A method of coloring hair comprising the application of a composition comprising a cyanoacrylate, followed by the application of a composition comprising at least one (poly)carbodiimide and a coloring agent

Abstract

Title: Process for coloring hair comprising the application of a composition comprising a cyanoacrylate, followed by the application of a composition comprising at least one (poly)carbodiimide and a coloring agent The present invention relates to a process for coloring hair comprising: a) the application to the hair of at least one composition T comprising at least one cyanoacrylate compound; followed by b) the application to the hair of at least one composition C comprising: i) at least one (poly)carbodiimide compound; ii) at least one coloring agent chosen from pigments, direct dyes and mixtures thereof; and iii) at least one polymer comprising at least one reactive group chosen from carboxylic acids.

Description

Title of the invention: Process for coloring hair comprising the application of a composition comprising a cyanoacrylate, followed by the application of a composition comprising at least one (poly)carbodiimide and a coloring agent

[0001] The present invention relates to a method for coloring hair comprising the application to the hair of at least one composition T comprising a cyanoacrylate compound; followed by the application to the hair of a composition C comprising a (poly)carbodiimide compound, a polymer comprising at least one reactive group chosen from carboxylic acids and a coloring agent chosen from pigments, direct dyes and mixtures thereof. 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 friction.

[0008] There therefore remains a need for a hair coloring process which has the advantage of obtaining a uniform colored coating on the hair, while forming a coating that is resistant to shampoos and various attacks that the hair may be subjected to such as brushing and / or friction.

[0009] Thus, the aim of the present invention is to develop a hair coloring process which has the advantage of obtaining a homogeneous and smooth colored coating on the hair, while forming a coating which is resistant to shampoos and to various aggressions which the hair may be subjected to such as brushing and / or rubbing. Presentation of the invention

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

[0011] a) the application to the hair of at least one composition T comprising at least one cyanoacrylate compound; followed by

[0012] b) applying to the hair at least one hair coloring composition C comprising:

[0013] i) at least one (poly)carbodiimide compound;

[0014] ii) at least one coloring agent chosen from pigments, direct dyes and their mixtures; and

[0015] iii) at least one polymer comprising at least one reactive group chosen from carboxylic acids.

[0016] Thanks to the hair coloring process according to the invention, homogeneous colored coatings are obtained on the hair, making it possible to obtain a visible coloring on all types of hair and lasting after shampooing. Such a coating can be resistant to external aggressions that the hair may be subjected to, such as brushing and perspiration.

[0017] The expression “at least one” means one or more.

[0018] 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 ...”.

[0019] The invention is not limited to the illustrated examples. The characteristics of the different examples may in particular be combined within non-illustrated variants.

[0020] For the purposes of the present invention and, unless otherwise indicated,

[0021] - an “alkyl” radical denotes a saturated linear or branched radical containing by example of 1 to 20 carbon atoms;

[0022] - an “aminoalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an NH2 group;

[0023] - a “hydroxyalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an OH group;

[0024] - an “alkylene” radical denotes a divalent saturated C2-C4 hydrocarbon group, linear or branched, such as methylene, ethylene, or propylene;

[0025] - 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,

[0026] - a “cycloalkylene” radical denotes a divalent cycloalkyl group with “cy “cloalkyl” as defined above, preferably C3-C12;

[0027] - 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;

[0028] - an “arylene” radical is a divalent aryl radical with “aryl” as defined above preferably arylene represents phenylene;

[0029] - 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;

[0030] - a “heterocycloalkylene” radical is a divalent heterocyclic group with “heterocyclic” as defined above;

[0031] - an “aryloxy” radical denotes an aryl-oxy radical with “aryl” as defined above cededly;

[0032] - an “alkoxy” radical denotes an alkyloxy radical with “alkyl” as defined previously;

[0033] - an “acyloxy” radical denotes an ester radical RC(O)-O- with R an alkyl group as defined above;

[0034] - a “reactive” group is a group capable of forming a bond covalent with another group, identical or different, by chemical reaction.

[0035] Unless otherwise indicated, when compounds are mentioned in the present application, their optical isomers, their geometric isomers, their tautomers, their salts, alone or in a mixture, are also understood.

[0036] 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.

[0037] 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. Composition T

[0038] The method according to the invention comprises the application to the hair of at least one composition T comprising at least one cyanoacrylate compound.

[0039] The cyanoacrylate compound(s) present in composition T according to the invention are preferably chosen from the compounds of the following formula (A): RI CN (A) y R2 COXR',.

[0040] in which:

[0041] - X denotes NH, S or O;

[0042] - RI and R2 each designate, independently of one another, a hydrogen atom, a saturated or unsaturated, linear, branched or cyclic hydrocarbon group, preferably comprising from 1 to 20, better still from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulfur atoms, and optionally substituted by one or more groups chosen from -OR, -COOR, -COR, -SH, -SR, -OH, and halogen atoms, a polyoxyalkylene group;

[0043] R denotes a saturated or unsaturated, linear, branched or cyclic hydrocarbon group, preferably comprising from 1 to 20, better still from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulfur atoms, and optionally substituted by one or more groups chosen from -OR', -COOR', -COR', -SH, -SR', -OH, halogen atoms, or a polymer residue which can be obtained by radical polymerization, by polycondensation or by ring opening; R' denoting a CrCio alkyl group;

[0044] - R'3 represents a hydrogen atom or a saturated or unsaturated hydrocarbon group, linear, branched or cyclic, preferably comprising from 1 to 20, better still from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulfur atoms, and optionally substituted by one or more groups chosen from -OR', -COOR', -COR', -SH, -SR', -OH, halogen atoms, or a polymer residue obtainable by radical polymerization, by polycondensation or by ring opening, R' denoting a CrCio alkyl group.

[0045] As saturated or unsaturated, linear, branched or cyclic hydrocarbon group, preferably comprising from 1 to 20 carbon atoms, mention may in particular be made of linear or branched alkyl, alkenyl or alkynyl groups, such as methyl, ethyl, n-butyl, tert-butyl, iso-butyl, pentyl, hexyl, octyl, butenyl or butynyl; cycloalkyl or aromatic groups.

[0046] As substituted hydrocarbon groups, examples that may be mentioned are hydroxyalkyl or polyhaloalkyl groups.

[0047] Among the polyoxyalkylene groups, mention may in particular be made of polyoxyethylene groups and polyoxypropylene groups preferably having 1 to 200 oxyalkylene units.

[0048] Among the cyanoacrylate compounds previously cited, preferred are the compounds of formula (A) in which:

[0049] - X denotes O;

[0050] - RI and R2 represent a hydrogen atom or a C1-C10 alkyl radical;

[0051] - R'3 represents an alkyl or alkoxyalkyl or hydroxyalkyl radical.

[0052] In the formulas of the cyanoacrylate compounds according to the invention, the alkyl or alkoxyalkyl radicals can be linear, branched and / or cyclic.

