Method for removing color from pre-colored hair keratin fibers

Abstract

The present invention relates to a method for removing color from hair keratin fibers, comprising applying at least one color removing composition to hair keratin fibers that have been previously colored using at least one hair coloring composition, the at least one hair coloring composition comprising at least one (poly)carbodiimide compound; and at least one colorant selected from pigments, direct dyes and mixtures thereof; said color removing composition comprising at least one glycol ether; and optionally at least one alkyl or alkylene carbonate.

Description

[Technical Field]

[0001] The present invention relates to a method for removing color from hair keratin fibers, comprising applying at least one composition for color removal to hair keratin fibers that have been previously colored using at least one composition for coloring hair keratin fibers, the composition comprising a (poly)carbodiimide compound and at least one colorant selected from pigments, direct dyes and mixtures thereof, wherein the color removal composition comprises at least one glycol ether.

[0002] The present invention relates to a composition for removing color from hair keratin fibers that have been previously colored with a composition for coloring hair keratin fibers, the composition comprising at least one coloring agent selected from pigments, direct dyes and mixtures thereof, - at least 5% by weight, based on the total weight of the color removal composition, of at least one glycol ether; - at least one alkyl or alkylene carbonate; - optionally at least one polyol different from a glycol ether The present invention also relates to a composition comprising:

[0003] The present invention also relates to the use of the composition of the present invention or the composition used in connection with the method of the present invention for removing color from hair keratin fibers that have been previously colored with a composition for coloring hair keratin fibers, the composition comprising at least one coloring agent selected from pigments, direct dyes and mixtures thereof. [Background technology]

[0004] In the field of coloring keratinous fibers, in particular human keratinous fibers, it is already known practice to color the keratinous fibers by various techniques, using direct dyes or pigments to produce non-permanent coloring, or dye precursors to produce permanent coloring.

[0005] There are three basic methods for coloring hair: a) "Permanent" coloring: its action makes it possible to significantly modify the original color and uses oxidative dyes that penetrate the hair fiber and produce pigments through an oxidative condensation process. b) Non-permanent, semi-permanent or direct coloring: without using an oxidative condensation process and withstanding 4 or 5 shampoo washes; this involves coloring the hair keratin fibers with a hair coloring composition containing a direct dye. c) Temporary coloring: corrects the natural color of the hair, remains from one shampooing to the next, and serves to enhance or correct the shade already obtained. This can also be related to the "make-up" method.

[0006] For the latter type of coloration, it is known to use colored polymers obtained by grafting one or more dyes of azo, triphenylmethane, azine, indoamine or anthraquinone nature onto the polymer chain. Such colored polymers are not entirely satisfactory, especially with regard to the uniformity of the color imparted and its durability, not to mention the problems associated with their preparation, especially with regard to reproducibility.

[0007] Other coloring methods include the use of pigments. Specifically, the use of pigments on the surface of keratin fibers generally makes it possible to achieve noticeable coloring on dark-colored hair, since the surface pigments hide the original color of the fibers. This coloring method also makes it possible to have available dye compositions that have the advantage of producing a uniform color coating on keratin fibers, especially on hair, while at the same time making it possible to form a coat that can withstand various attacking factors that hair may be subjected to, such as shampooing, brushing, and / or rubbing, without deteriorating the hair.

[0008] However, there is no method for using an efficient color removal composition with this type of temporary hair coloring composition that is durable with respect to shampoo washout.

[0009] Therefore, there remains a need for a method for efficiently removing color from hair keratin fibers that have been previously colored using said hair coloring compositions that is persistent with respect to shampoo washing. Summary of the Invention [Problem to be solved by the invention]

[0010] It is therefore an object of the present invention to develop a method for efficiently removing color from hair keratin fibers. [Means for solving the problem]

[0011] This object is achieved by the present invention, one subject of which is a method for removing color from hair keratin fibers, such as pre-colored hair, comprising applying at least one color-removing composition to hair keratin fibers that have been pre-colored using at least one composition for coloring said hair keratin fibers, such as hair, wherein the at least one composition for coloring hair keratin fibers comprises: at least one (poly)carbodiimide compound; and at least one colorant selected from pigments, direct dyes and mixtures thereof; Includes; The color removal composition comprises: at least one glycol ether; and - optionally at least one alkyl or alkylene carbonate Includes.

[0012] The present invention relates to a composition for removing color from hair keratin fibers that have been previously colored with a composition for coloring hair keratin fibers, the composition comprising at least one coloring agent selected from pigments, direct dyes and mixtures thereof, - at least 5% by weight, based on the total weight of the color removal composition, of at least one glycol ether; - at least one alkyl or alkylene carbonate; - optionally at least one polyol different from a glycol ether The present invention also relates to a composition comprising:

[0013] The present invention also relates to the use of the color removal composition of the present invention or the color removal composition used in connection with the method of the present invention for removing color from hair keratin fibers that have been previously colored with a hair coloring composition comprising at least one colorant selected from pigments, direct dyes and mixtures thereof. DETAILED DESCRIPTION OF THE INVENTION

[0014] Other objects, features, aspects and advantages of the present invention will become more apparent from reading the following description and examples.

[0015] In the text below, unless otherwise specified, the limits of numerical ranges are encompassed by the ranges, in particular the expressions "to" and "range of... to...".

[0016] As used in this description, the phrase "at least one" is equivalent to the phrase "one or more."

[0017] The invention is not limited to the illustrated embodiments, and features of the various embodiments may in particular be combined in variations not illustrated.

