meth)acrylamide units or (C8-Ci6)alkyl(meth)acrylate units relative to the polymer, such as those described in application EP-A750 899;

[0472] - terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and from 5 to 80 mol% of n-(C6-Ci8)alkylacrylamide units, such as those described in patent US-5089578.

[0473] Mention may also be made of copolymers of fully neutralized AMPS and dodecyl methacrylate as well as non-crosslinked and crosslinked copolymers of AMPS and n-dodecylmethacrylamide, such as those described in the Morishima articles cited above.

[0474] Preferably, the non-carboxylic anionic thickening agent(s) are chosen from the sodium 2-acrylamido-2-methylpropanesulfonate / hydroxyethylacrylate copolymer, marketed by the company SEPPIC (INCI name: hydroxyethylacrylate / sodium acryloyldimethyl taurate copolymer).

[0475] Advantageously, the total amount of the non-carboxylic anionic thickening agent(s) ranges from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight, better still from 0.1 to 5% by weight, and even better still from 0.1 to 3% by weight, relative to the total weight of composition C. Compound having at least one carboxylic function

[0476] Composition C used in the context of the process according to the invention may further comprise at least one compound having at least one carboxylic function.

[0477] Preferably, the compound having at least one carboxylic function is chosen from silicone compounds comprising at least one carboxylic group, polyurethanes, acrylic polymers and their mixtures. Polyurethanes and acrylic polymers:

[0478] According to a preferred embodiment, composition C comprises at least one compound having at least one carboxylic function chosen from polyurethanes, acrylic polymers and their mixtures.

[0479] Preferably, the compound(s) having at least one carboxylic function are in the form of aqueous dispersions of particles of polymer(s) chosen from polyurethanes, acrylic polymers, and mixtures thereof.

[0480] Preferably, composition C comprises at least one compound having at least one carboxylic function in the form of aqueous dispersions of polyurethane particles, acrylic polymers, and their mixtures.

[0481] The dispersion(s) may be simple dispersions in the aqueous medium of the cosmetic composition. As a particular case of dispersions, mention may be made of latexes.

[0482] The aqueous dispersion(s) of polymer particles may be chosen from aqueous dispersions of polyurethane particles.

[0483] More particularly, the polyurethane(s) present in the aqueous dispersions used in the present invention are derived from the reaction of

[0484] - a prepolymer of the following formula (A):

[0485] (A),

[0486] in which:

[0487] - Ri represents a bivalent radical of a dihydroxylated compound;

[0488] - R2 represents a radical of an aliphatic or cycloaliphatic polyisocyanate;

[0489] - R3 represents a radical of a low molecular weight diol, optionally substituted by one or more ionic groups;

[0490] - n represents an integer ranging from 1 to 5, and

[0491] - m is greater than 1;

[0492] - at least one chain extender according to the following formula (B):

[0493] H2N-R4-NH2 (B),

[0494] in which R4 represents an alkylene or alkylene oxide radical which is not substituted by one or more ionic or potentially ionic groups; and

[0495] - at least one chain extender according to the following formula (C):

[0496] H2N-R5-NH2 (C),

[0497] in which R5 represents an alkylene radical substituted by one or more ionic or potentially ionic groups.

[0498] Among the dihydroxylated compounds that can be used according to the present invention, mention may in particular be made of compounds having two hydroxyl groups and a number-average molecular weight of approximately 700 to approximately 16,000, and preferably of approximately 750 to approximately 5,000. As examples of dihydroxylated compounds having a high molecular weight, mention may be made of polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadienes, polyhydroxylated polythioethers and mixtures thereof. Preferably, the hydroxylated compounds are chosen from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates and mixtures thereof.

[0499] The polyisocyanates which can be used according to the present invention are in particular chosen from organic diisocyanates having a molecular weight of approximately 112 to 1000, and preferably of approximately 140 to 400.

[0500] Preferably, the polyisocyanates are chosen from diisocyanates and more particularly from those represented by the general formula R2(NCO)2, in which R2 represents a divalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having from 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having from 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

[0501] Preferably, R2 represents an organic diisocyanate. Examples of organic diisocyanates that may be chosen include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane, l,3-bis(isocyanatomethyl)-cyclohexane, l,4-bis(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, isomers of toluene diisocyanate (TDI) such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures with its isomers 2,4-diphenylmethane diisocyanate and optionally 2,2'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and their mixtures.

[0502] Preferably, the diisocyanates are aliphatic and cycloaliphatic diisocyanates, and are more preferably chosen from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate and mixtures thereof.

[0503] By "low molecular weight diol" is meant, according to the present invention, a diol having a molecular weight of about 62 to 700, and preferably of 62 to 200. These diols may comprise aliphatic, alicyclic or aromatic groups. Preferably, they comprise only aliphatic groups.

[0504] Preferably, R3 represents a low molecular weight diol, having more than 20 carbon atoms, more preferably chosen from ethylene glycol, diethylene glycol, propane 1,2-diol, propane 1,3-diol, butane 1,4-diol, butylene 1,3-glycol, neopentyl glycol, butyl-ethyl-propane diol, cyclohexane diol, 1,4-cyclohexane dimethanol, hexane 1,6-diol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), and mixtures thereof.

[0505] The low molecular weight diols may optionally comprise ionic or potentially ionic groups. Examples of low molecular weight diols containing ionic or potentially ionic groups are described in particular in US patent 3,412,054. Such compounds are preferably chosen from dimethylol butanoic acid, dimethylol propionic acid, polycaprolactone diols containing a carboxyl group and mixtures thereof.

[0506] If lower molecular weight diols containing ionic or potentially ionic groups are used, they are preferably used in an amount such that less than 0.30 meq of COOH per gram of polyurethane in the polyurethane dispersion is present.

[0507] The prepolymer is extended using two families of chain extenders. The first family of chain extenders corresponds to the compounds of general formula (B).