[0053] According to a preferred embodiment, the cyanoacrylate compound(s) correspond(s) to the following formula (B): Π(B) CO OR

[0054] in which R represents an alkyl or alkoxyalkyl or hydroxyalkyl radical, preferably comprising from 1 to 20, better still from 1 to 10 carbon atoms.

[0055] In the context of the invention, the cyanoacrylate compounds of formula (B) are monomers capable of polymerizing anionically in the presence of a nucleophilic agent, according to the mechanism defined in the work "Advanced Organic Chemistry", Third Edition by Jerry March, pages 151 to 161.

[0056] The cyanoacrylate compounds of formula (B) according to the present invention can be synthesized according to known methods described in the art. In particular, the cyanoacrylate compounds can be synthesized according to the teaching of US 3,527,224, US 3,591,767, US 3,667,472, US 3,995,641, US 4,035,334 and US 4,650,826.

[0057] As cyanoacrylate compounds of formula (B), mention may be made of ethyl 2-cyanoacrylate, methyl 2-cyanoacrylate, n-propyl 2-cyanoacrylate, isopropyl 2-cyanoacrylate, tert-butyl 2-cyanoacrylate, n-butyl, iso-butyl 2-cyanoacrylate, 3-methoxybutyl cyanoacrylate, n-decyl cyanoacrylate, hexyl 2-cyanoacrylate, 2-ethoxyethyl 2-cyanoacrylate, 2-methoxyethyl 2-cyanoacrylate, 2-octyl 2-cyanoacrylate, 2-propoxyethyl 2-cyanoacrylate, n-octyl 2-cyanoacrylate and iso-amyl cyanoacrylate.

[0058] According to a preferred embodiment, the cyanoacrylate compounds of formula (B) are chosen from those comprising alkyl or alkoxyalkyl radicals R of 1 to 10 carbon atoms, preferably of 6 to 10 carbon atoms.

[0059] According to a more preferred embodiment, the cyanoacrylate compound(s) of formula (B) are chosen from those comprising an alkyl radical R comprising from 6 to 10 carbon atoms (alkyl(C6-Ci0)-cyanoacrylates); preferably from those comprising an alkyl radical R which represents:

[0060] -(CH2)7-CH3,

[0061] -CH(CH3)-(CH2)5-CH3,

[0062] -CH2-CH(C2H5)-(CH2)3-CH3,

[0063] -(CH2)5-CH(CH3)-CH3,

[0064] -(CH2)4-CH(C2H5)-CH3.

[0065] According to an even more preferred embodiment, the cyanoacrylate compound is 2-octyl cyanoacrylate (or 2-octyl 2-cyanoacrylate), linear or branched.

[0066] Advantageously, the cyanoacrylate compound(s) as defined above are present in a total content ranging from 5 to 80% by weight, preferably from 15 to 75% by weight, more preferably from 25 to 65% by weight, better still from 40 to 60% by weight, relative to the total weight of the composition T.

[0067] The composition T used in the context of the process according to the invention may comprise one or more organic solvents.

[0068] As organic solvent, examples that may be mentioned are lower alkanols in 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.

[0069] Preferably, composition T comprises ethanol.

[0070] The organic solvents may be present in a total content of between 1 and 80% by weight, preferably between 5 and 70% by weight and more preferably inclusively between 10 and 60% by weight, relative to the total weight of the composition T.

[0071] According to a preferred embodiment, the composition T comprises at least one cyanoacrylate compound and at least one organic solvent.

[0072] According to a particular embodiment, the composition T comprising the cya- noacrylate is a composition that contains less than 5% water, preferably less than 3% water. Preferably the composition is anhydrous, the water content being solely due to the residual water of the raw materials used. (Poly)carbodiimide compound

[0073] Composition C used in the context of the process according to the invention comprises at least one (poly)carbodiimide compound.

[0074] The composition may comprise at least two distinct (poly)carbodiimide compounds, present as a mixture in the composition.

[0075] 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.

[0076] The term “carbodiimide group” means a divalent linear triatomic moiety of general formula - (N=C=N) -.

[0077] The (poly)carbodiimide compound(s) according to the invention may optionally comprise in their structure one or more reactive groups different from the carbodiimide groups, chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide groups such as propylepoxide or butylepoxide and azacyclopropane.

[0078] The reactive group(s) other than the carbodiimide groups may be pendant or terminal. Preferably, the (poly)carbodiimide compound(s) comprise one or more terminal groups other than the carbodiimide groups, preferably one or more terminal groups chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide groups such as propylepoxide or butylepoxide and azacyclopropane.

[0079] According to a particular embodiment, the (poly)carbodiimide compound is chosen from the compounds of the following formula (I): O H l J n H (I),

[0080] in which:

[0081] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0082] - Ri and R2 independently represent a group chosen from a radical hy carbon radical, preferably alkyl, optionally interrupted by one or more heteroatom(s), a group chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide, and azacyclopropane, and a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatom(s) and by one or more groups chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl groups,acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide, and azacyclopropane; ,

[0083] - n denotes an integer ranging from 1 to 1000; and

[0084] - A is a monomer chosen from the compounds below:

[0085] According to another embodiment, the (poly)carbodiimide compound is chosen from the compounds of the following formula (!): (D

[0086] in which:

[0087] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0088] - Yiet Y2 represent, independently, a divalent organic radical chosen from a C1-C36 saturated aliphatic group or a C6-C24 aromatic or alkylaromatic group, the aliphatic or aromatic group optionally comprising one or more non-pendant heteroatoms, such as nitrogen, oxygen, sulfur, or combinations thereof;

[0089] - Zi and Z2 represent, independently, a reactive terminal group or a group inert terminal;

[0090] - as an inert terminal group, Zi and Z2 can represent, independently, a saturated, linear or branched or cyclic aliphatic group, C1 to C50, or a group C6 to C[8 aromatic, said aliphatic and aromatic groups optionally comprising from 1 to 10 heteroatoms selected from nitrogen, oxygen, sulfur and combinations thereof, and the aliphatic or aromatic group may be partially or fully fluorinated; in this variant, Zi and Z2 comprise a CG linking group linking Zi to Yi and Z2 to Y2, the CG group being able to be a single covalent bond, a saturated CC bond, an unsaturated covalent CC bond, an amide group, an ester group, a carbonate group, a thioester group, an ether group, a urethane group, a thiourethane group or a urea group;

[0091] - as a reactive terminal group, Zi and Z2 may be chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide groups such as propylepoxide or butylepoxide and azacyclopropane;

[0092] - Q represents an organopolymer or an organo-oligomer comprising units re repeating groups of saturated, linear or branched or cyclic aliphatic groups, or aromatic groups or alkylaromatic groups, coupled by repeating carbonate, ester, ether, amide, urethane or urea bonds or combinations thereof;

[0093] - A represents a divalent aliphatic, aromatic, alkylaromatic or radical linear, saturated, branched or cyclic having from 2 to 30 carbon atoms, which may optionally include one or more non-pendant heteroatoms, such as the nitrogen atom, the oxygen atom, the sulfur atom, or combinations thereof, in the aliphatic chain or the aromatic chain;

[0094] - r denotes an integer equal to 0 or 1;

[0095] - m denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0096] - m' denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0097] - n denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1, with m+ (m'*n ) > 2.