[0018] For purposes of the present invention, unless otherwise specified: - "Alkyl" group refers to a linear or branched saturated group containing, for example, 1 to 20 carbon atoms; - an "aminoalkyl" group refers to an alkyl group as defined above, wherein said alkyl group contains an NH group; - a "hydroxyalkyl" group refers to an alkyl group as defined above, wherein said alkyl group contains an OH group; - "Alkylene" group denotes a linear or branched saturated C2-C4 hydrocarbon-based divalent group, such as methylene, ethylene or propylene; - "cycloalkyl" or "alicycloalkyl" group refers to a cyclic saturated monocyclic or bicyclic, preferably monocyclic hydrocarbon-based group containing 1 to 3 rings, preferably 2 rings, and containing 3 to 24 carbon atoms, in particular 3 to 20 carbon atoms, more particularly 3 to 13 carbon atoms, even more particularly 3 to 12 carbon atoms, preferably 5 to 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, wherein the cycloalkyl group can be substituted by one or more (C1-C4) alkyl groups, such as methyl; in that case it is understood that the cycloalkyl group is preferably an isobornyl group; - "Cycloalkylene" groups have the above-defined "cycloalkyl" and are preferably divalent C-C 12 refers to a cycloalkyl group; - "aryl" group is a monocyclic, bicyclic or tricyclic, fused or unfused, unsaturated aromatic hydrocarbon-based ring group containing 6 to 14 carbon atoms, preferably 6 to 12 carbon atoms; preferably, the aryl group contains one ring having 6 carbon atoms, such as phenyl, naphthyl, phenanthryl, where it is understood that the phenyl group may be substituted with one or more (C1-C4) alkyl groups, such as methyl, preferably tolyl, xylyl or methylnaphthyl; preferably, the aryl group represents phenyl; - an "arylene" group is a divalent aryl group with "aryl" as defined above; preferably, arylene represents phenylene; - "heterocyclic" group is a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based group containing one or more heteroatoms, preferably 1 to 5 atoms selected from O, S or N, and containing 3 to 20 ring members, preferably 5 to 10 ring members, such as imidazolyl, pyrrolyl and furanyl; - a "heterocycloalkylene" group is a divalent heterocyclic group having the above-defined "heterocyclic" group; - an "aryloxy" group refers to an aryloxy group with an "aryl" as defined above; - an "alkoxy" group refers to an alkyl-oxy group with "alkyl" as defined above; - an "acyloxy" group refers to an ester group RC(O)-O-, where R is an alkyl group as defined above; - A "reactive" group is a group that is capable of forming a covalent bond with another identical or different group by chemical reaction.

[0019] The term "hair keratinous fibers" means hair. In the remainder of this specification, the terms "keratinous fibers" and "hair keratinous fibers" have the same meaning.

[0020] The expression "composition for coloring hair keratin fibers" is equivalent to "hair coloring composition".

[0021] For the purposes of the present invention, the expression "hair" means hair on the head, and does not refer to eyelashes, eyebrows, or body hair.

[0022] The expression "bleaching composition" is equivalent to "composition for removing color from hair keratin fibers" and "composition for removing hair color from hair keratin fibers".

[0023] Polycarbodiimide Compounds As mentioned above, the composition for coloring hair keratinous fibers used in connection with the method according to the invention comprises at least one (poly)carbodiimide compound.

[0024] The composition may comprise at least two different (poly)carbodiimide compounds present as a mixture in the composition for coloring hair keratinous fibers.

[0025] The term "(poly)carbodiimide compound" means a compound comprising one or more carbodiimide groups, preferably at least two carbodiimide groups, more preferentially at least three carbodiimide groups; in particular, the number of carbodiimide groups does not exceed 200, preferably does not exceed 150, more preferentially does not exceed 100.

[0026] The term "carbodiimide group" refers to a divalent, linear, three-atom moiety of the general formula -(N=C=N)-.

[0027] The (poly)carbodiimide compound according to the present invention may optionally comprise in its structure one or more reactive groups different from the carbodiimide group selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, such as propylepoxide or butylepoxide, and azacyclopropane groups.

[0028] The reactive group other than the carbodiimide group may be a side group or a terminal group. Preferably, the (poly)carbodiimide compound comprises one or more terminal groups different from the carbodiimide group, preferably one or more terminal groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxides such as propylepoxide or butylepoxide, and azacyclopropane groups.

[0029] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (I): [ka] (In the formula, X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; R1 and R2 independently represent hydrocarbon-based groups optionally interrupted by one or more heteroatoms, preferably groups selected from alkyl, alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxides, such as propylepoxide or butylepoxide, and azacyclopropane groups, and represents a hydrocarbon-based group, preferably a group selected from alkyl, optionally interrupted by one or more heteroatoms and one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, such as propylepoxide or butylepoxide, and azacyclopropane groups; - n represents an integer ranging from 1 to 1000; and A is one of the following compounds: [ka] is a monomer selected from is selected from.

[0030] According to another embodiment, the (poly)carbodiimide compound has the following formula (Ia): [ka] (In the formula, X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; Y1 and Y2 are independently saturated C1 to C 36 Aliphatic group or C6~C 24 represents a divalent organic group selected from an aromatic or alkylaromatic group, wherein the aliphatic or aromatic group optionally contains one or more non-pendant heteroatoms such as nitrogen atoms, oxygen atoms, sulfur atoms, or combinations thereof; Z1 and Z2 independently represent a reactive end group or an inactive end group; As inert end groups, Z1 and Z2 are independently saturated, linear or branched chain or cyclic C1-C 50 Aliphatic group or C6~C 18 may represent an aromatic group, said aliphatic and aromatic groups optionally containing 1 to 10 heteroatoms selected from nitrogen, oxygen, sulfur and combinations thereof, and the aliphatic or aromatic groups may be partially or fully fluorinated; in this variation, Z1 and Z2 contain a linking group CG connecting Z1 to Y1 and Z2 to Y2, the group CG being optionally a single covalent bond, a saturated C-C bond, an unsaturated covalent C-C bond, an amide group, an ester group, a carbonate group, a thioester group, an ether group, a urethane group, a thiourethane group or a urea group; as reactive end groups, Z1 and Z2 may be selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxides such as propylepoxide or butylepoxide and azacyclopropane groups; - Q represents an organic polymer or oligomer comprising repeating units of saturated, linear or branched or cyclic aliphatic groups or aromatic groups or alkylaromatic groups linked via carbonate, ester, ether, amide, urethane or urea repeating bonds or combinations thereof; - A represents a divalent aliphatic, aromatic, alkylaromatic or straight-chain, saturated, branched or cyclic group containing 2 to 30 carbon atoms, which may optionally contain one or more non-pendant heteroatoms such as nitrogen atoms, oxygen atoms, sulfur atoms or combinations thereof in the aliphatic or aromatic chain; - r represents an integer equal to 0 or 1; m represents an integer ranging from 0 to 1000, preferably equal to 0 or 1; m' represents an integer ranging from 0 to 1000, preferably equal to 0 or 1; - n represents an integer ranging from 0 to 1000, preferably equal to 0 or 1, where m+(m'*n) is equal to or greater than 2. The compound is selected from the group consisting of:

[0031] Preferably, Z1 and Z2 independently represent a reactive end group; more preferably, Z1 and Z2 can be independently selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, such as propylepoxide or butylepoxide, and azacyclopropane group.

[0032] Such (poly)carbodiimide compounds are sold, for example, by Stahl BV under the names Permutex XR, RelcaLink 10 and Picassian XL, and by Nisshinbo Chemicals under the name Carbodilite, including 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 and V-05.

[0033] Preferably, the (poly)carbodiimide compound is represented by the following formula (II): [ka] (In the formula, X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; - R1 and R2 independently represent a hydrocarbon-based group optionally interrupted by one or more heteroatoms; - n and z represent integers ranging from 1 to 20, where n+z≧2, and w represents an integer ranging from 1 to 3; L1 is independently a divalent C1 to C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 arylene groups and mixtures thereof; - E independently - -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- (wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms. represents a group selected from The compound is selected from the group consisting of:

[0034] The term "hydrocarbon-based group" means a saturated or unsaturated, linear or branched group containing 1 to 300 carbon atoms, preferably 1 to 250 carbon atoms, more preferentially 1 to 200 carbon atoms. Preferably, the hydrocarbon-based group is a saturated linear group.

[0035] The hydrocarbon-based group can contain one or more cyclic groups.

[0036] The hydrocarbon-based group may be interrupted by one or more heteroatoms selected in particular from O, S or N, and / or may be substituted with one or more cations, anions or zwitterions, or cationic groups such as ammonium, anionic groups such as carboxylate, or zwitterionic groups, and / or may contain metal ions that can be incorporated in the form of salts.

[0037] The term "heteroatom" means an oxygen O, sulfur S or nitrogen N atom as well as a halogen atom such as Cl, F, Br and I. If a heteroatom is contained in the chain of a hydrocarbon-based group, this heteroatom is preferably selected from an oxygen O, sulfur S or nitrogen N atom.

[0038] Preferably, X1 and X2 independently represent an oxygen atom.

[0039] Preferably, R1 and R2 are independently selected from dialkylamino alcohols from which the hydroxyl groups have been removed, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof.

[0040] In a preferred embodiment, R1 and R2 are selected from the following groups (i) to (iv): (i) Formula (III): R7-OC(O)-C(R8)(H)- (III) (wherein R7 represents a C1-C3 alkyl group, and R8 represents a hydrogen atom or a C1-C3 alkyl group; preferably, R7 is methyl, and R8 is a hydrogen atom or methyl). The compound (ii) Formula (IV): R9-[O-CH2-C(H)(R 10 )] p - (IV) (wherein R9 represents a C1-C4 alkyl group, R 10 represents a hydrogen atom or a C1-C4 alkyl group, p represents an integer ranging from 1 to 3; preferably, R9 is methyl, ethyl or butyl, and R 10 is a hydrogen atom or methyl, and p is equal to 1. The compound (iii) Formula (V): (R 11 )2N-CH2-C(H)(R 12 )- (V) (In the formula, R 11 represents a C1-C4 alkyl group, and R 12 represents a hydrogen atom or a C1-C4 alkyl group; preferably, R 11 is methyl, ethyl or butyl, and R 12 is a hydrogen atom or methyl) The compound (iv) Formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) (In the formula, R 13 represents a C1-C4 alkyl group, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, and q represents an integer ranging from 4 to 30; preferably, R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl) Compounds of are independently selected from

[0041] Preferably, R1 and R2 independently represent a compound of formula (VI), wherein R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; and q represents an integer in the range of 4-30.

[0042] According to an alternative embodiment, R1 and R2 are different, and one of the R1 or R2 groups represents a compound of formula (IV) as described above, and the other of the R1 or R2 groups represents a compound of formula (VI) as described above.

[0043] Preferably, in formula (IV), R is methyl, ethyl or butyl, and R 10 is a hydrogen atom or methyl, and p is equal to 1.

[0044] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl, and q is an integer ranging from 4 to 30.

[0045] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), wherein R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; and q represents an integer in the range of 4-30.

[0046] Preferably, n represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0047] Preferably, z represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0048] Preferably, w is equal to one.

[0049] Preferably, w is equal to 1 and n+z represents an integer in the range 4-10.

[0050] Preferably, L1 is a divalent C1-C6 alkyl group such as methylene, ethylene, and propylene. 18 Aliphatic hydrocarbon groups, C3-C such as cyclopentylene, cycloheptylene, and cyclohexylene 15 C3-C such as cycloalkylene groups, imidazolene, pyrrolene, and furanylene 12 C6-C such as heterocycloalkylene group or phenylene 14 The aryl group is selected from arylene groups as well as mixtures thereof.

[0051] For example, L1 may be selected from groups derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-1,3-dioctylcyclobutane, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-napthethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, and phenylene diisocyanate, and mixtures thereof.

[0052] Preferably, L1 is C3 to C 15 Cycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, such as those of the following formula (VII): [ka] is selected from.