[0508] The chain extenders of formula (B) are preferably chosen from alkylene diamines, such as hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine; alkylene oxide diamines, such as 3-{2-[2-(3-aminopropoxy)ethoxy]-ethoxy}propylamine (also known as dipro-pylamine diethylene glycol or DPA-DEG ​​available from Tomah Products, Milton, Wis.), 2-methyl-1,5-pentanediamine (Dytec A from DuPont), hexane diamine, isophorone diamine, 4,4-methylenedi-(cyclohexylamine), DPA series ether amines available from Tomah Products, Milton, Wis., such as dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropyle- dipropylamine glycol, dipropylamine poly(propylene glycol), dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propane diol, dipropylamine 2-methyl-1,3-propane diol, dipropylamine 1,4-butane diol, dipropylamine 1,3-butane diol, dipropylamine 1,6-hexane diol and dipropylamine cyclohexane-1,4-dimethanol; and mixtures thereof.

[0509] The second family of chain extenders corresponds to compounds of general formula (C). Such compounds preferably have an ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Such compounds may optionally comprise two groups reactive with isocyanate groups and an ionic group or one capable of forming an ionic group.

[0510] The ionic or potentially ionic group may preferably be selected from ternary or quaternary ammonium groups or groups convertible into such groups, a carboxyl group, a carboxylate group, a sulfonic acid group and a sulfonate group. The conversion, at least partial, of the groups convertible into a salt of ternary or quaternary ammonium groups may take place before or during mixing with water.

[0511] The chain extenders of formula (C) are preferably chosen from diaminosulfonates, such as for example the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid, and mixtures thereof.

[0512] The polyurethane usable according to the present invention may optionally further comprise compounds which are respectively located at the ends of the chains and terminate said chains (chain terminators). Such compounds are notably described in patents US 7,445,770 and / or US 7,452,770.

[0513] Preferably, the aqueous dispersion of polyurethane particles has a viscosity of less than 2000 mPa.s at 23°C, more preferably less than 1500, and better still less than 1000. Even more preferably, the aqueous dispersion of polyurethane has a glass transition temperature of less than 0°C.

[0514] Also preferably, the aqueous polyurethane dispersion has a polyurethane content (or active material, or dry matter) based on the weight of the dispersion of 20 to 60% by weight, more preferably 25 to 55% by weight and better still 30 to 50% by weight. This means that the polyurethane content (dry matter) of the aqueous dispersion is preferably 20% to 60% by weight, more preferably 25% to 55% by weight and better still 30% to 50% by weight, relative to the total weight of the dispersion.

[0515] Also preferably, the aqueous dispersion of polyurethane particles has a glass transition temperature (Tg) equal to or less than -25°C, preferably less than -35°C, and more preferably less than -40°C.

[0516] The polyurethane particles may have an average diameter of up to about 1000 nm, for example from about 50 nm to about 800 nm, more preferably from about 100 nm to about 500 nm. These particle sizes may be measured with a laser particle size analyzer (for example Brookhaven BI90).

[0517] As a non-limiting example of aqueous polyurethane dispersions, mention may be made of those sold under the name Baycusan® by Bayer such as, for example, Baycusan® C1000 (INCI name: polyurethane-34), Baycusan® C1001 (INCI name: polyurethane-34), Baycusan® C1003 (INCI name: polyurethane-32), Baycusan® C1004 (INCI name: polyurethane-35) and Baycusan® C1008 (INCI name: polyurethane-48).

[0518] Mention may also be made of aqueous dispersions of polyurethane of isophthalic acid / adipic acid copolymer / hexylene glycol / neopentyl glycol / dimethylol Acid / isophorone diisocyanate (INCI name: Polyurethane-1, such as Luviset® PUR, BASF), polyurethane of polycarbonate, polyurethane and aliphatic polyurethane of aliphatic polyester (such as the NEOREZ® series, DSM, such as NEOREZ® R989, NEOREZ® and R-2202).

[0519] According to a preferred embodiment, the aqueous dispersion of polyurethane particles may be chosen from aqueous dispersions of particles of compounds having the INCI name polyurethane-35 or compounds having the INCI name polyurethane-34.

[0520] Preferably, the compound(s) having at least one carboxylic function are in the form of aqueous dispersions of acrylic polymer particles, more preferably in the form of aqueous dispersions of film-forming acrylic polymer particles.

[0521] For the purposes of the invention, the term "polymer" means a compound corresponding to the repetition of one or more units (these units being derived from compounds called monomers). This or these units are repeated at least twice and preferably at least 3 times.

[0522] By "film-forming polymer" is meant a polymer capable of forming, on its own or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, in particular on the hair, and preferably a cohesive film.

[0523] For the purposes of the present invention, the term "acrylic polymer" means a polymer synthesized from at least one monomer chosen from (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide.

[0524] The unit(s) derived from the (meth)acrylic acid monomers of the polymer may optionally be in the form of salt(s), in particular of alkali metal, alkaline earth metal, ammonium or organic base.

[0525] The esters of (meth)acrylic acid (also called (meth)acrylates) are advantageously chosen from alkyl (meth)acrylates, in particular C 1 to C 10 alkyl 30, preferably C1 to C2o, better still C1 to C10, aryl (meth)acrylates, in particular C6 to C10 aryl, hydroxyalkyl (meth)acrylates, in particular C2 to C6 hydroxyalkyl.

[0526] Among the alkyl (meth)acrylates, mention may be made of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate.

[0527] Among the hydroxyalkyl (meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.

[0528] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0529] The particularly preferred (meth)acrylic acid esters are alkyl (meth)acrylates, preferably C1 to C30 alkyl, more preferably C1 to C20, even better C1 to C10, and even more particularly C1 to C4.

[0530] According to the present invention, the alkyl group of the esters may be fluorinated, or even perfluorinated, that is to say that some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

[0531] As amides of (meth)acrylic acid, mention may be made, for example, of (meth)acrylamides, as well as N-alkyl (meth)acrylamides, in particular of C2 to C12 alkyl. Among the N-alkyl (meth)acrylamides, mention may be made of N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide and N-undecylacrylamide.

