A hair coloring process comprising the application of a (poly)carbodiimide compound, a compound having at least one carboxylic acid group, and a pigment having a particular particle size.

Abstract

The present invention relates to a hair coloring process comprising the application to the hair of at least one composition C comprising: - at least one (poly)carbodiimide compound; - at least one compound having at least one carboxylic acid group; and - at least one pigment having a D90 particle size less than or equal to 50 μm.

Description

Title of the invention: A hair coloring process comprising the application of a (poly)carbodiimide compound, a compound having at least one carboxylic acid group, and a pigment having a particular particle size

[0001] The present invention relates to a hair coloring process comprising the application to the hair of a composition C comprising a compound (poly)carbodiimide, a compound having at least one carboxylic acid group and a pigment having a particular particle size. technical field

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

[0003] There are essentially three types of hair coloring processes:

[0004] a) so-called permanent coloring which has the function of bringing about a significant change in the natural color and which uses oxidation dyes which penetrate 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 implement the oxidative condensation process and resists 4 or 5 shampoos; consists of dyeing the keratin fibers with dyeing compositions containing direct dyes;

[0006] c) Temporary hair coloring that results in a change to the natural hair color that lasts from one shampoo to the next and serves to enhance or correct a previously achieved shade. It can also be considered a "makeup" process.

[0007] This temporary coloring method involves using pigments. Indeed, the use of pigment on the surface of keratin fibers generally makes it possible to obtain visible colors on dark hair since the pigment on the surface masks the natural color of the fiber.

[0008] However, temporary hair coloring compositions can lead to cosmetic properties that do not give complete satisfaction, more particularly hair conditioning properties, especially in terms of detangling and smooth feel of the hair.

[0009] There therefore remains a need for a hair coloring process that has the advantage of obtaining a homogeneous colored coating on the hair, and which allows for improved hair conditioning properties, particularly in terms of detangling and smooth hair feel.

[0010] Thus, the aim of the present invention is to develop a hair coloring process which has the advantage of obtaining a homogeneous colored coating and allowing improved hair conditioning properties, particularly in terms of detangling and smooth hair feel. Description of the invention

[0011] The present invention therefore relates to a hair coloring process comprising the application to the hair of at least one composition C comprising:

[0012] - at least one (poly)carbodiimide compound;

[0013] - at least one compound having at least one carboxylic acid group; and

[0014] - at least one pigment having a D90 particle size less than or equal to 50 qm.

[0015] Thanks to the hair coloring process according to the invention, colored coatings are obtained on the hair, resulting in visible coloring on all hair types and excellent hair conditioning properties, particularly in terms of detangling and a smooth feel. It allows, in particular, for a homogeneous deposit.

[0016] The expression "at least one" means one or more.

[0017] Unless otherwise indicated, the bounds of a range of values ​​are included in that range, in particular in the expressions "between" and "ranging from ... to ...".

[0018] The invention is not limited to the illustrated examples. The features of the different examples can, in particular, be combined within non-illustrated variants.

[0019] For the purposes of the present invention and, unless otherwise indicated,

[0020] - an "alkyl" radical means a saturated linear or branched radical containing by example of 1 to 20 carbon atoms;

[0021] - an "aminoalkyl" radical means an alkyl radical as defined above, said alkyl radical comprising an NH2 group;

[0022] - a "hydroxyalkyl" radical means an alkyl radical as defined above, said alkyl radical comprising an OH group;

[0023] - an "alkylene" radical designates a divalent saturated hydrocarbon group at C2-C4, linear or branched, such as methylene, ethylene, or propylene;

[0024] - a "cycloalkyl" or "alicycloalkyl" radical designates a hydrocarbon group saturated cyclic mono- or bicyclic, preferably monocyclic, comprising 1 to 3 rings, preferably 2 rings, and comprising 3 to 24 carbon atoms, in particular comprising 3 to 20 carbon atoms, more particularly 3 to 13 carbon atoms, 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 a 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 isobotyl group,

[0025] - a "cycloalkylene" radical designates a divalent cycloalkyl group with " cycloalkyl” as defined above, preferably in C3-C12;

[0026] - an "aryl" radical is an unsaturated and aromatic hydrocarbon cyclic 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 ring of 6 carbon atoms such as phenyl, naphthyl, 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;

[0027] - an "arylene" radical is a divalent aryl radical with "aryl" as defined previously preferred arylene represents phenylene;

[0028] - a "heterocyclic" radical designates a mono or polycyclic, saturated or unsaturated, non-aromatic or aromatic, comprising one or more heteroatoms preferably of 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;

[0029] - a "heterocycloalkylene" radical is a divalent heterocyclic group with "heterocyclic" as defined above;

[0030] - an "aryloxy" radical designates an aryl-oxy radical with "aryl" as defined previously;

[0031] - an "alkoxy" radical designates an alkyl-oxy radical with "alkyl" as defined previously;

[0032] - an "acyloxy" radical designates an ester radical RC(O)-O- with R an alkyl group as defined previously;

[0033] - a "reactive" group is a group capable of forming a bond covalent with another group, identical or different, by chemical reaction.

[0034] For the purposes of this invention, "pigment having a D90 particle size less than or equal to 50 µm" means a pigment in the form of particles of which 90% of said particles have a size less than or equal to 50 µm (this is a number distribution).

[0035] For the purposes of the present invention, "particles" means small fractionated objects made up of solid particles aggregated together, and of varying shapes. They can be regular or irregular in shape. In particular, they can be square, rectangular, or plate-like.

[0036] For the purposes of the present invention, "particle having a size less than or equal to 50 sqm" means a particle having a size, in its largest dimension, less than or equal to 50 sqm.

[0037] Furthermore, the concept of "tone" is based on the classification of natural shades, with a tone separating each shade from the one that immediately follows or precedes it. This definition and the classification of natural shades are well known to hairdressing professionals and are published in the book "Sciences des traitements cheveux" by Charles ZVIAK, 1988, Ed. Masson, pp. 215 and 278.

[0038] The tone heights range from 1 (black) to 10 (light blonde), one unit corresponding to one tone; the higher the number, the lighter the shade.

[0039] By "capillary keratin fibers" is meant hair. In other words, the expressions "capillary keratin fibers" and "hair" are equivalent in the remainder of the description. Polycarbodiimide compound

[0040] Composition C used in the process according to the invention comprises at least one (poly)carbodiimide compound.

[0041] The composition may comprise at least two distinct (poly)carbodiimide compounds, present in mixture in the composition.

[0042] The term "(poly)carbodiimide compound" means a compound comprising one or more carbodihnide group(s), preferably at least two carbodiimide groups, more preferably at least three carbodihnide groups, in particular the number of carbodiimide groups not exceeding 200, preferably 150, more preferably 100.

[0043] The term “carbodiimide group” means a divalent linear triatomic fraction of general formula - (N=C=N) -.

[0044] The (poly)carbodiimide compound(s) according to the invention may optionally comprise in their structure one or more reactive groups other than carbodiimide groups, selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide and azacyclopropane.

[0045] The reactive group(s) other than the carbodiimide groups may be pendant or terminal. Preferably, the (poly)carbodiimide compound(s) include one or more terminal groups other than carbodiimide groups, preferably one or more terminal groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide and azacyclopropane.

[0046] According to a particular embodiment, the (poly)carbodiimide compound is chosen from the compounds of the following formula (I): OO I laughed. Ri——A—R, H l Jn H " (I),

[0047] in which:

[0048] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0049] - Ri and R2 independently represent a grouping chosen from a radical hydrocarbon, preferably alkyl, optionally interrupted by one or more heteroatoms, a group selected from the following groups: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylmylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide, and azacyclopropane, and a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatoms and by one or more groups selected from the following groups: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl,acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylmylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and azacyclopropane; ,

[0050] - n denotes an integer from 1 to 1000; and

[0051] - A is a monomer selected from the compounds below:

[0052] According to another embodiment, the (poly)carbodiimide compound is chosen from the compounds with the following formula (!): O (D

[0053] in which:

[0054] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0055] - Yiet Y2 represent, independently, a divalent organic radical chosen from a saturated aliphatic group in C36 at Ci or an aromatic or alkylaromatic group in C6 to C24, the aliphatic or aromatic group optionally comprising one or more non-pending heteroatoms, such as nitrogen atom, oxygen atom, sulfur atom, or combinations thereof;

[0056] - Zi and Z2 represent, independently, a reactive terminal group or a group inert terminal;

[0057] - as an inert terminal group, Zi and Z2 can represent, independently, a saturated aliphatic group, linear or branched or cyclic, in the C1 to C50 range, or an aromatic group in the C6 to C8 range, said aliphatic and aromatic groups optionally comprising from 1 to 10 heteroatoms selected from nitrogen, oxygen, sulfur and their combinations, and the aliphatic or aromatic group may be partially or totally fluorinated; in this variant, Zi and Z2 comprise a CG linking group connecting Zi to Yi and Z2 to Y2, the CG group being a single covalent bond, a saturated C-C bond, an unsaturated covalent C-C bond, an amide group, an ester group, a carbonate group, a thioester group, an ether group, a urethane group, a thiourethane group or a urea group;

[0058] - as a reactive terminal group, Zi and Z2 can be chosen from the alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide groups such as propyl epoxide or butyl epoxide and azacyclopropane;

[0059] - Q represents an organopolymer or an organo-oligomer comprising units repetitive saturated aliphatic groups, linear or branched or cyclic, or aromatic groups or alkylaromatic groups, coupled by repetitive carbonate, ester, ether, amide, urethane or urea bonds or their combinations;

[0060] - A represents a divalent aliphatic, aromatic, alkylaromatic or linear, saturated, branched or cyclic having from 2 to 30 carbon atoms, optionally including one or more non-pending heteroatoms, such as nitrogen atom, oxygen atom, sulfur atom, or combinations thereof, in the aliphatic chain or aromatic chain;

[0061] - r denotes an integer equal to 0 or 1;

[0062] - m denotes an integer from 0 to 1000, preferably equal to 0 or 1;

[0063] - m' designates an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0064] - n denotes an integer from 0 to 1000, preferably equal to 0 or 1, with m+ (m'*n ) > 2.

[0065] Preferably, Zi and Z2 represent, independently, a reactive terminal group; more preferably, Zi and Z2 represent, independently, a group selected from the following groups: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide, and azacyclopropane.

[0066] Such (poly)carbodiimide compounds are marketed for example by the company 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.

[0067] Preferably, the (poly)carbodiimide compound(s) is / are chosen from the compounds of the following formula (II): O ..¾ ■A Lf y*,"' x y, M \ A y H \ A----A ' A< U / H .Xl (II),

[0068] in which

[0069] - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

[0070] - Ri and R2 independently represent a hydrocarbon radical possibly interrupted by one or more heteroatom(s);

[0071] - n and z denote an integer from 1 to 20, with n+z > 2 and w denotes a integer ranging from 1 to 3;

[0072] - Li independently represents a divalent aliphatic hydrocarbon radical in Cr Cig, a C3-Ci5 cycloalkylene radical, a C3-Ci2 heterocycloalkylene group, or a C6-Ci4 arylene group, and mixtures thereof;

[0073] - E independently represents a grouping chosen from:

[0074] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-,

[0075] in which R3 and R4 independently represent a divalent hydrocarbon radical possibly interrupted by one or more heteroatom(s);

[0076] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, possibly interrupted by one or more heteroatom(s);

[0077] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

[0078] 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.

[0079] The hydrocarbon radical may comprise one or more cyclic groups.

[0080] The hydrocarbon radical can 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 can be incorporated in the form of a salt.