[0053] Preferably, L1 is represented by the following formula (VIII): [ka] The corresponding 4,4-dicyclohexylenemethane is

[0054] According to another embodiment, L1 is C6 to C 14 When L1 is an arylene group, it is represented by the following formula (IX): [ka] It is not an m-tetramethylxylylene group represented by the formula:

[0055] As mentioned earlier, E is independently - -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- (wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; and R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms. represents a group selected from

[0056] Preferably, R3 and R4 are C6-C alkyl groups, such as phenylene, optionally interrupted by one or more heteroatoms. 14 C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 alkylene groups as well as mixtures thereof.

[0057] More preferentially, R3 and R4 are linear or branched C1-C6 alkylenes, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms. 18 alkylene groups.

[0058] Preferably, when R5 is not a covalent bond, R5 is a C6-C6 alkyl group, such as phenylene, optionally interrupted by one or more heteroatoms. 14C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 The alkylene groups are selected from alkylene groups as well as mixtures thereof.

[0059] Preferably, R6 is a C6-C, such as phenylene, optionally interrupted by one or more heteroatoms. 14 C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 The alkylene groups are selected from alkylene groups as well as mixtures thereof.

[0060] Preferably, E represents a -O-R3-O- group, where R3 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 The alkylene group is selected from alkylene groups and mixtures thereof.

[0061] More preferentially, E represents a -O-R3-O- group, where R3 is a linear or branched C1-C6 alkyl group, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms. 18 Represents an alkylene group.

[0062] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (X): [ka] (wherein R independently represents an alkyl group containing 1 to 24 carbon atoms, a cycloalkyl group containing 3 to 24 carbon atoms, or an aryl group containing 6 to 24 carbon atoms; and n represents an integer ranging from 2 to 100. It is a copolymer derived from α-methylstyryl isocyanate.

[0063] The term "alkyl group" in this embodiment is as defined above.

[0064] The term "cycloalkyl group" in this embodiment is as defined above.

[0065] In this embodiment, n may represent an integer ranging from 2 to 50, preferably from 3 to 30, and even more preferentially from 5 to 10.

[0066] According to another particular embodiment, the (poly)carbodiimide compound has the following formula (XI): [ka] (wherein R independently represents an alkyl group containing 1 to 24 carbon atoms, a cycloalkyl group containing 3 to 24 carbon atoms, or an aryl group containing 6 to 24 carbon atoms). is a compound of

[0067] The "alkyl group", "cycloalkyl group" and "aryl group" are as defined above.

[0068] According to a preferred embodiment, the (poly)carbodiimide compound is selected from compounds of formula (I) or formula (II), wherein: X1 and X2 independently represent an oxygen atom; R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed, and more preferentially R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30; - when n and z are present, they represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - If L1 is present, it is a divalent C1-C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, preferably C3-C 15 cycloalkylene groups; - If A is present, it is a divalent C1-C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, preferably C3-C 15 cycloalkylene groups; - E, if present, is independently - -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- wherein R3 and R4 are independently a C6-C aryl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; - R5 is not a covalent bond, and if R5 is present, it is a C6-C6 bond optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; and - When R6 is present, it is a C-C bond optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof) represents a group selected from

[0069] Preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein X1 and X2 independently represent an oxygen atom; R1 and R2 are independently selected from dialkylamino alcohols from which the hydroxyl groups have been removed, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof; - n and z represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L1 is divalent C1 to C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 arylene groups and mixtures thereof; - E independently - -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- wherein R3 and R4 are independently a C6-C alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; When R5 is not a covalent bond, R5 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; and R6 is a C-C group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof) represents a group selected from

[0070] More preferentially, the (poly)carbodiimide compound is chosen from compounds of formula (II), in which X1 and X2 independently represent an oxygen atom; R1 and R2 are independently a monoalkyl ether of a (poly)alkylene glycol from which a hydroxyl group has been removed; - n and z represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L1 is C3~C 15 is a cycloalkylene group; - E independently - -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- wherein R3 and R4 are independently a C6-C aryl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; When R5 is not a covalent bond, R5 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; and R6 is a C-C group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof) represents a group selected from

[0071] Even more preferentially, the (poly)carbodiimide compound is chosen from compounds of formula (II), in which X1 and X2 independently represent an oxygen atom; R1 and R2 independently represent the following formula (VI): R13 -[O-CH2-C(H)(R 14 )] q - (VI) (In the formula, R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30. represents the compound of - n and z represent integers ranging from 2 to 20, where n+z ranges from 4 to 10 and w is equal to 1; - L1 is a C3-C alkyl group such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane. 15 is a cycloalkylene group; and E is an —O—R—O— group, where R is a C-C alkyl group optionally interrupted by one or more heteroatoms; 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof).

[0072] Even more preferentially, the (poly)carbodiimide compound is chosen from compounds of formula (II), in which X1 and X2 independently represent an oxygen atom; R1 and R2 independently represent the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) (In the formula, R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30. represents the compound of n and z represent integers ranging from 1 to 20, preferably from 2 to 20, where n+z ranges from 4 to 10 and w is equal to 1; - L1 is a C3-C alkyl group such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane. 15 a cycloalkylene group, preferably 4,4-dicyclohexylenemethane; and E is a -O-R-O- group, where R is a linear or branched C-C alkylene such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms; 18 represents an alkylene group).

[0073] According to a preferred embodiment, the (poly)carbodiimide compound has the following formula (XII): [ka] wherein L1 is 4,4-dicyclohexylenemethane, n and z represent integers ranging from 1 to 20, preferably from 2 to 20, where n+z is in the range of 4 to 10, and E is an -O-R3-O- group, where R3 is a linear or branched C1-C alkyl group such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms. 18 an alkylene group), and r and s represent integers ranging from 4 to 30. is a compound of

[0074] The total amount of (poly)carbodiimide compounds present in the hair colorant composition is preferably in the range of 0.01% to 30% by weight, more preferentially 0.1% to 25% by weight, even better 0.2% to 20% by weight, even better still 1% to 10% by weight, relative to the total weight of the hair colorant composition.