[0532] The acrylic polymer according to the invention may be a homopolymer or a copolymer, advantageously a copolymer, even better a copolymer of (meth)acrylic acid and (meth)acrylic acid esters.

[0533] Preferably, the acrylic polymer(s) according to the invention comprise one or more units derived from the following monomers:

[0534] a) (meth)acrylic acid; and

[0535] b) C1 to C30 alkyl (meth)acrylate, more preferably C1 to C20, even better C1 to C10, and even more particularly C1 to C4.

[0536] Preferably, the aqueous dispersion of acrylic polymer particles does not comprise a surfactant.

[0537] The term “surfactant” means any agent capable of modifying the surface tension between two surfaces.

[0538] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and ethyl acrylate such as the compound sold under the trade name LUVIMER MAE by the company BASF, or Polyacrylate-2 crosspolymer compound sold under the trade name FIXATE SUPERHOLD POLYMER by the company LUBRIZOL, or the Acrylate Copolymer compound sold under the trade name DAITOSOL 3000VP3 by the company DAITO KASEI KOGYO, or the Acrylate Copolymer compound sold under the trade name DAITOSOL 3000SLPN-PE1 by the company DAITO KASEI KOGYO.

[0539] The acrylic polymer may optionally comprise one or more additional monomers, other than the (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide monomers.

[0540] As additional monomer, examples that may be mentioned are styrenic monomers, in particular styrene and alpha-methylstyrene, and preferably styrene.

[0541] In particular, the acrylic polymer may be a styrene / (meth)acrylate copolymer, and in particular a polymer chosen from copolymers resulting from the polymerization of at least one styrene monomer and at least one C1 to C20, preferably C1 to C10, alkyl (meth)acrylate monomer.

[0542] The C 1 to C 10 alkyl (meth)acrylate monomer may be chosen from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethyl hexyl acrylate.

[0543] As acrylic polymer, mention may be made of the styrene / (meth)acrylate(s) copolymers marketed under the name JONCRYL 77 by the company BASF, under the name YODOSOL GH41F by the company AKZO NOBEL and under the name SYNTRAN 5760 CG by the company INTERPOLYMER.

[0544] Preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles.

[0545] More preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more units derived from the following monomers:

[0546] a) (meth)acrylic acid; and

[0547] b) C1 to C30 alkyl (meth)acrylate, more preferably C1 to C20, even better C1 to C10, and even more particularly C1 to C4.

[0548] Preferably, the aqueous dispersion of acrylic polymer particles has an acrylic polymer (or active material, or dry matter) content based on the weight of the dispersion of 20 to 60% by weight, more preferably of 22 to 55% by weight and more preferably of 25 to 50% by weight. Silicone acrylic copolymer

[0549] According to a particular embodiment, the silicone compound(s) comprising at least one carboxylic group are chosen from silicone acrylic copolymers.

[0550] Thus, according to a particular embodiment, the compound(s) having at least one carboxylic function are chosen from silicone acrylic copolymers.

[0551] Preferably, said silicone acrylic copolymer(s) comprise:

[0552] - at least one acrylic or methacrylic or crotonic unit; and

[0553] - at least one polydimethylsiloxane (PDMS) unit.

[0554] For the purposes of the present invention, the term "polydimethylsiloxanes" (also abbreviated as PDMS), in accordance with general acceptance, means 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 to said silicon atoms.

[0555] 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.

[0556] By polymerizable radical group is meant a radical capable of polymerizing with other polymerizable radical groups or monomers. Preferably, the polydimethylsiloxane unit comprises at least one polymerizable radical group.

[0557] Preferably, the polymerizable radical group comprises at least one vinyl group.

[0558] 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.

[0559] 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.

[0560] 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.

[0561] Preferably, said silicone acrylic copolymer(s) comprise:

[0562] - at least one acrylic or methacrylic or crotonic unit, and at least one unit acrylic ester or methacrylic ester or vinyl ester; and

[0563] - at least one polydimethylsiloxane (PDMS) unit.

[0564] 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.

[0565] By crotonic unit is meant a unit derived from a crotonic acid monomer or one of its salts.

[0566] 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.

[0567] 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.

[0568] By vinyl acetate unit is meant a unit derived from a vinyl acetate monomer.

[0569] 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 at least one vinyl group.

[0570] 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

[0571] - at least one polydimethylsiloxane (PDMS) unit comprising at least one group polymerizable radical comprising at least one vinyl group.

[0572] 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 group polymerizable radical comprising at least one vinyl group.

[0573] Even more preferably, the composition comprises one or more silicone acrylic copolymers comprising:

[0574] - 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

[0575] - at least one polydimethylsiloxane (PDMS) unit comprising at least one group polymerizable radical comprising at least one vinyl group.

[0576] Among the silicone acrylic copolymers that can be used in the context according to 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.

[0577] The total amount of the compound(s) having at least one carboxylic function preferably ranges from 0.1 to 30% by weight, more preferably from 0.5 to 20% by weight, better still from 1 to 15% by weight, and even more preferably from 2 to 10% by weight relative to the total weight of composition C.

[0578] The total quantity of the aqueous dispersion(s) of polymer particles chosen from polyurethanes, acrylic polymers, and their mixtures preferably ranges from 0.1 to 35% by weight, more preferably from 0.5 to 30% by weight, better still from 1 to 20% by weight, and even more preferably from 3 to 15% by weight relative to the total weight of composition C.

[0579] According to a particular embodiment, the total quantity of the aqueous dispersion(s) of acrylic polymer particles preferably ranges from 0.1 to 35% by weight, more preferably from 0.5 to 30% by weight, better still from 1 to 20% by weight, and even more preferably from 3 to 15% by weight relative to the total weight of composition C.

[0580] Advantageously, the total quantity of silicone acrylic copolymer(s) ranges from 0.1 to 30% by weight, more preferably from 0.5 to 20% by weight, better still from 1 to 15% by weight, and even more preferably from 2 to 10% by weight relative to the total weight of composition C. Associative polymers

[0581] Composition C according to the invention may further comprise at least one associative polymer different from the compound having at least one carboxylic function and different from the non-carboxylic anionic thickening agent as defined previously.