[0081] The term "heteroatom(s)" means an oxygen atom O, a sulfur atom S or a nitrogen atom N, 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 among the oxygen atoms O, sulfur atoms S or nitrogen atoms N.

[0082] Preferably, Xi and X2 independently represent an oxygen atom.

[0083] Preferably, Ri and R2 are chosen independently from dialkylaminoalcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, and mixtures thereof.

[0084] According to a preferred embodiment, Ri and R2 are chosen independently from the following groupings (i) to (iv):

[0085] (i) the compound of the following formula (III):

[0086] R7-OC(O)-C(R8)(H)-(III),

[0087] wherein R7 represents a Ci-C3 alkyl group, and R8 represents a hydrogen atom or a Ci-C3 alkyl group, preferably R7 is a methyl and R8 is a hydrogen atom or a methyl.

[0088] (ii) the compound of the following formula (IV):

[0089] R9-[0-CH2-C(H)(Rio)]p-(IV),

[0090] in which R9 represents a Ci-C4 alkyl group, Rio represents a hydrogen atom or a Ci-C4 alkyl group and p denotes an integer from 1 to 3; preferably, R9 is a methyl, ethyl or butyl and Ri0 is a hydrogen atom or a methyl and p is equal to 1.

[0091] (iii) the compound of the following formula (V):

[0092] (Rn)2N-CH2-C(H)(Ri2)- (V),

[0093] wherein Rn represents a Ci-C4 alkyl group and Rn represents a hydrogen atom or a Ci-C4 alkyl group; preferably Ru is a methyl, ethyl or butyl and Rn is a hydrogen atom or a methyl.

[0094] (iv) the compound of the following formula (VI):

[0095] R13-[O-CH2-C(H)(R14)]q- (VI),

[0096] wherein Rn represents a Ci-C4 alkyl group or a phenyl, R[4 represents a hydrogen atom or a CrC4 alkyl group and q denotes an integer from 4 to 30; preferably Rn is a methyl, ethyl or butyl and R[4 is a hydrogen atom or a methyl.

[0097] Preferably, Ri and R2 independently represent a compound of formula (VI) in which Rn represents a CrC4 alkyl group or a phenyl, preferably a Ci-C4 alkyl group, more preferably a methyl, R[4 represents a hydrogen atom or a CrC4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30.

[0098] 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.

[0099] Preferably, in formula (IV), R9 is a methyl, ethyl or butyl and Rio is a hydrogen atom or a methyl and p is equal to 1.

[0100] Preferably, in formula (VI), Rn is a methyl, ethyl or butyl and RM is a hydrogen atom or a methyl and q denotes an integer from 4 to 30.

[0101] According to another alternative embodiment, Ri and R2 are identical and represent a compound of formula (VI) in which Rn represents a CrC4 alkyl group or a phenyl, preferably a CrC4 alkyl group, more preferably a methyl, R[4] represents a hydrogen atom or a Ci-C4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30.

[0102] Preferably, n denotes an integer from 1 to 20, more preferably from 2 to 20.

[0103] Preferably, z denotes an integer from 1 to 20, more preferably from 2 to 20.

[0104] Preferably, w is equal to 1.

[0105] Preferably, w is equal to 1, n+z denotes an integer from 4 to 10.

[0106] Preferably, Li is selected from a divalent aliphatic hydrocarbon radical in C1-C18 such as methylene, ethylene, and propylene, a cycloalkylene radical in C3-C15 such as cyclopentylene, cycloheptylene, and cyclohexylene, a heterocycloalkylene group in C3-Ci2 such as imidazolene, pyrrolene and furanylene, or an arylene group in C6-Ci4 such as phenylene, and mixtures thereof.

[0107] For example, Li can be chosen from a radical derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-diisocyanate dodecane, norbornane diisocyanate, 2,4-bis-(8-isocyanateoctyl)-1,3-dioctylcyclobutane, 4,4'-dicylclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate and phenylene diisocyanate and mixtures thereof.

[0108] Preferably, Li is selected from a C3-Ci5 cycloalkylene radical, or a C6-Ci4 arylene group and mixtures thereof, such as the compounds of the following formula (VII):

[0109] Preferably, L1 is the 4,4-dicyclohexylene methane corresponding to the following formula (VIII): (VIII).

[0110] According to another embodiment, when L1 is an arylene group at C6-Ci4, Li is not the m-tetramethylxylylene radical represented by the following formula (IX): (IX).

[0111] As stated previously, E independently represents a grouping chosen from:

[0112] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0113] in which R3 and R4 independently represent a divalent hydrocarbon radical possibly interrupted by one or more heteroatom(s);

[0114] - R5 independently represents a covalent bond or a hydrocarbon radical saturated divalent, possibly interrupted by one or more heteroatom(s); and

[0115] - R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

[0116] Preferably, R3 and IC are chosen independently from a C6-CM arylene radical such as phenylene, a C3-Ci2 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Ci8 alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatom(s) and mixtures thereof.

[0117] More preferably, R3 and IC are chosen independently from a linear or Ci-Ci8 branched alkylene radical such as methylene, butylene, propylene, ethylene, optionally interrupted by one or more heteroatom(s).

[0118] Preferably, when R5 is not a covalent bond, R5 is selected from a C6-Ci4 arylene radical such as phenylene, a C3-Ci2 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Ci8 alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

[0119] Preferably, R6 is selected from a C6-Ci4 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.

[0120] Preferably, E represents an -O-R3-O- group in which R3 is selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a radical linear or branched CrCi8 alkylene, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

[0121] More preferably, E represents a -O-R3-O- group in which R3 represents a linear or CrCi8 branched alkylene radical such as methylene, butylene, propylene, ethylene, optionally interrupted by one or more heteroatom(s).

[0122] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from alpha-methylstyryl-isocyanates of the following formula (X): (X),

[0123] in which 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,

[0124] n denotes an integer from 2 to 100.

[0125] In this embodiment, the term "alkyl group" is as defined above.

[0126] In this embodiment, the term "cycloalkyl group" is as defined above.

[0127] In this embodiment, n can denote an integer from 2 to 50, preferably from 3 to 30, more preferably from 5 to 10.

[0128] According to another particular embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI): (XI),

[0129] in which 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.

[0130] The "alkyl group", the "cycloalkyl group" and the "aryl group" are as defined above.

[0131] According to a preferred embodiment, the (poly)carbodiimide compound is selected from compounds of formula (I) or formula (II) in which:

[0132] - Xi and X2 independently represent an oxygen atom;

[0133] - Ri and R2 are chosen independently from among the dialkylaminoalcohols, the alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, more preferably the compound of formula (VI) as previously described in which R13 represents a CrC4 alkyl group or a phenyl, preferably a CrC4 alkyl group, more preferably a methyl, RM represents a hydrogen atom or a CrC4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30;

[0134] - n and z, when present, denote an integer from 1 to 20, with n +z > 2 and w is equal to 1;

[0135] - Li, when present, is chosen from an aliphatic hydrocarbon radical divalent in CrCi8, a cycloalkylene radical in C3-Ci5, a heterocycloalkylene group in C3-Ci2, or an arylene group in C6-Ci4, and mixtures thereof, preferably a cycloalkylene radical in C3-Ci5;

[0136] - A, when present, is chosen from an aliphatic hydrocarbon radical divalent in CrCi8, a cycloalkylene radical in C3-Ci5, a heterocycloalkylene group in C3-Ci2, or an arylene group in C6-Ci4, and mixtures thereof, preferably a cycloalkylene radical in C3-Ci5;

[0137] - E, when present, independently represents a grouping chosen from:

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

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

[0140] - when R5 is not a covalent bond, R5, when present, is chosen including a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched Ci-Ci8 alkylene radical, possibly interrupted by one or more heteroatoms, and mixtures thereof; and

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

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

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

[0144] - Ri and R2 are chosen independently from among the dialkylaminoalcohols, the alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, and mixtures thereof;

[0145] - n and z denote an integer from 1 to 20, with n+z > 2 and w is equal to 1;

[0146] - Li is chosen from a divalent aliphatic hydrocarbon radical in CrCi8, a cycloalkylene radical at C3-Ci5, a heterocycloalkylene group at C3-Ci2, or an arylene group at C6-Ci4, and mixtures thereof;

[0147] - E independently represents a grouping chosen from:

[0148] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0149] wherein R3 and R4 are independently selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

[0150] - when R5 is not a covalent bond, R5 is chosen from an arylene radical in C6-Ci4, a cycloalkylene radical in C3-Ci2, a linear or branched alkylene radical in CrCi8, possibly interrupted by one or more heteroatoms, and mixtures thereof; and

[0151] -R6 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

[0152] More preferably, the (poly)carbodiimide compound is chosen from compounds of formula (II) in which:

[0153] - Xi and X2 independently represent an oxygen atom;

[0154] - Ri and R2, are independently of (poly)alkylene glycol monoalkyl ethers, in which a hydroxy group has been removed;

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

[0156] - Li is a C3-Ci5 cycloalkylene radical;

[0157] - E independently represents a grouping chosen from:

[0158] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0159] wherein R3 and R4 are independently selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched Ci-Ci8 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

[0160] - when R5 is not a covalent bond, R5 is chosen from an arylene radical at C6-Ci4, a cycloalkylene radical at C3-Ci2, a linear or branched alkylene radical in C1-C18, possibly interrupted by one or more heteroatoms, and their mixtures; and

[0161] -R6 is chosen from a C6-C14 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

[0162] Even more preferably, the (poly)carbodiimide compound is chosen from compounds of formula (II) in which:

[0163] - Xi and X2 independently represent an oxygen atom;

[0164] - Ri and R2, independently represent the compound of the following formula (VI):

[0165] R13-[O-CH2-C(H)(R14)]q- (VI),

[0166] in which Rn represents a Ci-C4 alkyl group or a phenyl, preferably a CrC4 alkyl group, more preferably a methyl, R14 represents a hydrogen atom or a Ci-C4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30;

[0167] - n and z denote an integer from 2 to 20, with n+z from 4 to 10 and w is equal to 1;

[0168] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, the cycloheptylene, cyclohexylene, and 4,4-dicyclohexylene methane; and

[0169] - E represents a grouping -O-R3-O- in which R3 is chosen from a radical arylene in C6-Ci4, a cycloalkylene radical in C3-Ci2, a linear or branched alkylene radical in CrCi8, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

[0170] Even more preferably, the (poly)carbodihnide compound is chosen from compounds of formula (II) in which:

[0171] - Xi and X2 independently represent an oxygen atom;

[0172] - Ri and R2, independently represent the compound of the following formula (VI):

[0173] R13-[O-CH2-C(H)(R14)]q- (VI)

[0174] wherein R[3 represents a Ci-C4 alkyl group or a phenyl, preferably a CrC4 alkyl group, more preferably a methyl, R14 represents a hydrogen atom or a Ci-C4 alkyl group, preferably a hydrogen atom and q denotes an integer from 4 to 30;

[0175] - n and z denote an integer from 2 to 20, with n+z from 4 to 10 and w is equal to 1;

[0176] - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, the cycloheptylene, cyclohexylene, 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and

[0177] - E represents a group- -O-R3-O- in which R3 represents a radical linear or branched Ci-Ci8 alkylene such as methylene, propylene, butylene ethylene, possibly interrupted by one or more heteroatom(s).