[0098] Preferably, Zi and Z2 represent, independently, a reactive terminal group, more preferably, Zi and Z2 represent, independently, a group chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norborenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide groups such as propylepoxide or butylepoxide, and azacyclopropane.

[0099] Such (poly)carbodiimide compounds are for example marketed by the Stahl BV, under the name Permutex XR, or under the name RelcaLinklO., under the name Picassian XL and Nisshinbo compounds marketed under the name CARBODILITE with the series V-02, V-02-L2, SV-02, E-02, V-10, SW-12G, E-03A, E-04DG-T, E-05, V-04, V-02B, V-04PF, V-05.

[0100] Preferably, the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) below:

[0101] in which:

[0102] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0103] - Ri and R2 independently represent a hydrocarbon radical optionally in interrupted by one or more heteroatom(s);

[0104] - 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;

[0105] - 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;

[0106] - E independently represents a group chosen from:

[0107] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-,

[0108] in which R3 and R4 independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s);

[0109] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, possibly interrupted by one or more heteroatom(s);

[0110] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

[0111] 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.

[0112] The hydrocarbon radical may comprise one or more cyclic groups.

[0113] 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.

[0114] 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.

[0115] Preferably, X1 and X2 independently represent an oxygen atom.

[0116] 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.

[0117] According to a preferred embodiment, Ri and R2 are independently chosen from the following groups (i) to (iv):

[0118] (i) the compound of formula (III) following:

[0119] R7-OC(O)-C(R8)(H)-(III),

[0120] wherein 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.

[0121] (ii) the compound of formula (IV) following:

[0122] R9-[0-CH2-C(H)(Rio)]p-(IV),

[0123] 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.

[0124] (iii) the compound of formula (V) following:

[0125] (Rn)2N-CH2-C(H)(R12)-(V),

[0126] wherein Ru represents a C1-C4 alkyl group and R[2 represents a hydrogen atom or a C1-C4 alkyl group; preferably Ru is methyl, ethyl or butyl and R[2 is a hydrogen atom or methyl.

[0127] (iv) the compound of formula (VI) following:

[0128] R13-[O-CH2-C(H)(R14)]q- (VI),

[0129] in which Rn represents a C1-C4 alkyl group or a phenyl, RM represents a hydrogen atom or a C1-C4 alkyl group and q denotes an integer ranging from 4 to 30; preferably Rn is a methyl, ethyl or butyl and Ru is a hydrogen atom or a methyl.

[0130] Preferably, R1 and R2 independently 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, R14 represents a hydrogen atom or a Cr-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.

[0131] 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.

[0132] Preferably, in formula (IV), R9 is methyl, ethyl or butyl and R10 is hydrogen or methyl and p is 1.

[0133] Preferably, in formula (VI), Rb is methyl, ethyl or butyl and R[4 is hydrogen or methyl and q denotes an integer ranging from 4 to 30.

[0134] According to another alternative embodiment, R1 and R2 are identical and 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, 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.

[0135] Preferably, n denotes an integer ranging from 1 to 20, more preferably from 2 to 20.

[0136] Preferably, z denotes an integer ranging from 1 to 20, more preferably from 2 to 20.

[0137] Preferably, w is equal to 1.

[0138] Preferably, w is equal to 1, n+z denotes an integer ranging from 4 to 10.

[0139] 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-Ci2 heterocycloalkylene group such as imidazolene, pyrrolene, and furanylene, or a C6-Ci4 arylene group such as phenylene, and mixtures thereof.

[0140] 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.

[0141] 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:

[0142] Preferably, L1 is 4,4-dicyclohexylene methane corresponding to the following formula (VIII):

[0143] 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).

[0144] As indicated previously, E independently represents a group chosen from:

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

[0146] in which R3 and R4 independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s);

[0147] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, possibly interrupted by one or more heteroatom(s); and

[0148] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

[0149] 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.

[0150] 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).

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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).

[0155] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from alpha-methylstyryl-isocyanates of the following formula (X): (X),

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166] 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, n denotes an integer ranging from 2 to 100. In this embodiment, the term "alkyl group" is as defined above. In this embodiment, the term "cycloalkyl group" is as defined above. In this embodiment, n can denote an integer ranging from 2 to 50, preferably from 3 to 30, more preferably from 5 to 10. According to another particular embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI): (XI), Z 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. “Alkyl group”, “cycloalkyl group” and “aryl group” are as defined above. According to a preferred embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) or of formula (II) in which: - Xi and X2 independently represent an oxygen atom; - 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, preferably (poly)alkylene glycol monoalkyl ethers, in which a hydroxy group has been removed, more preferably, the compound of formula (VI) as previously described in which Rn represents a group C1-C4 alkyl 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

[0167] - n and z, when present, denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0168] - 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;

[0169] - 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;

[0170] - E, when present, independently represents a group chosen from:

[0171] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0172] in which R3 and R4 are independently chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1-Ci8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

[0173] - 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

[0174] - 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.

[0175] Preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0176] - Xi and X2 independently represent an oxygen atom;

[0177] - 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;

[0178] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0179] - Li is chosen from a divalent aliphatic hydrocarbon radical in C1-C18, a C3-Ci5 cycloalkylene radical, a C3-Ci2 heterocycloalkylene group, or a C6-Ci4 arylene group, and mixtures thereof;

[0180] - E independently represents a group chosen from:

[0181] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0182] 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;

[0183] - 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

[0184] - 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.

[0185] More preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0186] - Xi and X2 independently represent an oxygen atom;

[0187] - Ri and R2, are independently monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed;

[0188] - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

[0189] - Li is a C3-Ci5 cycloalkylene radical;

[0190] - E independently represents a group chosen from:

[0191] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0192] 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;

[0193] - 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

[0194] - 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.

[0195] Even more preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0196] - Xi and X2 independently represent an oxygen atom;

[0197] - R1 and R2, independently represent the compound of formula (VI) following:

[0198] R13-[O-CH2-C(H)(R14)]q- (VI),

[0199] 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 an atom hydrogen or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;

[0200] - 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;

[0201] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cyclo- heptylene, cyclohexylene and 4,4-dicyclohexylene methane; and

[0202] - 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.