[0582] As recalled above, “associative polymers” are polymers capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

[0583] Their chemical structure more particularly comprises at least one hy- zone drophile and at least one hydrophobic zone.

[0584] By “hydrophobic group” is meant a radical or polymer with a hydrocarbon chain, saturated or not, linear or branched, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms.

[0585] Preferably, the hydrocarbon group originates from a monofunctional compound. For example, the hydrophobic group may originate from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It may also designate a hydrocarbon polymer such as, for example, polybutadiene.

[0586] The associative polymers can be non-ionic, anionic, cationic or amphoteric in nature.

[0587] Preferably, the associative polymer(s) are chosen from anionic associative polymers.

[0588] Among the anionic type associative polymers, we can cite:

[0589] - (a) those comprising at least one hydrophilic unit, and at least one ether unit of fatty chain allyl, more particularly those whose hydrophilic unit is constituted by an ethylenically unsaturated anionic monomer, more particularly still by a vinyl carboxylic acid and very particularly by an acrylic acid or a methacrylic acid or mixtures thereof.

[0590] Among these anionic associative polymers, particularly preferred according to the invention are polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60% by weight of lower alkyl (meth)acrylates, from 2 to 50% by weight of fatty chain allyl ether, and from 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable polyethylene unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

[0591] Among the latter, particularly preferred are crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) stearyl alcohol ether (Steareth 10), in particular those sold by the company CIBA under the names SALCARE SC80® and SALCARE SC90® which are 30% aqueous emulsions of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40 / 50 / 10).

[0592] - (b) those comprising i) at least one hydrophilic unit of carboxylic acid type olefinically unsaturated, and ii) at least one hydrophobic unit of the unsaturated carboxylic acid (C10-C30) alkyl ester type.

[0593] Alkyl esters (Ci0-C30) of unsaturated carboxylic acids useful in the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and the corresponding methacrylates. pondants, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

[0594] Anionic polymers of this type are for example described and prepared, according to US patents 3,915,921 and 4,509,949.

[0595] Among this type of anionic associative polymers, those consisting of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of Cio-C3o alkyl acrylate (hydrophobic unit), and 0 to 6% by weight of crosslinking polymerizable monomer, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of Cio-C3o alkyl acrylate (hydrophobic unit), and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above, will be used more particularly.

[0596] Among the above polymers, the products sold by the company GOODRICH under the trade names PEMULEN TRI®, PEMULEN TR2®, CARBOPOL 1382®, and even more preferably PEMULEN TRI®, and the product sold by the company SEPPIC under the name COATEX SX® are particularly preferred according to the present invention.

[0597] Mention may also be made of the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer marketed under the name Acrylidone LM by the ISP Company.

[0598] - (c) maleic anhydride / C30-C38 α-olefin / alkyl maleate terpolymers such as that the product (maleic anhydride / C30-C38 a-olefin / isopropyl maleate copolymer) sold under the name PERFORMA V 1608® by the company NEWPHASE TECHNOLOGIES.

[0599] - (d) acrylic terpolymers comprising:

[0600] i) about 20 to 70% by weight of an α,[3-monoethylenically unsaturated carboxylic acid [A],

[0601] ii) about 20 to 80% by weight of a non-surfactant α,[3-monoethylenically unsaturated monomer different from [A],

[0602] iii) about 0.5 to 60% by weight of a non-ionic mono-urethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate,

[0603] such as those described in patent application EP-A-0173109 and more particularly that described in example 3, namely, a methacrylic acid / methyl acrylate / ethoxylated behenyl alcohol dimethyl metaisopropenyl benzyl isocyanate terpolymer (40 EO) in 25% aqueous dispersion.

[0604] - (e) copolymers comprising among their monomers a carboxylic acid with α,[3-monoethylenic saturation and an α,[3-monoethylenic unsaturated carboxylic acid ester of an oxyalkylenated fatty alcohol.

[0605] Preferably, these compounds also comprise an ester as monomer. of α,β-monoethylenically unsaturated carboxylic acid and C1-C4 alcohol.

[0606] As an example of this type of compound, we can cite ACULYN 22® sold by the company ROHM and HAAS, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer as well as ACULYN 88 also sold by the company ROHM and HAAS.

[0607] Advantageously, the associative polymer(s), different from the compounds having at least one carboxylic function and different from the non-carboxylic anionic thickening agents previously described, are chosen from acrylic associative polymers, more preferably carboxylic acrylic associative polymers.

[0608] In a particularly preferred manner, the associative polymer(s), different from the compounds having at least one carboxylic function and different from the non-carboxylic anionic thickening agents previously described, are chosen from copolymers comprising among their monomers an α,[3-monoethylenically unsaturated carboxylic acid and an ester of an α,[3-monoethylenically unsaturated carboxylic acid and an oxyalkylenated fatty alcohol.

[0609] Advantageously, the total quantity of the associative polymer(s) different from the compound(s) having at least one carboxylic function and different from the non-carboxylic anionic thickening agent(s) as defined previously ranges from 0.05 to 15% by weight, preferably from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight, and even more preferably from 0.1 to 1% by weight relative to the total weight of composition C. Solvents

[0610] The composition C used in the context of the process according to the invention may be aqueous. The water content may range from 1 to 90% by weight, preferably from 10 to 80% by weight, more preferably from 20 to 75% by weight relative to the total weight of the composition C.

[0611] In addition, composition C may comprise one or more organic solvents.

[0612] Examples of organic solvents that may be mentioned are lower alkanols of CrC 4, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols, in particular aromatic monoalcohols such as benzyl alcohol, phenoxyethanol, and mixtures thereof.

[0613] The organic solvents may be present in a total amount of between 0.01 and 60% by weight, preferably between 0.05 and 50% by weight and more preferably inclusively between 0.1 and 45% by weight relative to the total weight of composition C. Additives

[0614] Composition C used in the context of the process according to the invention may contain any adjuvant or additive usually used.