[0178] According to a preferred embodiment, the (poly)carbodiimide compound is a compound with the following formula (XII): (XII),

[0179] in which L1 is 4,4-dicyclohexylene methane, n and z denote an integer from 2 to 20, with n+z ranging from 4 to 10, E represents an -O-R3-O- group in which R3 represents a linear or CrCi8 branched alkylene radical such as methylene, propylene, butylene ethylene, optionally interrupted by one or more heteroatom(s), and r and s denote an integer from 4 to 30.

[0180] Advantageously, the total amount of the (poly)carbodiimide compound(s) ranges from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, even more preferably from 0.5 to 8%, better from 1 to 6% by weight relative to the total weight of composition C.

[0181] Compound having at least one carboxylic acid group

[0182] Composition C according to the invention used in the context of the coloring process according to the invention comprises at least one compound having at least one carboxylic acid group.

[0183] Preferably, the compound having at least one carboxylic acid group is chosen from silicone compounds comprising at least one carboxylic group, polyurethanes, acrylic polymers, and mixtures thereof. Polyurethanes and acrylic polymers:

[0184] According to a preferred embodiment, composition C comprises at least one compound having at least one carboxylic acid group selected from polyurethanes, acrylic polymers and their mixtures.

[0185] Preferably, the compound(s) having at least one carboxylic acid group are in the form of aqueous dispersions of polymer particles selected from polyurethanes, acrylic polymers, and their mixtures.

[0186] Preferably, composition C comprises at least one compound having at least one carboxylic acid group in the form of an aqueous dispersion of polyurethane particles, acrylic polymers, and mixtures thereof.

[0187] The dispersion(s) may be simple dispersions in the aqueous medium of the cosmetic composition. Latexes are a particular example of a dispersion.

[0188] The aqueous dispersion(s) of polymer particles can be chosen from aqueous dispersions of polyurethane particles.

[0189] More particularly, the polyurethane(s) present in the aqueous dispersions used in the present invention are derived from the reaction of

[0190] - a prepolymer of the following formula (A):

[0191] (A),

[0192] in which

[0193] - Ri represents a divalent radical of a dihydroxylated compound;

[0194] - R2 represents a radical of an aliphatic or cycloaliphatic polyisocyanate;

[0195] - R3 represents a radical of a low molecular weight diol, possibly substituted by one or more ionic groups;

[0196] - n represents an integer from 1 to 5, and

[0197] - m is greater than 1;

[0198] - at least one chain extender according to the following formula (B):

[0199] H2N-R4-NH2 (B),

[0200] wherein R4 represents an alkylene radical or alkylene oxide that is not substituted by one or more ionic or potentially ionic groups; and

[0201] - at least one string extender according to the following formula (C):

[0202] H2N-R5-NH2 (C),

[0203] wherein R5 represents an alkylene radical substituted by one or more ionic or potentially ionic groups.

[0204] Among the dihydroxylated compounds usable according to the present invention, particular examples include compounds having two hydroxyl groups and a number molecular weight of approximately 700 to approximately 16,000, and preferably of approximately 750 to approximately 5,000. Examples of dihydroxylated compounds having a high molecular weight include polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadienes, polyhydroxylated polythioethers, and mixtures thereof. Preferably, the hydroxylated compounds are selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0205] The polyisocyanates usable according to the present invention are in particular chosen from among the organic diisocyanates having a molecular weight of about 112 to 1000, and preferably of about 140 to 400.

[0206] Preferably, the polyisocyanates are chosen from among the diisocyanates and more particularly from those represented by the general formula R2(NCO)2, in which R2 represents a divalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having from 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having from 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having from 6 to 15 carbon atoms.

[0207] Preferably, R2 represents an organic diisocyanate. Examples of organic diisocyanates include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, bis-(4-isocyanato-3-methylcyclohexyl)methane, and toluene diisocyanate (TDI) isomers such as 2,4-toluene diisocyanate and 2,6-diisocyanate. toluene and mixtures thereof, hydrogenated toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures with its isomers 2,4-diphenylmethane diisocyanate and possibly 2,2'-diphenylmethane diisocyanate, naphthalene-1,5 diisocyanate, and mixtures thereof.

[0208] Preferably, the diisocyanates are aliphatic and cycloaliphatic diisocyanates, and are more preferably chosen from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate and mixtures thereof.

[0209] By "low molecular weight diol," the present invention means a diol having a molecular weight of about 62 to 700, and preferably of 62 to 200. These diols may comprise aliphatic, alicyclic, or aromatic groups. Preferably, they comprise only aliphatic groups.

[0210] Preferably, R3 represents a low molecular weight diol, having more than 20 carbon atoms, more preferably selected from ethylene glycol, diethylene glycol, propane 1,2-diol, propane 1,3-diol, butane 1,4-diol, butylene 1,3-glycol, neopentyl glycol, butyl-ethyl-propane diol, cyclohexane diol, 1,4-cyclohexane dimethanol, hexane 1,6-diol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), and mixtures thereof.

[0211] Low molecular weight diols may optionally include ionic or potentially ionic groups. Examples of low molecular weight diols containing ionic or potentially ionic groups are described in particular in US patent 3,412,054. Such compounds are preferably selected from dimethylol butanoic acid, dimethylol propionic acid, polycaprolactone diols containing a carboxyl group, and mixtures thereof.

[0212] If lower molecular weight diols containing ionic or potentially ionic groups are used, they are preferably used in an amount such that less than 0.30 meq of COOH per gram of polyurethane in the polyurethane dispersion are present.

[0213] The prepolymer is elongated using two families of chain extenders. The first family of chain extenders corresponds to compounds of general formula (B).

[0214] The chain extenders of formula (B) are preferably chosen from among the alkylene diamines, such as hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine; Alkylene oxide diamines, such as 3-{2-[2-(3-aminopropoxy)ethoxy]-ethoxy}propylamine (also called dipropylamine diethylene glycol or DPA-DEG, available from Tomah Products, Milton, Wis.), 2-methyl-1,5-pentanediamine (Dytec A from DuPont), hexanediamine, isophoronediamine, 4,4-methylenedi-(cyclohexylamine), and DPA series ethers available from Tomah Products, Milton, Wis., such as dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropylene glycol, dipropylamine poly(propylene glycol), and dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propane diol, dipropylamine 2-methyl-1,3-propane diol, dipropylamine 1,4-butane diol, dipropylamine 1,3-butane diol, dipropylamine 1,6-hexane diol and dipropylamine cyclohexane-1,4-dimethanol; and mixtures thereof.

[0215] The second family of chain extenders corresponds to compounds of general formula (C). Such compounds preferably have one ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Such compounds may optionally comprise two groups reactive with isocyanate groups and one ionic group or one capable of forming an ionic group.

[0216] The ionic or potentially ionic group may preferably be selected from ternary or quaternary ammonium groups or groups convertible into such groups, a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group. The conversion, at least partial, of the convertible groups into salts of ternary or quaternary ammonium groups may take place before or during mixing with water.

[0217] The chain extenders of formula (C) are preferably chosen from among the diaminosulfonates, such as for example the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid, and mixtures thereof.

[0218] The polyurethane usable according to the present invention may optionally further comprise compounds that are respectively located at the ends of the chains and terminate said chains (chain terminators). Such compounds are described in particular in US patents 7,445,770 and / or US patents 7,452,770.

[0219] Preferably, the aqueous dispersion of polyurethane particles has a viscosity of less than 2000 mPa.s at 23°C, more preferably less than 1500, and even better less than 1000. Even more preferably, the aqueous dispersion of polyurethane has a glass transition temperature of less than 0°C.

[0220] Preferably, the aqueous polyurethane dispersion has a polyurethane (or active ingredient, or dry matter) content, based on the weight of the dispersion, of 20 to 60% by weight, more preferably 25 to 55% by weight, and even better 30 to 50% by weight. This means that the polyurethane (dry matter) content of the aqueous dispersion is preferably 20% to 60% by weight, more preferably 25% to 55% by weight, and even better 30% to 50% by weight, relative to the total weight of the dispersion.

[0221] Also preferably, the aqueous dispersion of polyurethane particles has a glass transition temperature (Tg) equal to or less than -25°C, preferably less than -35°C, and more preferably less than -40°C.

[0222] Polyurethane particles can have an average diameter of up to about 1000 nm, for example from about 50 nm to about 800 nm, better from about 100 nm to about 500 nm. These particle sizes can be measured with a laser particle size analyzer (for example Brookhaven BI90).

[0223] By way of non-limiting example of aqueous polyurethane dispersions, one can cite those sold under the name Baycusan® by Bayer such as, for example, Baycusan® C1000 (INCI name: polyurethane-34), Baycusan® C1001 (INCI name: polyurethane-34), Baycusan® C1003 (INCI name: polyurethane-32), Baycusan® C1004 (INCI name: polyurethane-35) and Baycusan® C1008 (INCI name: polyurethane-48).

[0224] We may also mention aqueous polyurethane dispersions of isophthalic acid / adipic acid copolymer / hexylene glycol / neopentyl glycol / dimethylol acid / isophorone diisocyanate (INCI name: Polyurethane-1, such as Luviset® PUR, BASF), polycarbonate polyurethane, polyurethane and aliphatic polyester polyurethane (such as the NEOREZ® series, DSM, such as NEOREZ® R989, NEOREZ® and R-2202).

[0225] According to a preferred embodiment, the aqueous dispersion of polyurethane particles can be selected from aqueous dispersions of particles of compounds having the INCI name polyurethane-35 or compounds having the INCI name polyurethane-34.

[0226] Preferably, the compound(s) having at least one carboxylic acid group 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

[0227] For the purposes of this invention, "polymer" means a compound consisting of the repetition of one or more motifs (these motifs being derived from compounds called monomers). This motif or these motifs are repeated at least twice and preferably at least three times.

[0228] By "film-forming polymer" is meant a polymer capable of forming, either alone or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, in particular on hair, and preferably a cohesive film.

[0229] For the purposes of this invention, "acrylic polymer" means a polymer synthesized from at least one monomer selected from (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide.

[0230] The motif(s) derived from the (meth)acrylic acid monomers of the polymer may (may) possibly be in the form of salt(s), in particular of alkali metal, alkaline earth metal, ammonium or organic base.

[0231] Esters of (meth)acrylic acid (also called (meth)acrylates) are advantageously chosen from alkyl (meth)acrylates, in particular alkyl methyl in C1 to C30, preferably in C1 to C20, better in C1 to Cm, aryl (meth)acrylates, in particular aryl in C6 to C10, hydroxyalkyl (meth)acrylates, in particular hydroxyalkyl in C2 to C6.

[0232] Among the alkyl (meth)acrylates, we can mention methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, ethyl-2 hexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate.

[0233] Among the hydroxyalkyl (meth)acrylates, we can mention hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.

[0234] Among the aryl (meth)acrylates, benzyl acrylate and phenyl acrylate can be cited.

[0235] The particularly preferred (meth)acrylic acid esters are alkyl (meth)acrylates, preferably alkyl in C1 to C30, more preferably in C1 to C20, even better in C1 to C10, and even more particularly in C1 to C4.

[0236] According to the present invention, the alkyl group of the esters can be fluorinated, or even perfluorinated, that is to say that part or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

[0237] Examples of (meth)acrylic acid amides include (meth)acrylamides, as well as N-alkyl (meth)acrylamides, particularly alkyl in C2 to C12. Among the N-alkyl (meth)acrylamides, examples include N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide and N-undecylacrylamide.

[0238] The acrylic polymer according to the invention can be a homopolymer or a copolymer, advantageously a copolymer, even better a copolymer of (meth)acrylic acid and (meth)acrylic acid esters.