[0203] Even more preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

[0204] - Xi and X2 independently represent an oxygen atom;

[0205] - R1 and R2, independently represent the compound of formula (VI) following:

[0206] R13-[O-CH2-C(H)(R14)]q- (VI)

[0207] 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;

[0208] - 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;

[0209] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cyclo- heptylene, cyclohexylene, 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and

[0210] - E represents a group -O-R3-O- in which R3 represents a radical linear or branched CrCi8 alkylene such as methylene, propylene, butylene ethylene, optionally interrupted by one or more heteroatom(s).

[0211] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of the following formula (XII):

[0212] 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.

[0213] Advantageously, the (poly)carbodiimide compound(s) as defined above are present in a total content ranging 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% by weight, better still from 1 to 6% by weight relative to the total weight of composition C. Coloring agent

[0214] 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.

[0215] Preferably, the composition C used in the context of the process according to the invention comprises at least one pigment.

[0216] 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%.

[0217] The pigments which can be used are in particular chosen from organic and / or mineral pigments known in the art, in particular those which are described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.

[0218] They can be natural, of natural origin, or not.

[0219] These pigments can be in the form of powder or pigment paste. They can be coated or uncoated.

[0220] 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.

[0221] 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.

[0222] The pigment may be an organic pigment. By "organic pigment" is meant any pigment that meets the definition of the Ullmann encyclopedia in the organic pigment chapter.

[0223] 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.

[0224] 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.

[0225] As an example, we can also cite organic pigment pigment pastes such as the products sold by the company HOECHST under the name:

[0226] - COSMENYL YELLOW IOG: Pigment YELLOW 3 (Cl 11710);

[0227] - COSMENYL YELLOW G: Pigment YELLOW 1 (Cl 11680);

[0228] - ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);

[0229] - COSMENYL RED R: Pigment RED 4 (Cl 12085);

[0230] - CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);

[0231] - VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);

[0232] - COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);

[0233] - COSMENYL GREEN GG: Pigment GREEN 7 (Cl 74260);

[0234] - COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

[0235] 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.

[0236] 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.

[0237] 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.

[0238] 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).

[0239] As examples of lacquers, we can cite the product known under the following name: D & C Red 7 (CI 15 850:1).

[0240] The pigment may also be a special effect pigment. Special effect pigments are understood to mean pigments which generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) which is non-uniform and changes depending on the observation conditions (light, temperature, observation angles, etc.). They are thus opposed to colored pigments which provide a conventional uniform opaque, semi-transparent or transparent shade.

[0241] 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.

[0242] Examples of special effect pigments include pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxides, mica coated with iron oxide, mica coated with titanium and in particular ferric blue or chromium oxide, mica coated with titanium and an organic pigment as defined above 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).

[0243] 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.;

[0244] Still as an example of nacres, we can also cite particles comprising a borosilicate substrate coated with titanium oxide.

[0245] Particles with a glass substrate coated with titanium oxide are notably sold under the name METASHINE MC1080RY by the company TOYAL.

[0246] Finally, as examples of mother-of-pearl, we can also cite polyethylene terephthalate flakes, in particular those marketed by the company Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver glitter). Multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate, and aluminum can also be considered.

[0247] 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.

[0248] 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.

[0249] These particles can have various shapes, in particular being platelet-shaped or globular, in particular spherical.

[0250] 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.

[0251] 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.

[0252] 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.

[0253] 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.

[0254] The reflective material may comprise a layer of metal or a metallic material.

[0255] Reflective particles are described in particular in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0256] 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.

[0257] 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.

[0258] 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.

[0259] Examples include aluminum, bronze or copper powders coated with SiO2 marketed under the name VISIONAIRE by the company ECKART.

[0260] 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.

[0261] 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.

[0262] 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.

[0263] The pigments may be dispersed in the composition using a dispersing agent.

[0264] 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 further have at least one functional group compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid, in particular, and of C8 to C20 fatty acids and polyols 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 mixtures thereof, are used.

[0265] 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.

[0266] The pigments used in the composition may be surface-treated with an organic agent.

[0267] 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; alkanoamines; silicone compounds, for example silicones, in particular polydimethylsiloxanes; fluorinated organic compounds, for example perfluoroalkyl ethers; fluorosilicon compounds.

[0268] 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.

[0269] 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.

[0270] Preferably, the surface-treated pigments are covered by a layer organic.

[0271] 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.

[0272] 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.

[0273] Preferably, an organic agent covalently bound to the pigments will be used.

[0274] 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.

[0275] Preferably, the surface treatments of the pigments are chosen from the following treatments:

[0276] - a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW;

[0277] - a Methicone treatment such as the SI surface treatment marketed by LCW;

[0278] - a Dimethicone treatment such as Covasil 3.05 com surface treatment marketed by LCW;

[0279] - a Dimethicone / Trimethylsiloxysilicate treatment as the surface treatment Covasil 4.05 marketed by LCW;

[0280] - a Magnesium Myristate treatment such as the MM com surface treatment marketed by LCW;

[0281] - an Aluminum Dimyristate treatment such as MI com surface treatment sold by Miyoshi;

[0282] - a Perfluoropolymethylisopropyl ether treatment as the surface treatment FHC marketed by LCW;

[0283] - an Isostearyl Sebacate treatment like the commercialized HS surface treatment by Miyoshi;

[0284] - a Perfluoroalkyl Phosphate treatment such as PF surface treatment marketed by Daito;

[0285] - an acrylate / Dimethicone and Perfluoroalkyl Phosphate Copolymer treatment such as the FSA surface treatment marketed by Daito;

[0286] - a Polymethylhydrogen siloxane / Perfluoroalkyl Phosphate treatment such as the FS01 surface treatment marketed by Daito;

[0287] - an Acrylate / Dimethicone Copolymer treatment as the surface treatment ASC marketed by Daito;

[0288] - an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito;

[0289] - an Acrylate copolymer treatment such as APD surface treatment com sold by Daito;

[0290] - a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito.

[0291] 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.

[0292] 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.

[0293] 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.

[0294] The dispersing agent(s) may therefore have a silicone backbone, such as silicone polyether and amino-silicone dispersants. Suitable dispersing agents include:

[0295] - 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,

[0296] - silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik,

[0297] - 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.

[0298] According to a particular embodiment, the dispersing agent(s) are of amino-silicone type and are cationic.

[0299] Preferably, the pigment(s) is (are) chosen from mineral, mixed mineral-organic or organic pigments.

[0300] 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) pigments are mineral pigments.

[0301] 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.

[0302] Direct dye

[0303] Composition C used in the context of the process according to the invention may comprise one or more direct dye(s).

[0304] By "direct dye" is meant natural and / or synthetic dyes, different from oxidation dyes. These are dyes which will diffuse superficially on the fiber. They can be ionic, for example cationic or anionic, or non-ionic.

[0305] 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.

[0306] 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.