[0615] Among the additives that may be contained in the composition, mention may be made of reducing agents, softeners, anti-foaming agents, moisturizing agents, UV filters, peptizers, perfumes, anionic, cationic, non-ionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers previously described, preservatives, silicones, oils, waxes other than silicones in wax form, and mixtures thereof.

[0616] 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 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.

[0617] 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

[0618] 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.

[0619] Preferably, the silicone compound comprising at least one carboxylic group is a silicone compound different from the silicone acrylic copolymer as described previously.

[0620] 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.

[0621] 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.

[0622] Silicones are notably described in detail in the work of Walter NOLL "Chemistry and Technology of Silicones" (1968), Academie Press.

[0623] Preferably, the silicone compound(s) comprising at least one carboxylic group are chosen from the organosiloxanes of the following formula (XXVII): _ (XXVII) 81 RI | | RI î Ri R 5----S | —0 ™L Si—O ---)—«-U Si --0 —I—Si------------R 3 m [ri R2

[0624] 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 denotes 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.

[0625] In particular, the silicone compound(s) comprising at least one carboxylic group may be chosen from the organosiloxanes of the following formula (XXVIII): (XXVIII), Rt —Ri ---If----51-- «4—COOM Ai Ai

[0626] 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 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;

[0627] - organosiloxanes of the following formula (XXIX): (XXIX),

[0628] 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 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 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; - p denotes an integer ranging from 1 to 1000; - n denotes an integer ranging from 1 to 1000;

[0629] - organosiloxanes of the following formula (XXX):

[0630] 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 atom oxygen 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, 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;

[0631] - organosiloxanes of the following formula (XXXI):

[0632] 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 designated an integer ranging from 1 to 1000.

[0633] -and their mixtures.

[0634] Among the organosiloxanes of formula (XXVIII), mention may be made of polydimethylsiloxane (PDMS) with a carboxy terminal function such as the compounds sold by the company Momentive under the trade name SILFORM INX (INCI name: Bis-Carboxydecyl dimethicone).

[0635] 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.

[0636] 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.

[0637] 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).

[0638] The 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.

[0639] Preferably, the silicone compound(s) comprising at least one carboxylic group are chosen from organopolysiloxanes of formula (XXVIII), organopolysiloxanes of formula (XXIX) and mixtures thereof.

[0640] More preferably, the silicone compound(s) comprising at least one carboxylic group are chosen from the organopolysiloxanes of formula (XXVIII) below: (XXVIII)

[0641] in which:

[0642] - 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.

[0643] 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 the composition D. Oils

[0644] Composition D may comprise one or more oil(s) different from the silicone compounds comprising at least one carboxylic group previously described.

[0645] Preferably, composition D comprises one or more oil(s). More preferably, composition D comprises one or more oil(s) chosen from alkanes.

[0646] By “oil” is meant a fatty substance which is liquid at room temperature (25°C) and atmospheric pressure (760 mm Hg or 1.013 105 Pa).

[0647] The oil may be volatile or non-volatile.

[0648] 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.

[0649] 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.

[0650] Preferably, the composition comprises one or more oil(s) chosen from C6-C16 alkanes and / or their mixtures.

[0651] As regards C6-Ci6 alkanes, these can be linear, branched, possibly cyclic.

[0652] 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.

[0653] 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.

[0654] 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 Company.

[0655] 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.

[0656] As an example 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.

[0657] According to a particular embodiment, the composition comprises isododecane. Such a compound is for example isododecane sold under the reference ISO-DODECANE by INEOS.

[0658] Preferably, composition D comprises one or more oil(s) chosen from C8-C16 alkanes, more preferably from isododecane, isohexadecane, tetradecane and / or mixtures thereof.

[0659] More preferably, composition D comprises isododecane.

[0660] Composition D may comprise one or more oils different from the compounds silicones comprising at least one carboxylic group 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.

[0661] Composition D may comprise at least one coloring agent chosen from pigments, direct dyes, and their mixtures as described previously. Protocol

[0662] The treatment with a composition T comprising at least one alcohol as defined above can be carried out on dry or damp hair, as well as on all types of hair, light or dark, natural or colored, permed, bleached or straightened.

[0663] According to a particular embodiment of the invention, the hair is rinsed with water or washed after treatment with a composition T comprising at least one alcohol as defined previously.

[0664] Preferably, a washing or rinsing, spinning or drying step is carried out after the treatment with a composition T comprising at least one alcohol as defined previously.

[0665] More preferably, a drying step is carried out after the treatment with a composition T comprising at least one alcohol as defined previously.

[0666] The treatment with a composition T comprising at least one alcohol as defined previously can be carried out between 15 and 40°C.

[0667] After treatment with a composition T comprising at least one alcohol as defined above, it is possible to wait between 1 minute and 12 hours, in particular between 1 minute and 10 hours, more particularly between 1 minute and 7 hours, more preferably Leave for between 1 minute and 6 hours, before applying composition C to the hair.

[0668] Preferably, the exposure time is between 1 minute and 5 hours before applying composition C to the hair.

[0669] 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.

[0670] According to a preferred embodiment, composition C and optional composition D are applied simultaneously to the hair.

[0671] According to another preferred embodiment, composition D is applied to the hair after the application of composition C to the hair.

[0672] According to another preferred embodiment, composition D is applied to the hair before applying composition C to the hair.

[0673] More preferably, composition D is applied to the hair after the application of composition C to the hair.

[0674] According to a particular embodiment of the invention, the hair is rinsed before application of composition C and composition D.

[0675] Preferably, a rinsing, wringing and / or drying step is carried out after the application of composition C to the hair and before the application of composition D to the hair.

[0676] More preferably, a drying step is carried out after the application of composition C to the hair and before the application of the optional composition D to the hair.

[0677] 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.

[0678] The application of composition C and of the optional composition D to the hair is generally carried out at room temperature (between 15 and 25°C).

[0679] After applying composition C to the hair, it is possible to 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, applying composition D to the hair or, for example, a drying step.