[0239] Preferably, the acrylic polymer(s) according to the invention comprise one or more motifs derived from the following monomers:

[0240] a) (meth)acrylic acid; and

[0241] b) alkyl (meth)acrylate in C1 to C30, more preferably in C1 to C20, even better in C1 to C10, and even more particularly in C1 to C4.

[0242] Preferably, the aqueous dispersion of acrylic polymer particles does not include a surfactant.

[0243] The term “surfactant” means any agent capable of modifying the surface tension between two surfaces.

[0244] Among the acrylic polymers according to the invention, we can mention the copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, in particular the copolymers of methacrylic acid and ethyl acrylate such as the compound sold under the trade name LUVIMER MAE by BASF, or the Polyacrylate-2 crosspolymer compound sold under the trade name FIXATE SUPERHOLD POLYMER by LUBRIZOL, or the Acrylate Copolymer compound sold under the trade name DAITOSOL 3000VP3 by DAITO KASEI KOGYO, or the Acrylate Copolymer compound sold under the trade name DAITOSOL 3000SLPN-PE1 by DAITO KASEI KOGYO.

[0245] 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.

[0246] As an additional monomer, examples include styrenic monomers, in particular styrene and alpha-methylstyrene, and preferably styrene.

[0247] In particular, the acrylic polymer may be a styrene / (meth)acrylate copolymer, and in particular a polymer selected from copolymers resulting from the polymerization of at least one styrenic monomer and at least one alkyl (meth)acrylate monomer in Ci to C20, preferably in Ci to Ci0.

[0248] The alkyl (meth)acrylate monomer in C1 to C10 can be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethyl hexyl acrylate.

[0249] As an acrylic polymer, we can cite the styrene / (meth)acrylate(s) copolymers marketed under the name JONCRYL 77 by BASF, under the name YODOSOL GH41F by AKZO NOBEL and under the name SYNTRAN 5760 CG by INTERPOLYMER.

[0250] Preferably, composition C comprises at least an aqueous dispersion of acrylic polymer particles.

[0251] More preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more motifs derived from the following monomers:

[0252] a) (meth)acrylic acid; and

[0253] b) alkyl (meth)acrylate in C1 to C30, more preferably in C1 to C20, even better in C1 to C10, and even more particularly in C1 to C4.

[0254] Preferably, the aqueous dispersion of acrylic polymer particles has an acrylic polymer (or active material, or dry matter) content based on weight of the dispersion of 20 to 60% by weight, more preferentially of 22 to 55% by weight and even better of 25 to 50% by weight. Silicone acrylic copolymer

[0255] According to a particular embodiment, the silicone compound(s) comprising at least one carboxylic group are chosen from silicone acrylic copolymers.

[0256] Preferably, said silicone acrylic copolymer(s) comprise:

[0257] - at least one acrylic, methacrylic, or crotonic motif; and

[0258] - at least one polydimethylsiloxane (PDMS) motif.

[0259] For the purposes of this invention, "polydimethylsiloxanes" (also referred to as PDMS), in accordance with general acceptance, means any linear structure organosilicon polymer or oligomer of variable molecular weight, obtained by polymerization and / or polycondensation of suitably functionalized silanes, and consisting essentially of a repetition of principal motifs in which silicon atoms are linked together by oxygen atoms (Si-O-Si siloxane bond), comprising methyl radicals directly linked via a carbon atom to said silicon atoms.

[0260] The PDMS chains that can be used to obtain the copolymer used according to the invention comprise at least one polymerizable radical group, preferably located on at least one of the ends of the chain, i.e. the PDMS can have for example a polymerizable radical group on each of the two ends of the chain or have a polymerizable radical group on one end of the chain and a trimethylsilyl terminal group on the other end of the chain.

[0261] By polymerizable radical group is meant a radical capable of polymerizing with other polymerizable radical groups or monomers. Preferably, the polydimethylsiloxane motif comprises at least one polymerizable radical group.

[0262] Preferably, the polymerizable radical group comprises at least one vinyl group.

[0263] Preferably, the polydimethylsiloxane (PDMS) motif comprises at least one polymerizable radical group comprising at least one vinyl group, preferably at least two polymerizable radical groups comprising at least one vinyl group, preferably located on at least one end of the chain.

[0264] As indicated above, said or said silicone acrylic copolymers preferably comprise at least one acrylic or methacrylic or crotonic motif, that is to say at least one motif comprising a carboxylic group.

[0265] The term “carboxylic group” means a functional group COOH or COO, the counter-ion of the COO group being able to be chosen from among the alkali metals, the alkaline earth metals, the quaternary ammoniums.

[0266] Preferably, said silicone acrylic copolymer(s) comprise:

[0267] - at least one acrylic or methacrylic or crotonic motif, and at least one motif acrylic ester or methacrylic ester or vinyl ester; and

[0268] - at least one polydimethylsiloxane (PDMS) motif.

[0269] More preferably, the composition comprises one or more silicone acrylic copolymers comprising: - at least one crotonic motif and at least one motif selected from an alkyl crotonate motif, the alkyl radical being a saturated linear or branched radical containing from 1 to 20 carbon atoms; a vinyl acetate motif; a vinyl alkyl ester motif, the alkyl radical being a saturated linear or branched radical containing from 2 to 20 carbon atoms; and mixtures thereof; and - at least one polydimethylsiloxane (PDMS) motif.

[0270] By crotonic motif is meant a motif derived from a crotonic acid monomer or one of its salts.

[0271] By alkyl crotonate motif is meant a motif derived from a crotonic acid ester monomer, having a linear or branched, saturated alkyl radical containing from 1 to 20 carbon atoms.

[0272] By vinyl alkyl ester motif is meant a motif derived from a vinyl ester monomer having a saturated linear or branched alkyl radical containing from 2 to 20 carbon atoms.

[0273] A vinyl acetate motif is defined as a motif derived from a vinyl acetate monomer.

[0274] In a preferred embodiment, said silicone acrylic copolymer(s) comprise: - at least one crotonic motif, at least one vinylacetate motif and at least one vinyl alkyl ester motif, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms, and - at least one polydimethylsiloxane (PDMS) motif, preferably comprising at least one polymerizable radical group including at least one vinyl group.

[0275] According to a particularly preferred embodiment, said silicone acrylic copolymer(s) comprise: - at least one crotonic motif, at least one vinylacetate motif and at least one vinyl alkyl ester motif, the alkyl radical being a linear or branched, saturated radical containing from 6 to 16 carbon atoms, and

[0276] - at least one polydimethylsiloxane (PDMS) motif comprising at least one group polymerizable radical comprising at least one vinyl group.

[0277] More preferably, the composition comprises one or more silicone acrylic copolymers comprising: - at least one crotonic motif, at least one vinylacetate motif and at least one vinyl alkyl ester motif, the alkyl radical being a linear or branched, saturated radical containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms; and - at least one polydimethylsiloxane (PDMS) motif comprising at least one polymerizable radical group including at least one vinyl group.

[0278] Even more preferably, the composition comprises one or more silicone acrylic copolymers comprising:

[0279] - at least one crotonic motif, at least one vinylacetate motif and at least one vinyl alkyl ester motif, the alkyl radical being a linear or branched, saturated radical containing 6 to 16 carbon atoms; and

[0280] - at least one polydimethylsiloxane (PDMS) motif comprising at least one group polymerizable radical comprising at least one vinyl group.

[0281] Among the silicone acrylic copolymers that can be used in the context of the invention, mention can be made of the compound sold by the company Wacker Chemie AG under the trade name Belsil® PI 101, with the INCI name Crotonic Acid / Vinyl C8-12 Isoalkyl Esters / VA / Bis-Vinyldimethicone Crosspolymer.

[0282] The total quantity of the compound or compounds having at least one carboxylic acid group is preferably from 0.1 to 30% by weight, more preferably from 0.5 to 20% by weight, better still from 0.5 to 15% by weight, and even more preferably from 1 to 10% by weight relative to the total weight of composition C.

[0283] The total quantity of the aqueous dispersion(s) of polymer particle(s) selected from polyurethanes, acrylic polymers, and their mixtures is preferably from 0.1 to 50% by weight, more preferably from 0.5 to 40% by weight, better still from 0.5 to 30% by weight, and even more preferably from 1 to 20% by weight relative to the total weight of composition C.

[0284] According to a particular embodiment, the total quantity of the aqueous dispersion(s) of acrylic polymer particle(s) preferably ranges from 0.1 to 50% by weight, more preferably from 0.5 to 40% by weight, better still from 0.5 to 30% by weight, and even more preferably from 1 to 20% by weight relative to the total weight of composition C. Pigment

[0285] Composition C used in the process according to the invention comprises at least one pigment having a particle size D90 less than or equal to 50 qm.

[0286] The particle size can be assessed by any means known to those skilled in the art. In particular, it can be assessed using a RETSCH AS 200 DIGIT particle size analyzer; Oscillation height: 1.25 mm / Sieving time: 5 minutes.

[0287] Advantageously, the pigment(s) have a D90 particle size less than or equal to 20 pm, preferably from 10 nm to 20 pm, more preferably from 50 nm to 20 pm, even more preferably from 100 nm to 20 pm, better still from 1 pm to 20 pm.

[0288] The term "pigment" means all pigments that impart color to capillary keratin fibers. Their solubility in water at 25 °C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

[0289] The pigments that can be used are chosen in particular from among the organic and / or mineral pigments known to the technique, in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.

[0290] They may be natural, of natural origin, or not.

[0291] These pigments may be in the form of a powder or pigment paste. They may be coated or uncoated.

[0292] Pigments can, for example, be chosen from mineral pigments, organic pigments, lacquers, special effect pigments such as mother-of-pearl or glitter, and mixtures thereof.

[0293] The pigment may be a mineral pigment. By mineral pigment is meant any pigment that meets the definition in the Ullmann Encyclopedia in the chapter on inorganic pigments. Examples of mineral pigments useful in the present invention include iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium oxide.

[0294] The pigment may be an organic pigment. By "organic pigment" is meant any pigment that meets the definition in the Ullmann encyclopedia in the chapter on organic pigment.

[0295] The organic pigment may in particular be selected from the following compounds: nitroso, nitro, azo, xanthene, pyrene, quinoline, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane, quinophthalone.

[0296] In particular, white or colored organic pigments may be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments coded in the Color Index under references Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments coded in the Color Index under references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments coded in the Color Index under reference Cl 61565, 61570, 74260, the orange pigments coded in the Color Index under references CI 11725, 45370, 71105, the red pigments coded in the Color Index under 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 and phenolic derivatives as described in the patent FR 2 679 771.

[0297] By way of example, one can also cite organic pigment pastes such as the products sold by the company HOECHST under the name:

[0298] - COSMENYL YELLOW IOG: Pigment YELLOW 3 (Cl 11710);

[0299] - COSMENYL YELLOW G: Pigment YELLOW 1 (Cl 11680);

[0300] - ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);

[0301] - COSMENYL RED R: Pigment RED 4 (Cl 12085);

[0302] - CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);

[0303] - VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);

[0304] - COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);

[0305] - COSMENYL GREEN GG: Pigment GREEN 7 (Cl 74260);

[0306] - COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

[0307] The pigments according to the invention can also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments can be composed in particular of particles comprising an inorganic core, at least one binder ensuring the fixation of organic pigments on the core, and at least one organic pigment covering at least partially the core.

[0308] The organic pigment can also be a lacquer. By lacquer, we mean colorants adsorbed onto insoluble particles, the whole thus obtained remaining insoluble during use.

[0309] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

[0310] Among the colorants, we can mention carminic acid. We can also mention the colorants known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).

[0311] As examples of lacquers, we can cite the product known under the following name: D & C Red 7 (CI 15 850 :1).