[0307] A titre d’exemple de colorants acides 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; Acid Red 111, Acid Red 134, Acid yellow 38 ;

[0308] A titre d’exemple de colorants azo anioniques pyrazolones on peut citer : Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76Acid Yellow 17 ;

[0309] As an example of anthraquinone dyes, 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 Acid Black 48;

[0310] Examples of nitrated dyes include: Acid Brown 13; Acid Orange 3; examples of dyes of formula (XXII') include: 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;

[0311] Examples of triarylmethane dyes include: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50.

[0312] Examples of xanthene dyes include: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9.

[0313] Examples of indolic dyes include: Acid Blue 74;

[0314] Examples of quinoline dyes include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0315] 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.

[0316] 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.

[0317] 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.

[0318] The direct dye(s) may be present in a total amount ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight relative to the total weight of composition C.

[0319] Polymer comprising at least one reactive group chosen from carboxylic acids

[0320] Composition C used in the context of the process according to the invention comprises at least at least one polymer comprising at least one reactive group chosen from carboxylic acids, preferably at least one acrylic polymer.

[0321] Preferably, the acrylic polymer(s) 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.

[0322] Thus, preferably, composition C comprises at least one acrylic polymer in the form of aqueous dispersions of acrylic polymer particles.

[0323] 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.

[0324] 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.

[0325] 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.

[0326] 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.

[0327] 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.

[0328] The esters of (meth)acrylic acid (also called (meth)acrylates) are advantageously chosen from alkyl (meth)acrylates, in particular C1 to C30 alkyl, preferably C1 to C20, better still C1 to C10, aryl (meth)acrylates, in particular C6 to C10 aryl, hydroxyalkyl (meth)acrylates, in particular C2 to C6 hydroxyalkyl.

[0329] 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.

[0330] Among the hydroxyalkyl (meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.

[0331] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0332] Particularly preferred (meth)acrylic acid esters are Alkyl (meth)acrylates, preferably C1 to C30 alkyl, more preferably C1 to C20, even better C1 to Cm, and even more particularly C1 to C4.

[0333] 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.

[0334] 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 C 2 to C 10 alkyl. Among the N-alkyl (meth)acrylamides, mention may be made of N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide and N-undecylacrylamide.

[0335] 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.

[0336] Preferably, the acrylic polymer(s) according to the invention comprise one or more units derived from the following monomers:

[0337] a) (meth)acrylic acid; and

[0338] b) C1 to C30 alkyl (meth)acrylate, more preferably C1 to C20, even better C1 to C10, and even more particularly C1 to C4.

[0339] Preferably, the aqueous dispersion of acrylic polymer particles does not comprise a surfactant. The term "surfactant" means any agent capable of modifying the surface tension between two surfaces.

[0340] 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 the compound Polyacrylate-2 crosspolymer sold under the trade name FIXATE SUPERHOLD POLYMER by the company LUBRIZOL, or the compound Acrylate Copolymer sold under the trade name DAITOSOL 3000VP3 by the company DAITO KASEI KOGYO, or the compound Acrylate Copolymer sold under the trade name DAITOSOL 3000SLPN-PE1 by the company DAITO KASEI KOGYO.

[0341] 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.

[0342] As additional monomer, examples that may be mentioned are styrenic monomers, in particular styrene and alpha-methylstyrene, and preferably styrene.

[0343] 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 alkyl (meth)acrylate monomer. in C1 to C2o, preferably in C1 to C2o.

[0344] 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.

[0345] 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.

[0346] Preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles. More preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more units derived from the following monomers:

[0347] a) (meth)acrylic acid; and

[0348] b) C1 to C30 alkyl (meth)acrylate, preferably C1 to C20, more preferably C1 to C10, and even more particularly C1 to C4.

[0349] Preferably, the aqueous dispersion of acrylic polymer particles has a content of acrylic polymer(s) (or active material, or dry matter) based on the weight of the dispersion of 20 to 60% by weight, more preferably of 22 to 55% by weight and better still of 25 to 50% by weight.

[0350] Advantageously, the total content of the polymer(s) comprising at least one reactive group chosen from carboxylic acids 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.

[0351] Advantageously, the total content of the acrylic polymer(s) 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.

[0352] According to a particular embodiment, the total content 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. Non-carboxylic anionic thickening agent

[0353] Composition C used in the context of the process according to the invention may further comprise at least one non-carboxylic anionic thickening agent.

[0354] 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.

[0355] 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).

[0356] Preferably, the non-carboxylic anionic thickening agent(s) are chosen from non-carboxylic anionic polymers, more preferably from anionic polymers with sulfonic group(s).

[0357] 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.

[0358] 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.

[0359] These polymers may be crosslinked or non-crosslinked. They are preferably crosslinked.

[0360] These polymers may be associative or not, preferably non-associative.

[0361] It is recalled that “associative polymers” are polymers capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

[0362] Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0363] 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.

[0364] 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.

[0365] The ethylenically unsaturated monomers with a sulfonic group are chosen in particular from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci-C22)alkylsulfonic acids, N-(Ci-C22)alkyl(meth)acrylamido-(Ci-C22)alkylsulfonic acids such as undecyl-acrylamido-methane-sulfonic acid as well as their partially or totally neutralized forms.

[0366] More preferably, (meth)acrylamido(Ci-C22) alkylsul- acids will be used. fonic acids 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 and their partially or completely neutralized forms.

[0367] More particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or totally neutralized forms will be used.

[0368] 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.

[0369] 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).

[0370] 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.

[0371] The preferred polymers of this family are chosen from associative copolymers of AMPS and at least one hydrophobic monomer with ethylenic unsaturation.

[0372] 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).

[0373] Advantageously, the total content 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. Associative polymers

[0374] Composition C used in the context of the process according to the invention may further comprise at least one associative polymer different from the acrylic polymer and different from the non-carboxylic anionic thickening agent as defined previously.

[0375] As recalled above, “associative polymers” are polymers capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

[0376] Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0377] 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.

[0378] The associative polymers may be non-ionic, anionic, cationic or amphoteric in nature. Preferably, the associative polymer(s) are chosen from anionic associative polymers.

[0379] Among the associative polymers of anionic type, mention may be made of 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.

[0380] Preferably, these compounds also comprise as monomer an ester of carboxylic acid with α,[3-monoethylenic unsaturation and C1-C4 alcohol.

[0381] 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.

[0382] Preferably, the associative polymer(s), different from the acrylic polymers 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.

[0383] Advantageously, the total content of the associative polymer(s) different from the acrylic polymer(s) and different from the non-carboxylic anionic thickening agent(s) as defined above 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

[0384] Composition C according to the invention may comprise one or more organic solvents.

[0385] As organic solvent, examples that may be mentioned are lower C 1 -C 4 alkanols, 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.

[0386] The organic solvents may be present in a total content of between 0.01 and 50% by weight, preferably between 0.05 and 40% by weight and more preferably inclusively between 0.1 and 30% by weight relative to the total weight of composition C.