[0680] Preferably, there is no application time after the application of composition C to the hair and before the application of the optional composition D to the hair.

[0681] After applying composition C and optional composition D, the hair may be left to dry or dried, for example at a temperature greater than or equal to 30°C.

[0682] The method according to the invention can thus comprise a step of applying heat to the keratin fibers using a heating tool.

[0683] 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,

[0684] Preferably, the heat application step of the method of the invention is carried out using a hair dryer.

[0685] 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 optional composition D to the hair.

[0686] 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.

[0687] 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.

[0688] 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.

[0689] 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.

[0690] Step (cl) can be carried out before step (c2).

[0691] 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.

[0692] 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.

[0693] During drying, a mechanical action on the strands can be exerted such as combing, brushing, passing the fingers.

[0694] 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.

[0695] 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.

[0696] The hair coloring process according to the invention comprises:

[0697] (i) a step of treating the hair with a composition T comprising at least minus one alcohol as described previously, then

[0698] (ii) a step consisting of applying to the hair at least one coloring composition C comprising: 1. at least one (poly)carbodiimide compound as described above; and 2. at least one coloring agent as described above.

[0699] Preferably, the invention is a hair coloring process comprising:

[0700] (i) a step of treating the hair with a composition T comprising at least minus one alcohol as described previously, then

[0701] (ii) optionally a time for leaving said composition T on the hair of 1 minute to 6 hours, preferably of 1 to 5 hours; then

[0702] (iii) a step consisting of applying to the hair at least one coloring composition C comprising: 1. at least one (poly)carbodiimide compound as described above; 2. at least one coloring agent as described above.

[0703] (iv) optionally a time for leaving said composition C on the hair of 1 minute to 30 minutes, preferably of 1 to 20 minutes; then (v) optionally a step of washing, rinsing, wringing and / or drying said hair, then

[0704] (vi) optionally 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; then (vii) optionally a time for leaving said composition D on the hair of 1 minute to 30 minutes, preferably of 1 to 20 minutes; then (viii) optionally a step of washing, rinsing, wringing and / or drying the hair.

[0705] Preferably, composition C further comprises at least one non-carboxylic anionic thickening agent and / or at least one compound having at least one carboxylic function, as described previously.

[0706] Advantageously, the coloring process comprises step (vi) of applying to the hair a composition D comprising at least one silicone compound comprising at least one carboxylic group as described previously.

[0707] Advantageously, in the coloring process according to the invention, the step (ii) consists 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 (1) at least one (poly)carbodihnide compound such that previously defined; - composition B comprising (2) at least one coloring agent as defined previously.

[0708] According to a preferred embodiment, the coloring process according to the invention is a hair coloring process comprising:

[0709] (i) a step of treating the hair with a composition T comprising at least minus one alcohol as described previously, then

[0710] (ii) a step 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:

[0711] - composition A comprising (1) at least one (poly)carbodihnide compound such as described previously; - composition B comprising (2) at least one coloring agent as described previously; composition A and / or composition B optionally comprising at least one non-carboxylic anionic thickening agent and / or at least one compound having at least one carboxylic function, as described previously.

[0712] 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.

[0713] Preferably, composition A does not comprise at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof.

[0714] 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.

[0715] 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.

[0716] According to a preferred embodiment, the coloring process according to the invention is a hair coloring process comprising:

[0717] (i) a step of treating the hair with a composition T comprising at least minus one alcohol as described previously, then

[0718] (ii) a step 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:

[0719] - composition A comprising (1) at least one (poly)carbodiimide compound such as described previously; - composition B comprising (2) at least one coloring agent as described previously; composition A and / or composition B optionally comprising at least one non-carboxylic anionic thickening agent and / or at least one compound having at least one carboxylic function, as described previously, and

[0720] - the application to the hair of at least one composition D comprising at least a 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.

[0721] Preferably, composition A optionally comprises at least one non-carboxylic anionic thickening agent as described above.

[0722] More preferably, composition A comprises at least one non-carboxylic anionic thickening agent as described previously.

[0723] Preferably, composition B does not comprise at least one non-carboxylic anionic thickening agent as described previously.

[0724] The total amount of the (poly)carbodiimide compound(s) 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.

[0725] The total amount of the compound(s) having at least one carboxylic function preferably ranges from 0.2 to 60% by weight, more preferably from 1 to 40% by weight, better still from 1 to 30% by weight, and even more preferably from 2 to 20% by weight relative to the total weight of composition B.

[0726] The total quantity of the aqueous dispersion(s) of polymer particles chosen from polyurethanes, acrylic polymers, and their mixtures preferably ranges from 0.2 to 60% by weight, more preferably from 1 to 50% by weight, better still from 1 to 40% by weight, and even more preferably from 2 to 30% by weight relative to the total weight of composition B.

[0727] According to a particular embodiment, the total quantity of the aqueous dispersion(s) of acrylic polymer particles preferably ranges from 0.2 to 60% by weight, more preferably from 1 to 50% by weight, better still from 1 to 40% by weight, and even more preferably from 2 to 30% by weight relative to the total weight of composition B.

[0728] The non-carboxylic anionic thickening agent(s) may be present in a total amount varying from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight, better still from 0.1 to 5% by weight, and even better still from 0.1 to 3% by weight, by relative to the total weight of composition A. Multi-compartment device (kit)

[0729] The present invention also relates to a device for coloring hair comprising several compartments containing:

[0730] * in a first compartment, a composition T comprising at least one alcohol as previously described, and

[0731] * in a second compartment, a composition A comprising at least one (poly)carbodiimide compound as described above, and

[0732] * in a third compartment, a composition B comprising at least one agent colorant as defined above, and

[0733] ​​* optionally, in a fourth compartment, a composition D comprising at least one silicone compound comprising at least one carboxylic group as described previously.

[0734] Composition A and / or composition B, preferably composition B, may optionally further comprise at least one compound having at least one carboxylic function, as described previously.

[0735] 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

[0736] 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.