[0312] The pigment can also be a special effects pigment. Special effects pigments are defined as pigments that generally create an appearance colored (characterized by a certain shade, a certain vividness and a certain clarity) non-uniform and changing according to the conditions of observation (light, temperature, angles of observation...). They are thus opposed to colored pigments which provide a uniform opaque, semi-transparent or classic transparent tint.

[0313] 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 mother-of-pearl, interference pigments or glitter.

[0314] Examples of special effect pigments include pearlescent pigments such as titanium-coated mica or bismuth oxychloride, colored pearlescent pigments such as titanium-coated mica with iron oxides, iron oxide-coated mica, titanium-coated mica, particularly with ferric blue or chromium oxide, titanium-coated mica with an organic pigment as defined above, and bismuth oxychloride-based pearlescent pigments. Examples of pearlescent pigments include Cellini pearlescent pigments marketed by BASF (Mica-TiO2-lacquer), Prestige pearlescent pigments marketed by Eckart (Mica-TiO2), Prestige Bronze pearlescent pigments marketed by Eckart (Mica-Fe2O3), and Colorona pearlescent pigments marketed by Merck (Mica-TiO2-Fe2O3).

[0315] We can also mention gold-colored mother-of-pearl, notably marketed by BASF under the names Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); bronze mother-of-pearl, notably marketed by MERCK under the names Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super Bronze (Cloisonne); orange mother-of-pearl, notably marketed by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by MERCK under the names Passion Orange (Colorona) and Matte Orange (17449) (Microna); brown-tinted mother-of-pearl, notably marketed by BASF under the names Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); copper-tinted 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 sheen, notably marketed by BASF under the name Sunstone G012 (Gemtone); pink mother-of-pearl, notably marketed by BASF under the name Tan opale G005 (Gemtone); black mother-of-pearl with a gold sheen, notably marketed by BASF under the name Nu; antique bronze 240 AB (Timica), blue mother-of-pearls notably marketed by the MERCK company under the name Matte blue (17433) (Microna), white mother-of-pearls with a silvery sheen notably marketed by the MERCK company under the name Xirona Silver and orange-pink-green-gold mother-of-pearls notably marketed by the MERCK company under the name Indian summer (Xirona) and their mixtures.

[0316] As further examples of nacres, we can also mention particles comprising a borosilicate substrate coated with titanium oxide.

[0317] Particles with a glass substrate coated with titanium oxide are notably sold under the name METASHINE MC1080RY by the company TOYAL.

[0318] Finally, examples of mother-of-pearl include polyethylene terephthalate flakes, particularly those marketed by Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver flakes). Multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate, and aluminum can also be considered.

[0319] Special effect pigments may also be selected from reflective particles, that is to say, particles whose size, structure, including the thickness of the layer(s) that constitute them and their physical and chemical nature, and surface condition, enable them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create, on the surface of the composition or mixture, when applied to the makeup support, highlights visible to the naked eye, that is to say, brighter points that contrast with their surroundings by appearing to shine.

[0320] Reflective particles can 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, in particular, have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or reflection.

[0321] These particles can have various shapes, including being platelet-shaped or globular, particularly spherical.

[0322] Reflective particles, whatever their shape, may or may not have a multilayer structure and, in the case of a multilayer structure, for example at least one layer of uniform thickness, in particular of a reflective material.

[0323] When reflective particles do not have a multilayer structure, they can be composed, for example, of metal oxides, in particular titanium or iron oxides obtained by synthesis.

[0324] When reflective particles have a multilayer structure, they may, for example, comprise a natural or synthetic substrate, in particular a synthetic substrate at least partially coated by at least one layer of a reflective material, in particular at least one metal or metallic material. The substrate may be monomaterial, multimaterial, organic and / or inorganic.

[0325] More particularly, it may be selected from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica and mixtures thereof, this list not being exhaustive.

[0326] The reflective material may include a layer of metal or a metallic material.

[0327] Reflective particles are described in particular in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0328] As further examples of reflective particles comprising a mineral substrate coated with a layer of metal, one can also mention particles comprising a borosilicate substrate coated with silver.

[0329] Silver-coated glass substrate particles in the form of wafers are sold under the name MICROGLASS METASHINE REFSX 2025 PS by the company TOYAL. Nickel / chromium / molybdenum alloy-coated glass substrate particles are sold under the names CRYSTAL STAR GF 550, GF 2525 by the same company.

[0330] Particles comprising a metallic substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, titanium may also be used, 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.

[0331] An example can be cited as aluminium, bronze or copper powders coated with SiO2 marketed under the name VISIONAIRE by the company ECKART.

[0332] Other examples include non-substrate interference pigments such as liquid crystals (Wacker's Helicones HC) and interference holographic glitter (Spectratek's Geometry Pigments or Spectra f / x). Special effect pigments also include fluorescent pigments, whether daylight fluorescent or ultraviolet fluorescent, phosphorescent pigments, photochromic pigments, thermochromic pigments, and quantum dots, marketed, for example, by Quantum Dots Corporation.

[0333] 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, interference effects.

[0334] The pigments can be dispersed within the composition by means of a dispersing agent.

[0335] The dispersing agent serves to protect the dispersed particles from agglomeration or flocculation. This dispersing agent may be a surfactant, an oligomer, a polymer, or a mixture of several of these, possessing one or more functionalities with a strong affinity for the surface of the particles to be dispersed. In particular, they may bind physically or chemically to the surface of the pigments. These dispersants also have at least one functional group that is compatible with or soluble in the continuous medium.In particular, esters of 12-hydroxystearic acid are used, especially 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 Avecia, polyglyceryl-2 dipolyhydroxystearate (name CTFA) sold under the reference Dehymyls PGPH by Henkel or polyhydroxystearic acid such as that sold under the reference Arlacel P100 by Uniqema and their mixtures.

[0336] As another dispersant that can be used in the compositions of the invention, we can mention quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17 000 sold by Avecia, poly dimethylsiloxane / oxypropylene mixtures such as those sold by Dow Corning under the references DC2-5185, DC2-5225 C.

[0337] The pigments used in the composition can be surface treated with an organic agent.

[0338] Thus the pigments previously surface treated useful in the context of the invention are pigments which have undergone totally or partially a surface treatment of a chemical, electronic, electro-chemical, mechano-chemical or mechanical nature, with an organic agent such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, pp. 53-64 before being dispersed in the composition according to the invention.These organic agents may be chosen for example from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate motifs; alkanoamines; compounds. silicones, for example silicones, in particular polydimethylsiloxanes; fluorinated organic compounds, for example perfluoroalkyl ethers; fluoro-silicone compounds.

[0339] The surface-treated pigments useful in the composition may also have been treated by a mixture of these compounds and / or have undergone several surface treatments.

[0340] 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 in the commercial market.

[0341] Preferably, the surface-treated pigments are covered by an organic layer.

[0342] 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.

[0343] Surface treatment can thus be achieved, for example, by a chemical reaction of a surfactant with the surface of the pigments and the 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.

[0344] Preferably, an organic agent covalently linked to the pigments will be used.

[0345] The surface treatment agent can represent from 0.1 to 50% by weight of the total weight of the pigment treated on the surface, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 20% by weight of the total weight of the pigment treated on the surface.

[0346] Preferably, the surface treatments of the pigments are chosen from the following treatments:

[0347] - a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW;

[0348] - a Methicone treatment such as the SI surface treatment marketed by LCW;

[0349] - a Dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW;

[0350] - a Dimethicone / Trimethylsiloxysilicate treatment as the surface treatment Covasil 4.05 marketed by LCW;

[0351] - a Magnesium Myristate treatment such as MM surface treatment marketed by LCW;

[0352] - an Aluminium Dimyristate treatment such as the MI surface treatment marketed by Miyoshi;

[0353] - a Perfluoropolymethylisopropyl ether treatment as a surface treatment FHC marketed by LCW;

[0354] - an Isostearyl Sebacate treatment such as the commercially available HS surface treatment by Miyoshi;

[0355] - a Perfluoroalkyl Phosphate treatment as a PF surface treatment marketed by Daito;

[0356] - an acrylate / dimethicone copolymer and perfluoalkyl phosphate treatment such as the FSA surface treatment marketed by Daito;

[0357] - a Polymethylhydrogen siloxane / Perfluoroalkyl Phosphate treatment such as the FS01 surface treatment marketed by Daito;

[0358] - an Acrylate / Dimethicone Copolymer treatment as the surface treatment ASC marketed by Daito;

[0359] - an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito;

[0360] - an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito;

[0361] - a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito.

[0362] According to a particular embodiment of the invention, the dispersing agent is present with organic or inorganic pigments in submicron-sized particulate form in composition B.

[0363] 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.

[0364] According to one embodiment, the dispersing agent and the pigment(s) are present in quantity (dispersing agent: pigment), according to a weight ratio, 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.

[0365] The dispersing agent(s) may therefore have a silicone skeleton, such as silicone polyether and amino-silicone dispersants. Suitable dispersing agents include:

[0366] - amino-silicones i.e. silicones comprising one or more amino groups such than those marketed under the names and references: BYK LPX 21879, by BYK, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, marketed by Genesee les polymers,

[0367] - silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik,

[0368] - polydimethylsiloxane (PDMS) silicones 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.

[0369] According to a particular embodiment, the dispersing agent(s) are of the amino-silicone type and are cationic.

[0370] Preferably, the pigment(s) is / are chosen from mineral, mixed mineral-organic or organic pigments.

[0371] In one embodiment of the invention, the pigment(s) are organic pigments, preferably organic pigments surface-treated with an organic agent selected from silicone compounds. In another embodiment of the invention, the pigment(s) are mineral pigments.

[0372] Preferably, the pigment(s) according to the invention are selected from iron oxides, in particular red, brown, or black, pearlescent pigments, in particular titanium-coated mica or bismuth oxychloride mica, titanium-coated mica with iron oxides, iron oxide-coated mica, and titanium-coated mica. An example of an iron oxide is the iron oxide sold by Sun Chemical under the name SunPuro® Red Iron Oxide.

[0373] Preferably, the pigment(s) according to the invention are chosen from among the mother-of-pearls.

[0374] According to a particular embodiment, the composition may further comprise a pigment different from a pigment having a D90 particle size less than or equal to 50 pm.

[0375] The pigment(s) according to the invention may be present in a total quantity ranging from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, better from 0.5 to 10% by weight relative to the total weight of composition C. Non-carboxylic anionic thickening agent

[0376] Composition C may further comprise at least one non-carboxylic anionic thickening agent.

[0377] For the purposes of the present invention, "non-carboxylic agent" means an agent that does not include a carboxylic acid (-COOH) or carboxylate (-COO) function.

[0378] For the purposes of this invention, a thickening agent is defined as 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 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 similar).

[0379] Preferably, the non-carboxylic anionic thickening agent(s) are chosen from non-carboxylic anionic polymers, more preferably from anionic polymers with sulfonic group(s).

[0380] For the purposes of this invention, anionic polymer means a polymer comprising one or more anionic or anionizable groups and not comprising any cationic or cationizable group.

[0381] Advantageously, the non-carboxylic anionic thickening agent(s) are chosen from anionic polymers comprising at least one monomer with ethylenic unsaturation and a sulfonic group, in free form or partially or totally neutralized.

[0382] These polymers can be crosslinked or non-crosslinked. They are preferably crosslinked.

[0383] These polymers may be associative or non-associative, preferably non-associative.

[0384] It is recalled that "associative polymers" are polymers capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

[0385] Their chemical structure includes more particularly at least one hydrophilic zone and at least one hydrophobic zone.