[0387] 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 70% by weight relative to the total weight of the composition C. Additives

[0388] Composition C used in the context of the process according to the invention may contain any adjuvant or additive usually used.

[0389] Among the additives that may be contained in the composition, mention may be made of reducing agents, softeners, anti-foaming agents, moisturizing agents, clays, mineral fillers, UV filters, peptizers, perfumes, anionic, cationic, non-ionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers previously described, preservatives, amino and / or non-amino silicones, oils, waxes other than silicones in wax form, and mixtures thereof.

[0390] 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.

[0391] 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.

[0392] The above additives may generally be present in an amount of between 0 and 20% by weight for each of them, relative to the total weight of composition C. Process

[0393] The application to the hair of the composition T comprising at least one cyanoacrylate compound 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.

[0394] The composition T of the invention is applied to the hair, preferably in the presence of a nucleophilic agent.

[0395] According to a particular embodiment of the process of the invention, the nucleophilic agent capable of initiating the polymerization of the cyanoacrylate monomer can be applied beforehand to the keratin fibers. The nucleophilic agent can be used pure, in solution, in the form of an emulsion or be encapsulated. It can also be added to the anhydrous composition at the time of use just before application to the keratin fibers.

[0396] Preferably, this nucleophilic agent is water. This water can be provided for example by prior moistening of the keratin fibers. It can also be added directly into the composition before application.

[0397] According to a particular embodiment, it is possible to modulate the polymerization kinetics by previously moistening the fiber using an aqueous solution whose pH has been adjusted using a base, an acid or an acid / base mixture. The acid and / or the base may be inorganic or organic.

[0398] According to a particular embodiment of the invention, the hair is rinsed with water or washed after application of the composition T comprising at least one cyanoacrylate compound as defined previously.

[0399] Preferably, a washing or rinsing, spinning or drying step is carried out after application of the composition T comprising at least one cyanoacrylate compound as defined above. More preferably, a drying step is carried out after application of the composition T comprising at least one cyanoacrylate compound as defined above.

[0400] The application of the composition T comprising at least one cyanoacrylate compound as defined previously can be carried out at room temperature (between 15 and 25°C).

[0401] After the application of the composition T comprising at least one cyanoacrylate compound as defined above, 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 the application of the com- position C on the hair.

[0402] Preferably, the exposure time is between 1 minute and 20 minutes before applying composition C to the hair.

[0403] Composition C 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.

[0404] Preferably, a rinsing, wringing and / or drying step is carried out after the application of composition C to the hair. More preferably, a drying step is carried out after the application of composition C to the hair.

[0405] 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.

[0406] The application of composition C to the hair is generally carried out at room temperature (between 15 and 25°C).

[0407] After applying composition C, the hair may be left to dry or dried, for example at a temperature greater than or equal to 30°C.

[0408] The method according to the invention can thus comprise a step of applying heat to the keratin fibers using a heating tool.

[0409] The heat application step of the method of the invention can be implemented using a helmet, a hair dryer, a straightening or curling iron, a climazon, etc. Preferably, the heat application step of the method of the invention is implemented using a hair dryer.

[0410] 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.

[0411] 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.

[0412] 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.

[0413] Preferably, the invention is a hair coloring process comprising:

[0414] (i) the application to the hair, dry or wet, of at least one composition T comprising at least one cyanoacrylate compound as defined above, then

[0415] (ii) optionally, a step of washing, rinsing, wringing and / or drying the hair; then

[0416] (iii) the application to the hair of at least one composition C comprising:

[0417] (1) at least one (poly)carbodiimide compound as defined previously;

[0418] (2) at least one coloring agent as defined above; and

[0419] (3) at least one polymer comprising at least one reactive group chosen from carboxylic acids as defined above.

[0420] (iv) optionally, a step of washing, rinsing, wringing and / or drying said hair.

[0421] Advantageously, in the coloring process according to the invention, step b) consists of mixing extemporaneously at the time of use at least two compositions A and B to obtain a hair coloring composition C and applying the hair coloring composition C to the hair, with:

[0422] - composition A comprising at least one (poly)carbodiimide compound such as previously defined;

[0423] - composition B comprising at least one polymer comprising at least one reactive group chosen from carboxylic acids as defined above;

[0424] composition A and or B comprising a coloring agent as defined previously.

[0425] More preferably, in the coloring process according to the invention, step b) consists of mixing extemporaneously at the time of use at least two compositions A and B to obtain a hair coloring composition C and applying the hair coloring composition C to the hair, with:

[0426] - composition A comprising at least one (poly)carbodiimide compound such as previously defined;

[0427] - composition B comprising at least one coloring agent as defined above previously, and at least one polymer comprising at least one reactive group chosen from carboxylic acids as defined previously.

[0428] According to a preferred embodiment, the coloring process according to the invention is a hair coloring process comprising:

[0429] (i) the application to the hair of at least one composition T comprising at least a cyanoacrylate compound as defined above, then

[0430] (ii) optionally, a step of washing, rinsing, wringing and / or drying the hair; then

[0431] (iii) 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:

[0432] - composition A comprising i) at least one (poly)carbodiimide compound such as previously defined;

[0433] - composition B comprising ii) at least one coloring agent as defined above and iii) at least one polymer comprising at least one reactive group chosen from carboxylic acids as defined previously; then

[0434] (iv) optionally, a washing, rinsing, spinning and / or drying step of said hair.

[0435] Preferably, the polymer comprising at least one reactive group chosen from carboxylic acids is chosen from acrylic polymers.

[0436] Preferably, composition A does not comprise a coloring agent as defined above.

[0437] 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.

[0438] 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.

[0439] The total content of the (poly)carbodihnide compound(s) preferably ranges from 0.01 to 40% by weight, more preferably from 0.1 to 30% by weight, even more preferably from 0.5 to 20% by weight, better still from 1 to 15% by weight relative to the total weight of composition A.

[0440] The total content of polymer(s) comprising at least one reactive group chosen from carboxylic acids, preferably chosen from acrylic polymers, preferably ranges from 0.2 to 60% by weight, more preferably from 1 to 55% by weight, even more preferably from 5 to 55% by weight, better still from 10 to 45% by weight relative to the total weight of composition B.

[0441] According to a particular embodiment, composition B comprises at least one non-carboxylic anionic thickening agent. The total content of the non-carboxylic anionic thickening agent(s) preferably ranges from 0.01 to 20% by weight, more preferably from 0.1 to 10% by weight, even more preferably from 0.1 to 5% by weight, better still from 0.1 to 3% by weight, relative to the total weight of composition B.