[0737] 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 previously, which reacts in the presence of a carboimidation catalyst (2) such as those described in US 4,284,730, in particular phosphorus-containing catalysts particularly chosen from phospholene oxides and phospholene sulfoxides, diaza and oxazaphospholanes, preferably under an 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 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 previously. Halogenated benzoyl such as benzoyl chloride may be added to deactivate the catalyst.

[0738] 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.

[0739] 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.

[0740] According to a variant for obtaining compound (5) from (3) it is possible to first add 1 eq. of reagent Ri-XrH, then 0.5 eq. of reagent HEH.

[0741] 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'),

[0742] 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 dissymmetrical 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),

[0743] Formula (7) in which Rb Xb Lb R2, X2, n, z and E are as defined previously.

[0744] 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),

[0745] 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.

[0746] 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.

[0747] The (poly)carbodiimide compounds as well as all the 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.

[0748] Example 1: Process for the synthesis of the compound (poly)carbodiimide

[0749] 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.

[0750] The reaction medium was heated to 140°C under nitrogen for 4 hours, following the reaction by infrared spectroscopy through the absorption of the isocyanate functions between 2200 and 2300 cm1, then cooled to 120°C.

[0751] 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.

[0752] 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

[0753] Compositions A1 and B1 as described below were prepared: the quantities are expressed in g of raw material as is / 100g, unless otherwise stated.

[0754] [Tables 1] Compositions Al Polycarbodiimide (1) 17.5 Hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer (2) 3 Ethanol 20 Water qsp 100

[0755] (1) synthesized according to the synthesis method described in example 1 (at 40% material active in water),

[0756] (2) sold by the company SEPPIC under the name SEPINOV EMT10 (at 90% of active ingredient)

[0757] [Tables2] Compositions B1 Acrylates copolymer (3) 29.2 Red iron oxide (CI 77491) 12 Divinyldimethicone / dimethicone copolymer (and) C12-13 Pareth-3 (and) Ci2-b Pareth-23(4) 10.2 Bis-Hydroxy / Methoxy / Methyl Amodimethicone Crosspolymer (and) Trideceth-10 8.8 Acrylates / Steareth-20 methacrylate copolymer (5) 2.2 Preservative(s) qs Water qsp 100

[0758] (3) sold by the company DAITO KASEI KOGYO under the trade name DAITOSOL 3000SLPN-PE1 (aqueous dispersion with 30% active ingredient),

[0759] (4) sold by the company DOW CORNING under the name DOW CORNING HMW 2220 NON-IONIC EMULSION (Divinyldimethicone / dimethicone block copolymer in aqueous emulsion) (60% active ingredient)

[0760] (5) sold by the company ROHM and HAAS under the trade name ACULYN 22® (methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer at 30% active ingredient)

[0761] Composition Al was then mixed with composition B1 at a mass ratio of 50 / 50 to obtain a composition Cl according to the invention.

[0762] Then, composition D as described below was prepared: the quantities are expressed in g of raw material as is / 100g.

[0763] [Tables3] Composition D Organopolysiloxane with carboxylic group (6) 2 Isododecane qsp 100

[0764] (6) Silform INX sold by Momentive Performance Materials

[0765] Pre-treatment with alcohol:

[0766] Some wicks are pre-treated with one of the alcohols below. The quantities are expressed in g of raw material as is / 100g, unless otherwise stated.

[0767] [Tables4] Composition Tl Butylene glycol 100 Protocol

[0768] When a treatment step with composition Tl comprising butylene glycol is carried out, the following protocol was applied:

[0769] a treatment with composition Tl comprising butylene glycol is carried out on locks of 90% white natural hair, at a rate of 2 g of composition per gram of lock. The treatment is left to act for 5 minutes or 5 hours at a temperature of approximately 35°C. Then the locks were rinsed with water and dried with absorbent paper.

[0770] Composition Cl is then applied to the treated strands, at a rate of 0.8 g of composition per gram of strand. The strands of hair are then dried with a hair dryer.

[0771] Then, composition D was applied to the locks of hair previously treated or not with butylene glycol and composition Cl, at a rate of 0.5 g of composition per gram of lock. Then the locks of hair are dried with a hair dryer.

[0772] The hair strands were then stored at room temperature for 24 hours.

[0773] Three methods were applied and were summarized in Table 5 below:

[0774]

[0775]

[0776]

[0777]

[0778]

[0779]

[0780]

[0781]

[0782] [Tables 5] Processes Treatment with butylene glycol Application of compositions Exposure time of Tl 1 (invention) YES Tl + C1 +D 5 min 2 (invention) YES Tl + C1 +D 5h 3 (comparative) NO Cl + DN / A Thus, the locks of hair treated with composition Tl then Cl and D with a treatment time of composition Tl of 5 min or 5 h are treated by method 1 or 2 according to the invention. The hair strands treated with compositions Cl and D only are treated by comparative method 3. The locks of hair treated by processes 1 to 3 were then subjected to a test of several repeated shampoos in order to evaluate the tenacity (the persistence) of the coloring obtained from the shampoos. Results The color persistence of the highlights was evaluated in the CIE L*a*b* system, using a Minolta CM3610A spectrophotometer (illuminant D65, angle 10°, specular component included). 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. Color persistence is assessed by the color difference AErémanence between colored strands before shampooing, and then after 15 shampoos. The lower the AÉrémanence value, the more persistent the color is after shampooing. The value of AErémanence is calculated according to the following equation: In this equation, L*, a* and b* represent the values ​​measured after hair coloring and after shampooing, and Lo*, a0* and b0* represent the values ​​measured after hair coloring but before shampooing.

[0783] [Tableauxô] Processes Number of L* a* b* AE XJ—'remanence shampoos 4.14 1 (invention) 0 30.72 28.73 18.61 5 34.07 26.37 18.05 2 (invention) 0 32.99 27.85 18.88 4.76 5 34.68 24.29 16.21 3 (comparative) 0 34.3 27.15 16.84 10.88 5 43.74 21.75 16.56

[0784] The locks of hair treated with process 1 or 2 according to the invention and washed with five shampoos have a higher persistence than that of the locks of hair treated with comparative process 3.