[0386] By "hydrophobic group" is meant a hydrocarbon chain radical or polymer, saturated or unsaturated, linear or branched, comprising at least 8 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms and more preferably 18 to 30 carbon atoms.

[0387] Preferably, the hydrocarbon group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, or decyl alcohol. It may also refer to a hydrocarbon polymer such as polybutadiene.

[0388] Monomers with ethylenic unsaturation and a sulfonic group are selected in particular from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci-C22)alkylsulfonic acids, N-(Cr C22)alkyl(meth)acrylamido-(Ci-C22)alkylsulfonic acids such as undecyl-acrylamido-methane-sulfonic acid and their partially or totally neutralized forms.

[0389] More preferably, alkylsulfonic (meth)acrylamido(C1-C22) acids will be used, such as, for example, acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulfonic acid, 2- acrylamido-2,6-dimethyl-3-heptane-sulfonic acid and their partially or totally neutralized forms.

[0390] In particular, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or totally neutralized forms will be used.

[0391] 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 in particular mention may be made of the product described in Example 1 of document EP 503 853 and reference may be made to this document for information relating to these polymers.

[0392] We can also mention 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: hydroxyethylacrylate / sodium acryloyldimethyl taurate copolymer).

[0393] Associative AMPS polymers may, in particular, be selected from statistically 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 hydrophilic ethylenically unsaturated monomers selected, for example, from derivatives of (meth)acrylic acids, such as their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, or mixtures of these compounds.

[0394] Preferred polymers of this family are chosen from among associative copolymers of AMPS and at least one hydrophobic monomer with ethylenic unsaturation.

[0395] These same copolymers may further contain one or more ethylenically unsaturated monomers without a fatty chain such as (meth)acrylic acid derivatives, in particular their esters obtained with monoalcohols or mono- or poly-alkylene glycols, (meth)acrylamides, vinylpyrrolidone, or mixtures of these compounds.

[0396] These copolymers are described in particular in patent application EP-A-750899, US patent 5089578 and in the following publications by Yotaro Morishima:

[0397] - “Self-assembly amphiphilic polyelectrolytes and their nanostructures - Chinese Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336. » ;

[0398] - “Miscelle formation of random copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, Vol. 33, No. 10 (2000), 3694-3704”;

[0399] - “Solution properties of miscelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte: known effects on rheological behavior - Langmuir, Vol. 16, No. 12, (2000) 5324-5332”;

[0400] - “Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and associative macromonomers - Polym. Preprint, Div. Polym. Chem., 40(2), (1999), 220-221”.

[0401] Among these polymers, we can mention:

[0402] - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS motifs and from 40 to 85% by weight of (C8-Ci6)alkyl(meth)acrylamide or (C8-Ci6)alkyl(meth)acrylate motifs relative to the polymer, such as those described in application EP-A750 899;

[0403] - terpolymers comprising 10 to 90 mol% of acrylamide motifs, of 0.1 to 10 mole percent of AMPS motifs and 5 to 80 mole percent of n-(C6-Ci8)alkylacrylamide motifs, such as those described in US patent 5089578.

[0404] We can also mention copolymers of totally neutralized AMPS and dodecyl methacrylate as well as copolymers of uncrosslinked and crosslinked AMPS and n-dodecylmethacrylamide, such as those described in the articles by Morishima cited above.

[0405] Preferably, the non-carboxylic anionic thickening agent(s) are selected from the sodium 2-acrylamido-2-methylpropane-sulfonate / hydroxyethylacrylate copolymer, marketed by SEPPIC (INCI name: hydroxyethylacrylate / sodium acryloyldimethyl taurate copolymer).

[0406] Advantageously, the total amount of the non-carboxylic anionic thickening agent(s) ranges from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight, better from 0.1 to 5% by weight, and better still from 0.1 to 3% by weight, relative to the total weight of composition C. Associative polymers

[0407] Composition C according to the invention may further comprise at least one associative polymer different from the compound having at least one carboxylic acid group and different from the non-carboxylic anionic thickening agent as defined above.

[0408] It is recalled that "associative polymers" are polymers capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

[0409] Their chemical structure includes more particularly at least one hydrophilic zone and at least one hydrophobic zone.

[0410] By "hydrophobic group" is meant a hydrocarbon chain radical or polymer, saturated or unsaturated, linear or branched, comprising at least 10 atoms of carbon, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms and more preferably 18 to 30 carbon atoms.

[0411] Preferably, the hydrocarbon group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, or decyl alcohol. It may also refer to a hydrocarbon polymer such as polybutadiene.

[0412] Associative polymers can be of non-ionic, anionic, cationic or amphoteric nature.

[0413] Preferably, the associative polymer(s) are chosen from anionic associative polymers.

[0414] Among the anionic-type associative polymers, we can mention:

[0415] - (a) those comprising at least one hydrophilic motif, and at least one ether motif of fatty chain allyl, more particularly those whose hydrophilic motif is made up of an unsaturated ethylenic anionic monomer, more particularly still of a vinylic carboxylic acid and especially of an acrylic acid or a methacrylic acid or mixtures thereof.

[0416] Among these anionic associative polymers, polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, 5 to 60% by weight of lower alkyl (meth)acrylates, 2 to 50% by weight of fatty chain allyl ether, and 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylene monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

[0417] Among these, crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 OE) stearyl alcohol ether (Steareth 10) are particularly preferred, especially those sold by CIBA under the names SALCARE SC80® and SALCARE SC90®, which are aqueous emulsions of 30% of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40 / 50 / 10).

[0418] - (b) those comprising i) at least one hydrophilic motif of the carboxylic acid type unsaturated olefinic, and ii) at least one hydrophobic motif of the alkyl (C10-C30) ester type of unsaturated carboxylic acid.

[0419] Alkyl esters (Ci0-C30) of unsaturated carboxylic acids useful to the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

[0420] Anionic polymers of this type are described and prepared, for example, according to US patents 3,915,921 and 4,509,949.

[0421] Among this type of anionic associative polymers, more particularly those consisting of 95 to 60% by weight of acrylic acid (hydrophilic motif), 4 to 40% by weight of C10-C30 alkyl acrylate (hydrophobic motif), and 0 to 6% by weight of polymerizable crosslinking monomer will be used, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic motif), 1 to 4% by weight of C10-C30 alkyl acrylate (hydrophobic motif), and 0.1 to 0.6% by weight of polymerizable crosslinking monomer such as those described above.

[0422] Among the aforementioned polymers, the products sold by GOODRICH under the trade names PEMULEN TRI®, PEMULEN TR2®, CARBOPOL 1382®, and even more preferably PEMULEN TRI®, and the product sold by SEPPIC under the name COATEX SX®, are particularly preferred according to the present invention.

[0423] We can also mention the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer marketed under the name Acrylidone LM by the ISP Company.

[0424] - (c) maleic anhydride / α-olefin terpolymers in C30-C38 / alkyl maleate such as the product (maleic anhydride / C30-C38 α-olefin / isopropyl maleate copolymer) sold under the name PERFORMA V 1608® by the company NEWPHASE TECHNOLOGIES.

[0425] - (d) acrylic terpolymers comprising:

[0426] i) about 20 to 70% by weight of an unsaturated α,[3-monoethylenic [α],

[0427] ii) about 20 to 80% by weight of a non-surfactant α,[3-monoethylenic] unsaturation monomer other than [α],

[0428] iii) approximately 0.5 to 60% by weight of a non-ionic monourethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate,

[0429] such as those described in patent application EP-A-0173109 and more particularly that described in Example 3, namely, a methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate terpolymer of ethoxylated behenyl alcohol (40 OE) in 25% aqueous dispersion.

[0430] - (e) copolymers comprising among their monomers a carboxylic acid unsaturation α,[3-monoethylenic and an ester of carboxylic acid with unsaturation α,[3-monoethylenic and an oxyalkylated fatty alcohol.

[0431] Preferably these compounds also comprise as a monomer an ester of α,[3-monoethylenic carboxylic acid and Ci-C4 alcohol.

[0432] As an example of this type of compound, we can cite ACULYN 22® sold by ROHM and HAAS, which is a methacrylic acid / ethyl acrylate / oxyalkylened stearyl methacrylate terpolymer, as well as ACULYN 88 also sold by ROHM and HAAS.

[0433] Advantageously, the associative polymer(s), different from compounds having at least one carboxylic acid group and different from the non-carboxylic anionic thickening agents previously described, are chosen from acrylic associative polymers, more preferably carboxylic acrylic associative polymers.

[0434] In a particularly preferred manner, the associative polymer(s), different from compounds having at least one carboxylic acid group and different from the previously described non-carboxylic anionic thickening agents, are chosen from copolymers comprising among their monomers an α,[3-monoethylenic unsaturation carboxylic acid and an ester of an α,[3-monoethylenic unsaturation carboxylic acid and an oxyalkylated fatty alcohol.

[0435] Advantageously, the total quantity of the associative polymer(s) different from the compound(s) having at least one carboxylic acid group 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. Organic solvents

[0436] Composition C according to the invention may comprise one or more organic solvents.

[0437] Examples of organic solvents include lower C1-C4 alkanols such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, chlorphenesin, 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 or hydroxyacetophenone, and mixtures thereof.

[0438] Organic solvents may be present in a total quantity of between 0.01 and 60% by weight, preferably between 0.05 and 50% by weight and more preferably inclusively between 0.1 and 45% by weight relative to the total weight of composition C.

[0439] Composition C used in the process according to the invention may be aqueous. The water content may range from 1 to 80% by weight, preferably from 10 to 75%. in weight, more preferably from 20 to 70% by weight relative to the total weight of composition C. Additives

[0440] Composition C used in the process according to the invention may contain any adjuvant or additive usually used.

[0441] Among the additives that may be contained in the composition, we can mention reducing agents, softeners, antifoaming agents, moisturizing agents, UV filters, peptizers, perfumes, anionic, cationic, non-ionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers previously described, preservatives, silicones, oils, waxes other than silicones in wax form, and mixtures thereof.

[0442] The composition C used in the process according to the invention may be in particular in the form of a suspension, dispersion, gel, emulsion, in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion, or multiple (W / O / O or polyol / O / O or O / W / O), in the form of a cream, foam, stick, dispersion of vesicles in particular of ionic or non-ionic lipids, bi-phase or multi-phase lotion.

[0443] A person skilled in the art will be able to choose the appropriate pharmaceutical form, as well as its method of preparation, on the basis of their 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. Protocol

[0444] Composition C described above can be used on dry or wet hair, as well as on all types of hair, light or dark, natural or colored, permed, bleached or straightened.

[0445] According to a particular embodiment of the invention, the hair is washed before application of composition C.

[0446] Preferably, a washing, rinsing, wringing or drying step is carried out after the application of composition C to the hair.

[0447] More preferably, a drying step is implemented after the application of composition C to the hair.

[0448] Application to the hair can be carried out by any conventional means, in particular by means of a comb, a brush, a sponge or the fingers.

[0449] The application of composition C to the hair is generally carried out at room temperature (between 15 and 25 °C).

[0450] After applying composition C to the hair, one can wait between 1 minute and 6 hours, in particular between 1 minute and 2 hours, more particularly between 1 minute and 1 hour, more preferably between 1 minute and 30 minutes, before for example a washing, rinsing, spinning and / or drying step.

[0451] After application of composition C, the hair may be left to dry or dried, for example at a temperature of 30 °C or higher.

[0452] The process according to the invention can thus include a step of applying heat to the hair using a heating tool.