[0075] coloring agent As mentioned above, the composition for coloring hair keratin fibers used in connection with the method according to the invention comprises at least one coloring agent chosen from pigments, direct dyes and mixtures thereof.

[0076] Preferably, the composition for coloring hair keratinous fibers comprises one or more pigments.

[0077] The term "pigment" refers to any pigment that colors keratinous materials, the solubility of which in water at 25°C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, preferably less than 0.01%.

[0078] Pigments that may be used are chosen in particular from organic and / or mineral pigments known in the art and in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.

[0079] These may be natural products of natural origin or non-natural products.

[0080] These pigments may be in the form of pigment powders or pastes. They may be coated or uncoated.

[0081] The pigments may be selected, for example, from mineral pigments, organic pigments, special effect pigments such as lakes, pearlescent agents or glitter flakes, and mixtures thereof.

[0082] The pigment may be a mineral pigment. The term "mineral pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann's encyclopaedia. Among the inorganic pigments that can be used in the present invention, mention may be made of iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium oxide.

[0083] The pigment may be an organic pigment. The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann's encyclopaedia.

[0084] The organic pigments may be chosen in particular from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal complexes, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

[0085] In particular, white or colored organic pigments are carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments classified in the Color Index under the reference numbers CI 42090, 69800, 69825, 74100, 74160, yellow pigments classified in the Color Index under the reference numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, green pigments classified in the Color Index under the reference numbers CI 61565, 61570, 74260, orange pigments classified in the Color Index under the reference numbers CI 11725, 45370, 71105, red ... The pigments may be selected from the red pigments classified under the reference numbers 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, and from the pigments obtained by oxidative polymerization of indole or phenol derivatives described in French Patent No. 2 679 771.

[0086] Examples of pigment pastes with organic pigments include those sold by Hoechst under the following names: - Cosmenyl Yellow 10G: Pigment Yellow 3 (CI 11710); - Cosmenyl Yellow G: Pigment Yellow 1 (CI 11680); - Cosmenyl Orange GR: Pigment Orange 43 (CI 71105); - Cosmenyl Red R: Pigment Red 4 (CI 12085); - Cosmenyl Carmine FB: Pigment Red 5 (CI 12490); - Cosmenyl Violet RL: Pigment Violet 23 (CI 51319); - Cosmenyl Blue A2R; Pigment Blue 15.1 (CI 74160); - Cosmenyl Green GG: Pigment Green 7 (CI 74260); - Cosmenyl Black R: Pigment Black 7 (CI 77266).

[0087] The pigments according to the invention may be in the form of composite pigments, as described in EP 1 184 426. These composite pigments may in particular consist of particles comprising an inorganic core, at least one binder binding an organic pigment to the core, and at least one organic pigment covering at least a portion of the core.

[0088] The organic pigment may be a lake, the term "lake" referring to a dye adsorbed onto insoluble particles so that the resulting composite remains insoluble during use.

[0089] The mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.

[0090] Among the dyes, mention may be made of carminic acid, also known by the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green 5 (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

[0091] An example of a lake is the product known by the following name: D&C Red 7 (CI 15 850:1).

[0092] Pigments can also be special effect pigments. The term "special effect pigments" refers to pigments that generally produce a colored appearance (characterized by a specific hue, a specific vividness, and a specific level of brightness) that is not uniform and that varies depending on the conditions of observation (light, temperature, angle of observation, etc.), thereby differing from colored pigments that exhibit standard uniform opaque, translucent, or transparent shades.

[0093] There are several types of special effect pigments: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a high refractive index, such as pearlescent agents, interference pigments or glitter flakes.

[0094] Examples of special effect pigments that may be mentioned include pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxide, mica coated with iron oxide, mica coated with titanium, in particular with ferric blue or chromium oxide, mica coated with titanium and coated with the organic pigments defined above, and also pearlescent pigments based on bismuth oxychloride. As pearlescent pigments, mention may be made of pearlescent agents such as Cellini (mica-TiO2-lake) sold by BASF, Prestige (mica-TiO2) sold by Eckart, Prestige Bronze (mica-Fe2O3) sold by Eckart, or Colorona (mica-TiO2-Fe2O3) sold by Merck.

[0095] Gold pearlescent agents, in particular those sold by BASF under the names Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); bronze pearlescent agents, in particular those sold by Merck under the names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super bronze (Cloisonne); orange pearlescent agents, in particular those sold by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion orange (Colorona) and Matte orange (17449) (Microna); brown pearlescent agents, in particular those sold by BASF under the names Nu-antique Copper copper-tinted pearlescent agents, in particular those sold by BASF under the name Copper 340A (Timica); red-tinted pearlescent agents, in particular those sold by Merck under the name Sienna fine (17386) (Colorona); yellow-tinted pearlescent agents, in particular those sold by BASF under the name Yellow (4502) (Chromalite); gold-tinted red pearlescent agents, in particular those sold by BASF under the name Sunstone G012 (Gemtone); pink-tinted pearlescent agents, in particular those sold by BASF under the name Tan opale G005 (Gemtone); gold-tinted black pearlescent agents, in particular those sold by BASF under the name Nu antique bronze 240 blue pearlescent agents, in particular those sold under the name AB (Timica); blue pearlescent agents, in particular those sold under the name Matte blue (17433) (Microna) by Merck; silvery white pearlescent agents, in particular those sold under the name Xirona Silver by Merck;Mention may also be made of gold-green to pink to orange-shifting pearlescent agents, in particular those sold under the name Indian summer (Xirona) by Merck; and mixtures thereof.

[0096] Further examples of pearlescent agents may include particles comprising a borosilicate substrate coated with titanium oxide.