[0442] According to a particular embodiment, composition B comprises at least one associative polymer. The total content of the associative polymer(s) preferably 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 B. Multi-compartment device (kit)

[0443] The present invention also relates to a device for coloring hair comprising several compartments containing:

[0444] * in a first compartment, a composition T comprising at least one cyanoacrylate compound as defined above, and

[0445] * in a second compartment, a composition C comprising:

[0446] (1) at least one (poly)carbodiimide compound as defined previously;

[0447] (2) at least one coloring agent as defined previously;

[0448] (3) at least one polymer comprising at least one reactive group chosen from carboxylic acids as defined above.

[0449] The present invention also relates to a device for coloring hair comprising several compartments containing:

[0450] * in a first compartment, a composition T comprising at least one cyanoacrylate compound as defined above,

[0451] * in a second compartment, a composition A comprising at least one (poly)carbodiimide compound as defined above,

[0452] * in a third compartment, a composition B comprising at least one polymer comprising at least one reactive group chosen from carboxylic acids as defined previously, and at least one coloring agent as defined previously.

[0453] 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

[0454] 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.

[0455] More particularly, the process for preparing the (poly)carbodiimides of the invention uses, during a first step, a diisocyanate reagent (1): O=C=N-LrN=C=O (1), formula (1) in which Li is as defined above which reacts in the presence of a carboimidation catalyst (2) such as those described in US 4,284,730 in particular phosphorus catalysts particularly chosen from phospholene oxides and phospholene sulfoxides, diaza and oxazaphospholanes, preferably under an inert atmosphere (nitrogen or Argon), and in particular in a polar solvent, preferably aprotic, such as THF, glyme, diglyme, 1,4-dioxane, and DMF, at a temperature between room temperature and solvent reflux, preferably around 140°C; to yield the carbodiimide diisocyanate compound (3): O=C=N-L1-(N=C=N-L1)nN=C=O (3), formula (3) in which Li and n are as defined previously. Benzoyl halogen such as benzoyl chloride can be added to deactivate the catalyst.

[0456] 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.

[0457] 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.

[0458] 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.

[0459] 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'),

[0460] 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),

[0461] Formula (7) in which Rb Xb Lb R2, X2, n, z and E are as defined previously.

[0462] 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),

[0463] 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.

[0464] 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 lead to the (poly)carbodiimide of the invention (9): Ri-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.

[0465] 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.

[0466] Example 1: Process for the synthesis of the compound (poly)carbodiimide

[0467] 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.

[0468] The reaction medium was heated to 140°C under nitrogen for 4 hours, monitoring the reaction by infrared spectroscopy through the absorption of the isocyanate functions between 2200 and 2300 cm1, then cooled to 120°C.

[0469] 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.

[0470] 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

[0471] The following compositions as described in Tables 1, 2 and 3 below were prepared: the quantities are expressed in g of raw material as is / 100g, unless otherwise stated.

[0472] [Tables 1] Composition T 2-Octyl-2-cyanoacrylate 50 Ethanol Qsp 100

[0473] [Tables2] Composition A Polycarbodiimide (1) 17.5 Hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer (2) 3 Ethanol 20 Water Qsp 100

[0474] (1) synthesized according to the synthesis method described in example 1 (at 40% material active in water),

[0475] (2) sold by the company SEPPIC under the name SEPINOV EMT10 (at 90% of active ingredient).

[0476] [Tables3] Composition B Acrylates copolymer (3) 29.2 Acrylates / Steareth-20 methacrylate copolymer (4) 2.2 Triethanolamine 0.45 Bis-Hydroxy / Methoxy / Methyl Amodimethicone Crosspolymer (and) Trideceth-10 8.8 Iron oxide CI 77491 12 Divinyldimethicone / dimethicone copolymer (and) C12-13 Pareth-3 (and) Ci2-b Pareth-23 (5) 10.2 Ethanol 3.75 Preservative(s) qs Water Qsp 100

[0477] (3) Acrylic polymer: sold by the company DAITO KASEI KOGYO under the name commercial mination DAITOSOL 3000SLPN-PE1 (aqueous dispersion with 30% active ingredient),

[0478] (4) Associative polymer sold by the company ROHM and HAAS under the name commercial ACULYN 22® (methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer with 30% active ingredient),

[0479] (5) 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).

[0480] Composition A was then mixed with composition B at a ratio of 1:1 to obtain composition C according to the invention. Protocol for the method according to the invention

[0481] When the application of the composition T comprising at least one cyanoacrylate compound as defined previously is carried out, the following protocol was applied:

[0482] Composition T comprising at least one cyanoacrylate compound as defined above is applied using a mascara brush to locks of 90% white natural hair, at a rate of 0.5 g of composition per gram of lock. The locks are then dried with a hair dryer while being combed using a comb.

[0483] Composition C is then applied to the strands treated with composition T, using a mascara brush, at a rate of 0.8 g of composition per gram of strand. Then the strands of hair are dried with a hair dryer while being combed using a comb.

[0484] The hair strands were then stored at room temperature for 24 hours. Protocol for the comparative process

[0485] The comparative protocol is identical to the protocol according to the invention, except that the locks are not treated with composition T.

[0486] Two methods 1 and 2 were implemented and were summarized in Table 4 below:

[0487] [Tables4] Methods 1 (invention) 2 (comparative) Treatment with a cyanoacrylate compound YES NO Application of compositions T + CC

[0488] Thus, the locks of hair treated with compositions T then C are treated by method 1 according to the invention.

[0489] The locks of hair treated with composition C only are treated by comparative method 2.

[0490] The locks of hair treated by the processes let 2 were then subjected to a test of several repeated shampoos, so as to evaluate the tenacity (the persistence) of the coloring obtained from the shampoos. Shampoo protocol

[0491] The colored hair strands are combed, moistened under water at 35°C before being passed between the fingers 5 times for 5 seconds. The hair strands are then wrung out between two fingers.

[0492] A standard shampoo (Garnier Ultra Doux) is applied evenly to the colored strands at a rate of 0.4g of standard shampoo per gram of strands, gently kneading the strands of hair lengthwise (6 strokes) for 15 seconds, from root to tip.

[0493] The strands of hair are then placed in a watch glass and left to stand for 1 minute.

[0494] Then, the strands of hair are rinsed with water by passing the strand between the fingers (15 passes). The strands of hair are then wrung out between two fingers before the next shampoo.

[0495] Once the 5 shampoo tests are carried out, the hair strands are combed and dried with a hairdryer. Results

[0496] Colorimetric measurements were performed using a KONICA MINOLTA-3600 spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.

[0497] In this L*a*b* system, L* represents the lightness of the color, a* indicates the green / red color axis and b* the blue / yellow color axis.

[0498] The persistence of the color is evaluated by the color difference AE between the colored strands before shampooing, then after having undergone 5 shampoos according to the protocol described above. The lower the AE value, the more the color persists after shampooing.

[0499] The value of AE is calculated according to the following equation:

[0500] + ) 2 4- ( b*-b0*}2

[0501] In this equation, L*, a* and b* represent the values ​​measured after coloring the hair and after having undergone 5 shampoos, and Lo*, a0* and b0* represent the values ​​measured after coloring the hair but before the 5 shampoos.