[0453] The heat application step of the process of the invention can be carried out using a helmet, a hair dryer, a straightener or curling iron, a climazon...

[0454] Preferably, the heat application step of the process of the invention is carried out using a hair dryer.

[0455] When the process of the invention implements a step of applying heat to the hair, the step of applying heat to the hair takes place after the application of composition C to the hair.

[0456] During the heat application step on the hair, a mechanical action on the strands can be exerted such as combing, brushing, passing with fingers.

[0457] 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.

[0458] When the step of applying heat to the hair is carried out using a straightening iron, the temperature is preferably between 110 and 220°C, preferably between 140 and 200°C.

[0459] In a particular embodiment, the process of the invention implements a step (c1) of applying heat using a helmet, a hair dryer or a climazon, preferably a hair dryer and a step (c2) of applying heat using a straightening or curling iron, preferably a straightening iron.

[0460] Step (cl) can be carried out before step (c2).

[0461] During step (cl), also called the drying step, the hair can be dried, for example, at a temperature of 30°C or higher. In one particular embodiment, this temperature is higher than 40°C. In another particular embodiment, this temperature is higher than 45°C and lower than 110°C.

[0462] Preferably, if the hair is dried, it is dried not only with heat but also with an airflow. This airflow during drying helps to improve the individualization of the coating.

[0463] During drying, mechanical action on the strands can be exerted such as combing, brushing, passing with fingers.

[0464] During step (c2), the passage of the straightening or curling iron, preferably the straightening iron, may be carried out at a temperature ranging from 110 to 220°C, preferably between 140 and 200°C.

[0465] After the heating step, a shaping step can be implemented with, for example, a straightening iron; the temperature for the shaping step can be between 110 and 220°C, preferably between 140 and 200°C.

[0466] Preferably, the invention is a hair coloring process comprising the following steps: (i) the application to the hair of at least one composition C comprising:

[0467] - at least one (poly)carbodiimide compound;

[0468] - at least one compound having at least one carboxylic acid group; and

[0469] - at least one pigment having a D90 particle size less than or equal to 50 qm; Then ii) optionally, a processing time of said composition C on the hair of 1 to 30 minutes, preferably 1 to 20 minutes; then iii) optionally a step of washing, rinsing, wringing and / or drying said hair.

[0470] Preferably, composition C further comprises at least one non-carboxylic anionic thickening agent as described above.

[0471] Preferably, composition C further comprises at least one associative polymer as described above, different from the compound having at least one carboxylic acid group and different from the non-carboxylic anionic thickening agent as defined above.

[0472] Advantageously, the step of applying composition C to the hair is repeated several times.

[0473] According to a preferred embodiment, the coloring process according to the invention is a hair coloring process consisting of mixing at least two compositions A and B extemporaneously at the time of use to obtain a composition C and applying composition C to the hair, with: - composition A comprising at least one (poly)carbodiimide compound as described above; - composition B comprising at least one compound having at least one carboxylic acid group as described above,

[0474] composition A and / or composition B comprising at least one pigment having a D90 particle size less than or equal to 50 sqm. Composition A and / or composition B may optionally include at least one non-carboxylic anionic thickening agent as described above and / or at least one associative polymer as described above, different from the compound having at least one carboxylic acid group and different from the non-carboxylic anionic thickening agent as defined above.

[0475] Preferably, composition B comprises at least one pigment having a D90 particle size less than or equal to 50 pm.

[0476] Preferably, composition A does not include at least one pigment having a D90 particle size less than or equal to 50 pm.

[0477] According to a particularly preferred embodiment, composition B comprises at least one pigment, more preferably a nacre, having a D90 particle size less than or equal to 50 pm.

[0478] According to another particularly preferred embodiment, composition A does not comprise at least one pigment, more preferably a nacre, having a D90 particle size less than or equal to 50 pm.

[0479] According to this embodiment, compositions A and B are mixed preferably less than 15 minutes before application to the hair, more preferably less than 10 minutes before application, better less than 5 minutes before application.

[0480] The weight ratio between composition A and composition B is preferably from 0.1 to 10, preferably from 0.2 to 5, better 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.

[0481] According to a particular embodiment, the hair coloring process according to the invention is a hair coloring process consisting of extemporaneously mixing at least two compositions A and B at the time of use to obtain a composition C, and applying composition C to the hair, with: - composition A comprising at least one (poly)carbodiimide compound as described above; and - composition B comprising at least one compound having at least one carboxylic acid group as described above, and at least one pigment having a D90 particle size less than or equal to 50 qm; Composition A and / or composition B optionally comprising at least one non-carboxylic anionic thickening agent as described above and / or at least one associative polymer as described above, different from the compound having at least one carboxylic acid group and different from the non-carboxylic anionic thickening agent as defined above.

[0482] Advantageously, composition A and / or composition B comprises (include) at least one non-carboxylic anionic thickening agent as previously described, and at least one associative polymer as described above, different from the compound having at least one carboxylic acid group and different from the non-carboxylic anionic thickening agent as previously defined.

[0483] The total amount of the (poly)carbodiimide compound(s) preferably ranges from 0.01 to 40% by weight, more preferably from 0.1 to 30% by weight, better from 0.5 to 20% by weight. weight, even more preferably from 1 to 12% by weight relative to the total weight of composition A.

[0484] The total quantity of the compound or compounds having at least one carboxylic acid group is preferably from 0.2 to 60% by weight, more preferably from 1 to 40% by weight, better still from 1 to 30% by weight, and even more preferably from 2 to 20% by weight relative to the total weight of composition B.

[0485] The total quantity of the aqueous dispersion(s) of polymer particle(s) selected from polyurethanes, acrylic polymers, and their mixtures is preferably from 0.2 to 60% by weight, more preferably from 1 to 50% by weight, better still from 2 to 40% by weight, and even more preferably from 5 to 35% by weight relative to the total weight of composition B.

[0486] According to a particular embodiment, the total quantity of the aqueous dispersion(s) of acrylic polymer particle(s) preferably ranges from 0.2 to 60% by weight, more preferably from 1 to 50% by weight, better still from 1 to 40% by weight, and even more preferably from 5 to 35% by weight relative to the total weight of composition B. Multi-compartment device (kit)

[0487] The present invention also relates to a hair coloring device comprising several compartments containing: - in a first compartment, a composition A comprising: a) at least one (poly)carbodiimide compound as described above,

[0488] - in a second compartment, a composition B comprising: b) at least one compound having at least one carboxylic acid group as described above,

[0489] Composition A and / or Composition B comprising: c) at least one pigment having a D90 particle size less than or equal to 50 µm as described above.

[0490] The present invention will now be described more specifically by means of examples, which are in no way limiting of the scope of the invention. However, the examples allow for the support of specific features, variants, and preferred embodiments of the invention. EXAMPLES

[0491] The (poly)carbodihnide(s) of the invention are accessible by synthetic methods known to those skilled in the art, from commercial products or from reagents synthesizable according to chemical reactions also known to those skilled in the art. For example, see Sciences of Synthesis - Houben - Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D-70469 Stuttgart, or US patent US 4,284,730 or Canadian application CA 2 509 861.

[0492] More particularly, the process for preparing the (poly)carbodiimides of the invention uses in a first step a diisocyanate reagent (1): O=C=N-LrN=C=O (1), formula (1) in which Li is as defined previously which reacts in the presence of a carboimidation catalyst (2) such as those described in US 4,284,730 in particular phosphorus catalysts particularly chosen from among 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 ambient temperature and solvent reflux, preferably around 140 °C; to lead to the compound carbodihnide diisocyanate (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 halogens such as benzoyl chloride can be added to deactivate the catalyst.

[0493] To obtain "symmetrical" (poly)carbodiimides, in the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq) of nucleophilic reagent Ri-XrH, then with 0.5 eq of HEH reagent with Rb Xi and E as defined above, to give 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 Rh Xb Lb n, and E are as defined above. According to an embodiment for obtaining compound (4) from (3), it is possible to first add 0.5 eq of HEH reagent, then 1 eq of Ri-XrH reagent.

[0494] To obtain "dissymmetric" (poly)carbodiimides, in the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq) of nucleophilic reagent RrXi-H and then 1 eq. of HEH reagent with Rb Xi and E as defined above, to give the compound (5): R1-X1-C(O)-NH-L1-(N=C=N-L1)n-NH-C(O)-EH (5), formula (5) in which Rh Xb Lb n, and E are as defined above.

[0495] According to one variant for obtaining compound (5) from (3) it is possible to add first 1 eq. of reagent Ri-XrH, then 0.5 eq. of reagent HEH.

[0496] 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'),

[0497] 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 give rise to the asymmetric compound (7): RrX1-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),

[0498] Formula (7) in which Rb Xb Lb R2, X2, n, z and E are as defined previously.

[0499] 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 give the compound (8): H-[EC(O)-NH-L1-(N=C=N-L1)z]w-NH-C(O)-X2-R2(8),

[0500] formula (8) in which Lb R2, X2, z and E are as defined previously, and w is an integer from 1 to 3, more preferably w = 1.

[0501] This latter 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') being able to be synthesized by reaction of 0.5 eq. of nucleophilic reagent Ri-XrH with 1 equivalent of compound (3)), to give rise to the (poly)carbodihnide 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 above.

[0502] (Poly)carbodiimide compounds, as well as all reaction intermediates and reactants, 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.

[0503] Example 1: Process for the synthesis of the (poly)carbodiimide compound

[0504] 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 under stirring.

[0505] The reaction medium was heated to 140°C under nitrogen for 4 hours, following the reaction by infrared spectroscopy through the absorption of isocyanate functions between 2200 and 2300 cm1, then cooled to 120°C.

[0506] 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 while stirring. The temperature of 120°C is maintained until the complete disappearance of the isocyanate groups, monitored by infrared spectroscopy at 2200-2300 cm1, and then cooled to room temperature.

[0507] After cooling to room temperature, the reaction mixture is poured dropwise under vigorous stirring into a 500 mL glass beaker containing 85 g of distilled water to produce the desired product in the form of a translucent yellow liquid. Example 2

[0508] Compositions A, B1 and B2 as described below were prepared: quantities are expressed in g of raw material as is / 100g, unless otherwise stated.

[0509] [Tables 1] Compositions A Polycarbonate 1 17.5 Hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer (2) 3 Ethanol 20 Water q.s. 100

[0510] (1) synthesized according to the synthesis process described in Example 1 (at 40% of material active in water), (2) sold by the company SEPPIC under the name SEPINOV EMT10 (with 90% active material).

[0511] [Tables2] Compositions B1 B2 Acrylates copolymer (3) 29.2 29.2 Acrylates / Steareth-20 methacrylate copolymer (4) 2.2 2.2 Mica and red iron oxide (5) 12 - Mica and red iron oxide (6) - 12 Amodimethicone 8.8 8.8 Dimethicone 10.2 10.2 Preservative(s) qs qs Water qsp 100 qsp 100

[0512] (3) sold by the company DAITO KASEI KOGYO under the trade name DAITOSOL 3000SLPN-PE1 (aqueous dispersion with 30% active ingredient),

[0513] (4) sold by the company ROHM and HAAS under the trade name ACULYN 22® (methacrylic acid / ethyl acrylate / oxyalkylated stearyl methacrylate terpolymer with 30% active ingredient),

[0514] (5) Mica and red iron oxide in the form of particles having a D90 particle size of 17.05 µm,

[0515] (6) Mica and red iron oxide in the form of particles having a particle size D90 of 85.90 µm.

[0516] Two mixtures are then carried out. Composition A was mixed with each of compositions B1 and B2 at a mass ratio of 50 / 50 to obtain two compositions Cl and C2.