[0097] Particles comprising a glass substrate coated with titanium oxide are sold in particular under the name Metashine MC1080RY by the company Toyal.

[0098] Finally, as examples of pearlescent agents, mention may be made of polyethylene terephthalate glitter flakes, in particular those sold under the name Silver 1P 0.004X0.004 (silver glitter flakes) by Meadowbrook Inventions, Inc. Multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate, and aluminum, may also be envisaged.

[0099] The special effect pigments can also be chosen from reflective particles, i.e. particles that, due to their size, structure, in particular the thickness of the layer of which they are composed, as well as their physical and chemical properties and surface condition, are able to reflect incident light, where appropriate, this reflection can be strong enough to produce, when applied to the support to be made up, a bright spot visible to the naked eye on the surface of the composition or mixture, i.e. a brighter spot that appears to be noticeably brighter than its surroundings.

[0100] The reflective particles can be selected so as not to significantly alter the color effect of the colorant with which they are combined, more particularly to optimize this effect in terms of color rendering, which can more particularly have yellow, pink, red, bronze, orange, brown, gold and / or copper colors or shades.

[0101] These particles may have various morphologies, in particular in the form of platelets or spheres, in particular in the form of spheres.

[0102] Regardless of their morphology, the reflective particles may or may not have a multi-layer structure, and if they do have a multi-layer structure, they may have at least one layer of a particularly reflective material, for example of uniform thickness.

[0103] If the reflective particles do not have a multilayer structure, they may consist of metal oxides, in particular synthetically obtained titanium oxide or iron oxide.

[0104] When the reflective particles have a multilayer structure, they may comprise, for example, a natural or synthetic substrate, in particular a synthetic substrate, at least partially coated with at least one layer of a reflective material, in particular at least one metal or metallic material. The substrate can be made from one or more organic and / or inorganic materials.

[0105] More particularly, it can be chosen from glass, ceramic, graphite, metal oxides, alumina, silica, silicates, especially aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, without being limited to this list.

[0106] The reflective material may include a metal or a layer of metallic material.

[0107] Reflective particles are described in particular in the documents JP-A-09-188830, JP-A-10-158450, JP-A-10-158541, JP-A-07-258460 and JP-A-05-017710.

[0108] Further examples of reflective particles comprising an inorganic substrate coated with a metal layer may include particles comprising a borosilicate substrate coated with silver.

[0109] Silver-coated glass-based particles in platelet form are sold by Toyal under the name Microglass Metashine REFSX 2025 PS. Nickel / chromium / molybdenum alloy-coated glass-based particles are sold by the same company under the names Crystal Star GF 550 and GF 2525.

[0110] Particles comprising a metal substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, or titanium may also be utilized, wherein the substrate is coated with at least one layer of at least one metal oxide such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxide, and mixtures thereof.

[0111] Mention may be made, by way of example, of the aluminum, bronze or copper powders coated with SiO2 sold under the name Visionaire by the company Eckart.

[0112] Mention may also be made of pigments that are not bound to a substrate and exhibit interference effects, such as liquid crystals (Helicones HC from Wacker) or holographic luminescent flakes (Geometric Pigments or Spectra f / x from Spectratek).Pigments with special effects also include fluorescent pigments (these are either substances that fluoresce in daylight or that exhibit ultraviolet fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, for example, as sold by Quantum Dots Corporation.

[0113] The variety of pigments that can be used in the present invention makes it possible to obtain a wide range of colors and also to obtain specific optical effects such as metallic or interference effects.

[0114] The size of the pigments used in the composition according to the invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm, and more preferentially between 30 nm and 50 μm.

[0115] The pigment can be dispersed in the composition with a dispersant.

[0116] Dispersants serve to prevent the aggregation or flocculation of dispersed particles. They can be surfactants, oligomers, polymers, or mixtures of several of these, each containing one or more functional groups with a strong affinity for the surface of the particles to be dispersed. In particular, they can be physically or chemically bound to the pigment surface. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid and esters of C8-C20 fatty acids and polyols such as glycerol or diglycerol are used, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g / mol, such as the product sold by Avecia under the name Solsperse 21000, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold by Henkel under the trade name Dehymyls PGPH, or other polyhydroxystearates, such as the product sold by Uniqema under the trade name Arlacel P100, and mixtures thereof.

[0117] Other dispersants that may be used in the compositions of the present invention include quaternary ammonium derivatives of polycondensed fatty acids, such as Solsperse 17000 sold by Avecia, and polydimethylsiloxane / oxypropylene mixtures, such as those sold by Dow Corning under the trade designations DC2-5185 and DC2-5225 C.

[0118] The pigments that can be used in the composition can be surface-treated with an organic agent.

[0119] Thus, pre-surface-treated pigments useful in the context of the present invention are pigments which have been subjected, in whole or in part, to a surface treatment of a chemical, electronic, electrochemical, mechanochemical or mechanical nature with organic agents, such as those described in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, and which, after such treatment, are dispersed in the compositions of the present invention. These organic agents may be selected, for example, from waxes such as carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithin; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, such as aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic acid polymers, such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, such as silicones, in particular polydimethylsiloxane; organic fluorine compounds, such as perfluoroalkyl ethers; fluorosilicone compounds.

[0120] The surface-treated pigments useful in the present compositions may be treated with mixtures of these compounds and / or may have been subjected to several surface treatments.

[0121] Surface-treated pigments useful in connection with the present invention can be prepared according to surface treatment techniques well known to those skilled in the art, or can be commercially available as is.

[0122] Preferably, the surface-treated pigment is coated with an organic layer.

[0123] The organic agent with which the pigment is treated may be deposited on the pigment by evaporating the solvent, by chemical reaction between molecules of the surface treatment agent, or by forming a covalent bond between the surface treatment agent and the pigment.

[0124] Thus, the surface treatment can be carried out, for example, by chemically reacting a surface treatment agent with the pigment surface to form a covalent bond between the surface treatment agent and the pigment or filler, as described, inter alia, in U.S. Pat. No. 4,578,266.