[0502] The results are collected in Table 5 below:

[0503] [Tables5] Methods 1 (invention) Number of shampoos L* a* b* AE 0 33.8 27.8 21.9 - 5 37.2 26.8 21.2 3.6 2 (comparative) 0 31.9 26.2 20.1 - 5 47.1 13.5 13.5 20.9

[0504] The locks of hair treated with method 1 according to the invention and washed with five shampoos have a lower AE value than that of the locks of hair treated with comparative method 2.

[0505] Thus, the colored coating obtained with the process according to the invention has improved persistence to shampooing.

Claims

Claims

1. A method for coloring hair comprising: a) applying to the hair at least one composition T comprising at least one cyanoacrylate compound; followed by b) applying to the hair at least one hair coloring composition C comprising: i) at least one (poly)carbodiimide compound; ii) at least one coloring agent chosen from pigments, direct dyes and mixtures thereof; and iii) at least one polymer comprising at least one reactive group chosen from carboxylic acids.

2. Process according to claim 1, characterized in that the cyanoacrylate compound(s) are chosen from the compounds of the following formula (A): RI Π(A) y / R2 coxr; in which: - X denotes NH, S or 0; - RI and R2 each denote, independently of one another, a hydrogen atom, a saturated or unsaturated, linear, branched or cyclic hydrocarbon group, preferably comprising from 1 to 20, better still from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulfur atoms, and optionally substituted by one or more groups chosen from -OR, -COOR, -COR, -SH, -SR, -OH, and halogen atoms, and a polyoxyalkylene group;R denotes a saturated or unsaturated, linear, branched or cyclic hydrocarbon group, preferably comprising from 1 to 20, better still from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulfur atoms, and optionally substituted by one or more groups chosen from -OR', -COOR', -COR', -SH, -SR', -OH, halogen atoms, and a polymer residue which can be obtained by radical polymerization, by polycondensation or by ring opening; R' denotes a CrCio alkyl group; - R'3 represents a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic hydrocarbon group, preferably comprising from 1 to 20, better still from 1 to 10 carbon atoms, and optionally containing; actually one or more atoms of nitrogen, oxygen, sulfur, and optionally substituted by one or more groups chosen from -OR', -COOR', -COR', -SH, -SR', -OH, halogen atoms, and a polymer residue which can be obtained by radical polymerization, by polycondensation or by ring opening, R' denoting a CrCio alkyl group.

3. Process according to any one of the preceding claims, characterized in that the cyanoacrylate compound(s) are chosen from the compounds of the following formula (B): CN (B) GOO-R in which R represents an alkyl or alkoxyalkyl or hydroxyalkyl radical, preferably comprising from 1 to 20, better still from 1 to 10 carbon atoms.

4. Process according to one of the preceding claims, characterized in that the cyanoacrylate compound(s) of formula (B) are chosen from those comprising an alkyl radical R comprising from 6 to 10 carbon atoms.

5. Process according to any one of the preceding claims, characterized in that the total content of the cyanoacrylate compound(s) ranges from 5 to 80% by weight, preferably from 15 to 75% by weight, more preferably from 25 to 65% by weight, better still from 40 to 60% 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 the following formula (I): OO ® A ri R —A— —A4—N " H l 4, H in which: - X1 and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group; - R1 and R2 independently represent a group chosen from a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatom(s), a group chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhy-

7. dridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide, and azacyclopropane, and a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatoms and by one or more groups chosen from the alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl groups, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide, and azacyclopropane; - n denotes an integer ranging from 1 to 1000; and - A is a monomer chosen from the compounds below: Process according to any one of claims 1 to 5, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) below: (II) in which: - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group; - R1 and R2 independently represent a hydrocarbon radical optionally interrupted by one or more heteroatom(s); - n and z denote an integer ranging from 1 to 20, with n+z > 2 and w denotes an integer ranging from 1 to 3; - Li independently represents a divalent C1-C18 aliphatic hydrocarbon radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group, or a C6-C14 arylene group, and mixtures thereof; - E independently represents a group chosen from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-, in which R3 and R4 independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s); - R5 independently represents a covalent bond or a divalent saturated hydrocarbon radical, optionally interrupted by one or more heteroatom(s); - R6 independently represents a hydrogen atom, or a hydrocarbon radical optionally interrupted by one or more heteroatom(s).

8. Process according to claim 7, 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 selected 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 selected 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 selected 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 C1-C18 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 heteroatoms, and mixtures thereof; and - 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 heteroatoms, and mixtures thereof.;

9. Process according to claim 7 or 8, 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 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-C15 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 radical linear or branched CrCi8 alkylene, 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 C1Ci8 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-C12 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

10. Process according to any one of claims 7 to 9, 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, 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; - 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.

11. Process according to any one of claims 7 to 10, 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, 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; - 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).

12. Process according to any one of claims 7 to 11, 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.

13. Process according to any one of the preceding claims, characterized in that the total content 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% by weight, better still from 1 to 6% by weight relative to the total weight of composition C.

14. Method according to any one of the preceding claims, characterized in that the total content of the 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.

15. Method according to any one of the preceding claims, characterized in that the polymer comprising at least one reactive group chosen from carboxylic acids is an acrylic polymer.

16. Method according to claim 15, characterized in that the acrylic polymer(s) comprise one or more units derived from the monomers a) (meth)acrylic acid and b) C1 to C30 alkyl (meth)acrylate, more preferably C1 to C10, even more particularly C1 to C4.

17. Method according to any one of the preceding claims, characterized in that step b) consists of extemporaneously mixing at the time of use at least two compositions A and B to obtain the hair coloring composition C and applying the hair coloring composition C to the hair, with: - composition A comprising i) at least one (poly)carbodiimide compound as defined in any one of claims 1 and 6 to 12; - composition B comprising ii) at least one coloring agent and at least one polymer comprising at least one reactive group chosen from carboxylic acids as defined in any one of claims 1, 15 and 16.

18. Method according to the preceding claim, characterized in that the quantity of polymer comprising at least one reactive group chosen from carboxylic acids ranges from 0.2 to 60% by weight, preferably from 1 to 55% by weight, more preferably from 5 to 50% by weight, even more preferably from 7 to 45% by weight of composition B.

19. Device for coloring hair comprising several com- compartments containing: - in a first compartment, a composition T comprising at least one cyanoacrylate compound as defined in any one of claims 1 to 5, - in a second compartment, a composition A comprising at least one (poly)carbodiimide compound as defined in any one of claims 1 and 6 to 12, - in a third compartment, a composition B comprising at least one polymer comprising at least one reactive group chosen from carboxylic acids as defined in any one of the preceding claims, and at least one coloring agent as defined in any one of claims 1, 15, 16 and 18.