[0785] Thus, the colored coating obtained with the methods according to the invention has improved persistence to shampooing. Example 3

[0786] Compositions A2, A3 and B2 as described below were prepared: the quantities are expressed in g of raw material as is / 100g, unless otherwise stated.

[0787] [Tables7] Compositions A2 A3 Polycarbodiimide (1) 100 - Polycarbodiimide m - 100

[0788] (1) synthesized according to the synthesis method described in example 1 (at 40% material active in water),

[0789] (7) sold by the company STAHL BV under the name PERMUTEX XR-13-554

[0790] [Tables8] Compositions B2 Crotonic Acid / Vinyl C8-12 Isoalkyl Esters / VA / Bis-Vinyldimethicone Crosspolymer (8) 10.3 Red Iron Oxide (CI 77491) 1 Phosphoric Acid 85% in Water 0.1 Ammonia 25% in Water 3.1 Isopropanol qsp 100

[0791] (8) sold by the company WACKER Chemie AG under the trade name Belsil® PI 101 (50% active ingredient in ethanol),

[0792] Compositions A2 and A3 are then mixed with composition B2 at a mass ratio of 2 / 98 to obtain compositions C2 (invention) and C3 (comparative).

[0793] Pre-treatment with alcohol:

[0794] The wicks are pretreated with the following composition T2. ​​The quantities are expressed in g of raw material as is / 100g, unless otherwise stated.

[0795] [Tables9] Composition T2 Isopropanol 100 Protocol

[0796] A treatment with composition T2 comprising isopropanol is carried out on locks of 90% white hair, at a rate of 2 g of composition per gram of lock. The treatment is left to act for 15 minutes at a temperature of approximately 35°C. The locks are then rinsed with water before being dried with a hair dryer.

[0797] Composition C2 and composition C3 are then applied to the treated strands, at a rate of 1 g of composition per gram of strand. The strands of hair are then dried with a hair dryer.

[0798] The hair strands were then stored at room temperature for 24 hours.

[0799] Two methods were applied and were summarized in Table 10 below:

[0800] [Tables 10] Methods 4 (invention) 5 (comparative) Treatment with isopropanol YES YES Application of compositions T2 + C2 T2 + C3

[0801] Thus, the locks of hair treated with composition T2 then C2 are treated by method 4 according to the invention.

[0802] The locks of hair treated with compositions T2 and C3 are treated by comparative method 5.

[0803] The locks of hair treated by methods 4 and 5 were then subjected to a test of several repeated shampoos in order to evaluate the tenacity (the persistence) of the coloring obtained from the shampoos.

[0804] [Tableauxll] Processes Number of shampoos L* a* b* AE ^^remanence 4 (invention) 0 38.2 25.4 20.6 1.3 5 39.0 24.5 20.1 5 (comparative) 0 41.7 24.5 21.0 3.3 5 41.4 21.8 19.2

[0805] The locks of hair treated with method 4 according to the invention and washed with five shampoos have a higher persistence than that of the locks of hair treated with the comparative method 5.

[0806] Thus, the colored coating obtained with the process according to the invention has improved persistence to shampooing.

Claims

1. Claims Hair coloring process comprising: (i) a step of treating the hair with a composition T comprising at least one alcohol, then (ii) a step consisting of applying to the hair at least one coloring composition C comprising: (1) at least one (poly)carbodiimide compound chosen from the 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 aliphatic hydrocarbon radical of CrCi8, a cycloalkylene radical of C3-Ci5, a heterocycloalkylene group of C3-Ci2, or a arylene group of C6-Ci4, 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 heteroatoms; - R6 independently represents a hydrogen atom, or a hydrocarbon radical optionally interrupted by one or more heteroatoms; and (2) at least one coloring agent chosen from pigments, direct dyes and their mixtures.

2. Process according to claim 1, characterized in that the alcohol(s) are chosen from monoalcohols having from 1 to 10 carbon atoms, polyols having from 2 to 32 carbon atoms and mixtures thereof.

3. Process according to claim 1 or 2, characterized in that the alcohol(s) are chosen from monoalcohols having from 1 to 10 carbon atoms, glycerol, polyglycerols, glycols having from 2 to 8 carbon atoms, glycerol oligomers such as polyethylene glycol or polypropylene glycol, glycol ethers, polyols comprising three or more hydroxyl functions, and mixtures thereof.

4. Method according to any one of the preceding claims, characterized in that the alcohol(s) are chosen from isopropanol, butylene glycol, and their mixture, preferably the alcohol is butylene glycol.

5. Process according to any one of the preceding claims, characterized in that the alcohol(s) are present in a content of 10% to 100% by weight, preferably 50% to 100% by weight, more preferably 80% to 100% by weight, even more preferably 90% to 100% by weight, better still equal to 100% by weight relative to the total weight of the composition T.

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 (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 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 CrCi8 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.

7. Process according to any one of the preceding claims, characterized in that the (poly)carbodihnide 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-C14 arylene radical, a cy- radical C3-Ci2 alkylene, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

8. 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 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 1 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 CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

9. 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 1 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 CrCi8 alkylene radical such as methylene, propylene, butylene, ethylene, optionally interrupted by one or more heteroatom(s).

10. 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 1 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.

11. 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.

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. 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.

14. Process according to claim 13, 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.

15. Method according to any one of claims 1 to 10, 13 and 14, characterized in that step (ii) consists 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 (1) at least one (poly)carbodiimide compound as defined in any one of claims 1 and 6 to 10; - composition B comprising (2) at least one coloring agent as defined in claim 1.

16. Device for coloring hair comprising several compartments containing: - in a first compartment, a composition T comprising at least one alcohol as defined in any one of claims 1 to 5, - in a second compartment, a composition A comprising at least one (poly)carbodihnide compound as defined in any one of claims 1 and 6 to 10, - in a third compartment, a composition B comprising at least one coloring agent as defined in claim 1, and - optionally, in a fourth compartment, a composition D comprising at least one silicone compound comprising at least one carboxylic group as defined in claim 13 or 14.