[0125] Preferably, an organic agent that is covalently bonded to the pigment will be used.

[0126] The surface treatment agent can account for 0.1% to 50% by mass, preferably 0.5% to 30% by mass, and more preferably 1% to 20% by mass of the total mass of the pigment to be surface treated.

[0127] Preferably, the surface treatment of the pigment is one of the following treatments: - PEG-silicone treatments, such as the AQ surface treatment sold by LCW; - methicone treatments, such as the SI surface treatment sold by LCW; - dimethicone treatments, such as Covasil 3.05 surface treatment sold by LCW; - Dimethicone / trimethylsiloxysilicate treatments, such as Covasil 4.05 surface treatment sold by LCW; - magnesium myristate treatments, such as the MM surface treatment sold by LCW; - aluminum dimyristate treatment agents, such as the MI surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - Perfluoropolymethyl isopropyl ether treatments, such as the FHC surface treatment sold by LCW; - isostearyl sebacate treatment agents, such as the HS surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - perfluoroalkylphosphate treatment agents, such as the PF surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - acrylate / dimethicone copolymer and perfluoroalkylphosphate treatment agents, such as the FSA surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - polymethylhydrogenosiloxane / perfluoroalkylphosphate treatment agents, such as the FS01 surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - acrylate / dimethicone copolymer treatment agents, such as the ASC surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - isopropyl titanium triisostearate treatment agents, such as ITT surface treatment agents sold by Daito Chemical Industry Co., Ltd.; - acrylate copolymer treatment agents, such as the APD surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - Perfluoroalkylphosphate / isopropyl titanium triisostearate treatment agent, such as PF+ITT surface treatment agent sold by Daito Kasei Kogyo Co., Ltd. is selected from.

[0128] According to a particular embodiment of the present invention, the dispersant is present together with the organic or mineral pigment in particulate form of submicron size.

[0129] The terms "submicron" or "submicron-rich" refer to pigments that have been micronized by a micronization process and have an average particle size of less than 1 micrometer (μm), particularly 0.1 to 0.9 μm, and preferably 0.2 to 0.6 μm.

[0130] According to one embodiment, the dispersant and the pigment are present in an amount (dispersant:pigment) of 1:4 to 4:1, in particular 1.5:3.5 to 3.5:1 or better still 1.75:3 to 3:1, by weight ratio.

[0131] Thus, the dispersant may have a silicone backbone, such as a silicone polyether, and may be an aminosilicone type dispersant. Suitable dispersants include: aminosilicones, i.e. silicones containing one or more amino groups, such as those sold by BYK under the name BYK LPX 21879, and the names GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1 sold by Genesee Polymers; silicone acrylates, such as Tego® RC 902, Tego® RC 922, Tego® RC 1041 and Tego® RC 1043 sold by Evonik; - polydimethylsiloxane (PDMS) silicones with carboxyl groups, such as X-22162 and X-22370 from Shin-Etsu Chemical Co., Ltd., epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682 and GP-695 from Genesee Polymers or Tego® RC 1401, Tego® RC 1403, Tego® RC 1412 from Evonik.

[0132] According to one particular embodiment, the dispersant is of the aminosilicone type and is cationic.

[0133] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments or organic pigments.

[0134] In one variant of the invention, the pigment is an organic pigment, preferentially an organic pigment surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment is a mineral pigment.

[0135] direct dye The hair keratin fiber coloring composition used in connection with the method according to the invention may comprise one or more direct dyes.

[0136] The term "direct dyes" means natural and / or synthetic dyes other than oxidation dyes. These are dyes that will diffuse superficially onto the fiber.

[0137] These can be ionic or non-ionic, preferably cationic or non-ionic.

[0138] Examples of suitable direct dyes include azo direct dyes, either alone or in mixtures; (poly)methine dyes, such as cyanine, hemicyanine and styryl; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes; and natural direct dyes.

[0139] The direct dyes are preferably cationic direct dyes, such as hydrazonocationic dyes of the following formulae (XIII) and (XIV) and azocationic dyes of the following formulae (XV) and (XVI). Het + -N(Ra)-N=C(Rb)-Ar,Q-(XIII), Het + -C(Ra)=NN(Rb)-Ar,Q(XIV), Het + -N=N-Ar,Q-(XV), Ar + -N=N-Ar'',Q-(XVI) In formulas (XIII) to (XVI), Het+ represents a cationic heteroaryl group, such as imidazolium, indolium or pyridinium, preferentially carrying a cationic charge in the ring and preferentially optionally substituted with at least one (C1-C8) alkyl group, such as methyl; - Ar+ represents an aryl group such as phenyl or naphthyl, carrying an exocyclic cationic charge, preferentially ammonium, in particular tri(C1-C8)alkylammonium, such as trimethylammonium; - Ar preferentially represents one or more electron-donating groups, such as i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8)(alkyl)amino, in which the alkyl group is optionally substituted with a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) an aryl group, in particular phenyl, optionally substituted with an optionally substituted N—(C1-C8) alkyl-N-aryl(C1-C8) alkylamino, or alternatively, Ar represents a julolidine group; Ar" represents an optionally substituted (hetero)aryl group, for example phenyl or pyrazolyl, preferentially optionally substituted with one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups; Ra and Rb may be identical or different and represent a hydrogen atom or an optionally substituted (preferentially by a hydroxyl group) (C1-C8) alkyl group; or Otherwise, Het + the substituents Ra together with the substituents of and / or Rb together with the substituents of Ar together with the atoms carrying them form a (hetero)cycloalkyl; in particular Ra and Rb represent a (C1-C4)alkyl group optionally substituted with a hydrogen atom or a hydroxyl group; - Q- represents an organic or inorganic anionic counterion such as a halide or alkyl sulfate.