[0517] Thus, the process using composition Cl is a process according to the invention. The process using composition C2 is a comparative process. Protocol

[0518] Each of the compositions Cl and C2 is applied to strands of natural HT 4 (tone height 4) hair, at a rate of 0.8g of composition per gram of strand. The hair strands are then blow-dried while being combed.

[0519] The hair strands are then stored at ambient temperature and humidity for 24 hours.

[0520] The properties in terms of detangling and smooth feel were then evaluated. Detangling evaluation

[0521] Detangling was carried out on the colored strands as previously prepared, without prior detangling.

[0522] It is assessed using a fine-toothed comb, in a single movement: the comb slides through the strand and when it gets stuck, the detangled length is measured.

[0523] This evaluation is carried out on a single strand per composition.

[0524] The results are summarized in Table 3 below.

[0525] [Tables3] Process using composition Cl (invention) C2 (comparative) Length of untangled strand (cm) 20.5 19

[0526] It is clear that the strands of hair treated with the process according to the invention have a greater strand length than the strands of hair treated with a comparative process.

[0527] Thus, the coloured coating obtained with the process according to the invention exhibits improved detangling. Evaluation of smooth touch

[0528] The performance in terms of smooth touch on previously prepared colored hair strands was evaluated by 5 experts. The performance was evaluated in a blind test during which each of the 5 experts assigned a score in the range from 0 (very poor level of smoothness) to 5 (very good level of smoothness) for each strand of hair.

[0529] To assess the property of smoothness to the touch, the expert grasps the strand of hair between the thumb and forefinger and slides the fingers along the strand from the top to the tips. The expert assesses whether the hair has any roughness or catches on the fingers.

[0530] The results are summarized in Table 4 below.

[0531] [Tables4] Process implementing composition Cl (invention) C2 (comparative) Expert 1 4 2.5 Expert 2 4 2.5 Expert 3 3.5 1.5 Expert 4 4 3 Expert 5 4 2.5 Mean 3.9 2.4 Standard deviation 0.22 0.55

[0532] It is clear that the strands of hair treated with the process according to the invention have a significantly smoother feel than the strands of hair treated with a comparative process.

[0533] Thus, the coloured coating obtained with the process according to the invention has an improved smooth feel.

Claims

Demands

1. Hair coloring process comprising the application to the hair of at least one composition C comprising: - at least one (poly)carbodiimide compound; - at least one compound having at least one carboxylic acid group; and - at least one pigment having a D90 particle size less than or equal to 50 µm.

2. A process according to claim 1, characterized in that the (poly)carbodihnide compound(s) is / are selected from the compounds of the following formula (I): O 0 J r 1 1 Ri—Xy' '14—A——A4—Nx '-X?— HL 3, H (I) in which: - Xi and X2 represent, independently, an oxygen atom O, a sulfur atom S or an NH group; - Ri and R2 independently represent a group chosen from a hydrocarbon radical, preferably alkyl, possibly interrupted by one or more heteroatom(s), a group chosen from the following groups: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylmylalkylsilyl, (meth)acrylalkyl, crotonylalkyl,alkyl epoxide such as propyl epoxide or butyl epoxide, and azacyclopropane, and a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatoms and by one or more groups selected from the following groups: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl,

3. sulfonylkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide, and azacyclopropane; - n denotes an integer ranging from 1 to 1000; and - A is a monomer chosen from the compounds below: A process according to claim 1, characterized in that the (poly)carbodiimide compound(s) is / are chosen from the compounds of the following formula (II): (II), in which - Xi and X2 independently represent an oxygen atom O, a sulfur atom S, or an NH group; - Ri and R2 independently represent a hydrocarbon radical possibly interrupted by one or more heteroatoms; - n and z denote an integer from 1 to 20, with n+z > 2, and w denotes an integer from 1 to 3; - Li independently represents a divalent aliphatic hydrocarbon radical in Ci-Ci8, a cycloalkylene radical in C3-Ci5, a heterocycloalkylene group in C3-Ci2, or an arylene group in C6-Ci4, and mixtures thereof; - E independently represents a group chosen from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-, in which R3 and R4 independently represent a divalent hydrocarbon radical possibly interrupted by one or more heteroatoms; - R5 independently represents a covalent bond or a divalent saturated hydrocarbon radical, possibly interrupted by one or more heteroatom(s);- R6 independently represents a hydrogen atom, or a hydrocarbon radical possibly interrupted by one or more heteroatom(s).

4. A process according to claim 3, characterized in that the (poly)carbodiimide compound(s) is / are selected from compounds of formula (II) in which: - Xi and X2 independently represent an oxygen atom; - Ri and R2 are selected independently from dialkylaminoalcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, and mixtures thereof; - n and z denote an integer from 1 to 20, with n+z > 2 and w equals 1; - L1 is selected from a divalent aliphatic hydrocarbon radical in C1-C18, a cycloalkylene radical in C3-Ci5, a heterocycloalkylene group in C3-Ci2, or an arylene group in C6-Ci4, and mixtures thereof; - E independently represents a grouping chosen from: - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are chosen independently from a C6-Ci4 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly interrupted by one or more heteroatoms, and mixtures thereof; - when R5 is not a covalent bond, R5 is chosen from a C6-Ci4 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly interrupted by one or more heteroatoms, and mixtures thereof; and - R6 is chosen from a C6-Ci4 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Ci8 alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof.

5. A process according to claim 3 or 4, characterized in that the (poly)carbodihnide compound(s) is / are selected from compounds of formula (II) in which: - Xi and X2 independently represent an oxygen atom; - Ri and R2 are independently monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed; - n and z denote an integer 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 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-Ci4 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly 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-C12 cycloalkylene radical, a linear or branched Ci-Ci8 alkylene radical, possibly interrupted by one or more heteroatoms, and mixtures thereof; and - R6 is chosen from a C6-Ci4 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Ci8 alkylene radical, possibly interrupted by one or more heteroatoms, and mixtures thereof.

6. A process according to any one of claims 3 to 5, characterized in that the (poly)carbodiimide compound(s) is / are selected from the compounds of formula (II) in which: - Xi and X2 independently represent an oxygen atom; - Ri and R2 independently represent the compound of the following formula (VI): R13-[O-CH2-C(H)(R14)]q- (VI), in which Rn represents a Ci-C4 alkyl group or a phenyl group, preferably a CrC4 alkyl group, more preferably a methyl group, R14 represents a hydrogen atom or a Ci-C4 alkyl group, preferably a hydrogen atom, and q denotes an integer from 4 to 30; - n and z denote an integer from 2 to 20, with n+z ranging from 4 to 10 and w is equal to 1;- Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, and - E represents an -O-R3-O- group in which R3 is selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched CrCi8 alkylene radical, possibly interrupted by one or more heteroatom(s), and mixtures thereof.;

7. A process according to any one of claims 3 to 6, characterized in that the (poly)carbodiimide compound(s) is / are selected from the compounds of formula (II) in which: - Xi and X2 independently represent an oxygen atom; - Ri and R2 independently represent the compound of the following formula (VI): R13-[O-CH2-C(H)(R14)]q- (VI), in which R13 represents a CrC4 alkyl group or a phenyl group, preferably a CrC4 alkyl group, more preferably a methyl group, R[4] represents a hydrogen atom or a CrC4 alkyl group, preferably a hydrogen atom, and q denotes an integer from 4 to 30; - n and z denote an integer from 2 to 20, with n+z ranging from 4 to 10, and w is equal to 1; - Li is a C3-Ci5 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and

8. - E represents a group- -O-R3-O- in which R3 represents a linear or Ci-Ci8 branched alkylene radical such as methylene, propylene, butylene, ethylene, possibly interrupted by one or more heteroatom(s). A process according to any one of claims 3 to 7, characterized in that the (poly)carbodiimide compound(s) is / are chosen from the compounds of the following formula (XII):

9.

10. (XII), in which Li is 4,4-dicyclohexylene methane, n and z denote an integer from 2 to 20, with n+z ranging from 4 to 10, E represents a -O-R3-O- group in which R3 represents a linear or Ci-Ci8 branched alkylene radical such as methylene, propylene, butylene ethylene, possibly interrupted by one or more heteroatom(s), and r and s denote an integer from 4 to 30. A process according to any one of the preceding claims, characterized in that the total quantity of the (poly)carbodiimide compound(s) ranges from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, even more preferably from 0.5 to 8% by weight, better from 1 to 6% by weight relative to the total weight of composition C. A process according to any one of the preceding claims, characterized in that the compound(s) having at least one carboxylic acid groups are chosen from silicone compounds comprising at least one carboxylic group, polyurethanes, acrylic polymers and their mixtures, preferably from polyurethanes, acrylic polymers and their mixtures.

11. A process according to any one of the preceding claims, characterized in that the compound(s) having at least one carboxylic acid group are in the form of aqueous dispersions of polymer particle(s) selected from polyurethanes, acrylic polymers and their mixtures, preferably in the form of aqueous dispersions of acrylic polymer particles, more preferably in the form of aqueous dispersions of film-forming acrylic polymer particles.

12. A process according to the preceding claim, characterized in that the acrylic polymer(s) comprise one or more units derived from the following monomers: a) (meth)acrylic acid; and b) alkyl (meth)acrylate in C1 to C30, more preferably in C1 to C20, even more preferably in C1 to C10, and even more particularly in C1 to C10

13. ^4- A process according to any one of claims 1 to 10, characterized in that the total quantity of the compound(s) having at least one carboxylic acid group ranges from 0.1 to 30% by weight, more preferably from 0.5 to 20% by weight, better still from 0.5 to 15% by weight, and even more preferably from 1 to 10% by weight relative to the total weight of composition C.

14. A process according to claim 11 or 12, characterized in that the total quantity of the aqueous dispersion(s) of polymer particle(s) selected from polyurethanes, acrylic polymers, and their mixtures ranges from 0.1 to 50% by weight, more preferably from 0.5 to 40% by weight, even better from 0.5 to 30% by weight, and even more preferably from 1 to 20% by weight relative to the total weight of composition C.

15. A method according to any one of the preceding claims, characterized in that the pigment(s) have a D90 particle size less than or equal to 20 µm, preferably from 10 nm to 20 µm, plus preferentially from 50 nm to 20 µm, even more preferentially from 100 nm to 20 µm, better still from 1 µm to 20 µm.

16. A method according to any one of the preceding claims, characterized in that the pigment(s) are chosen from among the nacres.

17. A process according to any one of the preceding claims, characterized in that the total quantity of pigment(s) ranges from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, better from 0.5 to 10% by weight relative to the total weight of composition C.

18. A method according to any one of claims 1 to 16, characterized in that it consists of extemporaneously mixing at the time of use at least two compositions A and B to obtain a composition C and applying composition C to the hair, with: - composition A comprising at least one (poly)carbodiimide compound as defined in any one of claims 1 to 8; - composition B comprising at least one compound having at least one carboxylic acid group as defined in any one of claims 1 and 10 to 12, composition A and / or composition B comprising at least one pigment having a D90 particle size less than or equal to 50 pm as defined in any one of claims 1 and 15 to 16.

19. Hair coloring device comprising several compartments containing: - in a first compartment, a composition A comprising: a) at least one (poly)carbodiimide compound as defined in any one of claims 1 to 8, - in a second compartment, a composition B comprising: b) at least one compound having at least one carboxylic acid group as defined in any one of claims 1 and 10 to 12, composition A and / or composition B comprising: c) at least one pigment having a D90 particle size less than or equal to 50 pm as defined in any one of claims 1 and 15 to 16.