[0140] Mention may be made in particular of the azo and hydrazono direct dyes with an endocyclic cationic charge of the formulae (XIII) to (XVI) defined above, more particularly the cationic direct dyes with an endocyclic cationic charge described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954, preferentially the following direct dyes: [ka] In formulas (XVII) and (XVIII), -R 1 represents a (C1-C4) alkyl group such as methyl; -R 2 and R 3 may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl; -R 4 represents a hydrogen atom or an electron donating group, such as an optionally substituted (C1-C8) alkyl, an optionally substituted (C1-C8) alkoxy or a (di)(C1-C8)(alkyl)amino, wherein the alkyl group is optionally substituted with a hydroxyl group; in particular, R 4 is a hydrogen atom; Z represents a CH group or a nitrogen atom, preferentially CH, Q- is an anionic counterion as defined above, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0141] In particular, the dyes of formula (XV) and (XVI) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof, and Q′ is an anionic counterion as defined above, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0142] The direct dye can be selected from anionic direct dyes. The anionic direct dye of the present invention is a dye generally referred to as an "acid" direct dye, due to its affinity for alkaline substances. The term "anionic direct dye" refers to a direct dye containing at least one COR or SOR substituent in its structure, where R represents a hydrogen atom or a cation or ammonium ion derived from a metal or amine. The anionic dye can be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethanoic acid dyes, indoamine acid dyes, anthraquinonic acid dyes, indigoid dyes, and natural acid dyes.

[0143] Acid dyes useful in the present invention include dyes of the following formulae (XIX), (XIX'), (XX), (XX'), (XXI), (XXI'), (XXII), (XXII'), (XXIII), (XXIV), (XXV) and (XXVI). a) diaryl anionic azo dyes of formula (XIX) or (XIX'): [ka] In formulas (XIX) and (XIX'), - R7, R8, R9, R 10 , R'7, R'8, R'9 and R' 10 may be the same or different and are a hydrogen atom, or - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be identical or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); - R"-S(O)2- (wherein R" represents a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group); - R'''-S(O)2-X'-, where R''' represents an optionally substituted alkyl or aryl group and X' is as defined above; - (di)(alkyl)amino; - i) nitro; ii) nitroso; iii) (O)2S(O - )-, M + and iv) optionally substituted with one or more groups selected from alkoxy; M + aryl(alkyl)amino, wherein: - optionally substituted heteroaryl; preferentially a benzothiazolyl group; - cycloalkyl; in particular cyclohexyl; - Ar-N=N- (wherein Ar is an optionally substituted aryl group; preferentially one or more alkyl, (O)S(O - )-,M + or phenyl optionally substituted by a phenylamino group) selected from; or - two adjacent groups R7 and R8 or R8 and R9 or R9 and R 10 together form a fused benzo group A'; R'7 and R'8 or R'8 and R'9 or R'9 and R' 10 together form a fused benzo group B'; A' and B' are i) nitro; ii) nitroso; iii) (O)S(O - )-,M + iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N-; and xi) optionally substituted aryl(alkyl)amino; + , R°, X, X′, X″ and Ar are as defined above; - W represents a sigma bond σ, an oxygen or sulfur atom or a divalent radical: i) -NR-, where R is as defined above, or ii) methylene -C(Ra)(Rb)-, where Ra and Rb may be identical or different and represent a hydrogen atom or an aryl group, or alternatively, Ra and Rb together with the carbon atom carrying them form a spirocycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl; Formulas (XIX) and (XIX') contain at least one sulfonate group (O)S(O) on one of the rings A, A', B, B' or C. - )-,M + or one carboxylate group (O)CO - -,M + ; it is understood that it preferentially comprises sodium sulfonate.

[0144] Examples of dyes of formula (XIX) are Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or Sunset Yellow; as examples of dyes of formula (XIX'), mention may be made of Acid Red 111, Acid Red 134, Acid Yellow 38.

[0145] b) Pyrazolone anionic azo dyes of formula (XX) and (XX'): [ka] In formulas (XX) and (XX'), -R 11 , R 12 and R 13 may be the same or different and are hydrogen or halogen atoms, alkyl groups or -(O)S(O - ), M + (In the formula, M + is as defined above); -R 14 represents a hydrogen atom, an alkyl group, or -C(O)O - ,M + group (in the formula, M + is as defined above); -R 15 represents a hydrogen atom; -R 16 represents an oxo group, in which case R' 16 does not exist, or instead, R 15 is R 16 together to form a double bond; -R 17 and R 18 may be the same or different and are a hydrogen atom, or - (O)2S(O - )-,M + (In the formula, M + is as defined above); - Ar-OS(O)2-, where Ar represents an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups. represents a group selected from: -R 19 and R 20 together form either a double bond or an optionally substituted benzo group D'; - R' 16 , R' 19 and R' 20 may be the same or different and represent a hydrogen atom or an alkyl group or a hydroxyl group; -R 21represents a hydrogen atom, an alkyl group, or an alkoxy group; Ra and Rb may be identical or different and are as defined above, and preferentially, Ra represents a hydrogen atom and Rb represents an aryl group; Y represents either a hydroxyl group or an oxo group; - [ka] represents a single bond when Y is an oxo group; represents a double bond when Y is a hydroxyl group; Formulas (XX) and (XX') contain at least one sulfonate group (O)S(O) on one of the rings D or E. - )-,M + or one carboxylate group -C(O)O - ,M + ; it is understood that it preferentially comprises sodium sulfonate.

[0146] Examples of dyes of formula (XX) include Acid Red 195, Acid Yellow 23, Acid Yellow 27, and Acid Yellow 76; examples of dyes of formula (XX') include Acid Yellow 17.

[0147] c) Anthraquinone dyes of formula (XXI) and (XXI'): [ka] In formulas (XXI) and (XXI'), -R 22 , R 23 , R 24 , R 25 , R 26 and R 27 may be the same or different and represent a hydrogen or halogen atom, or - alkyl; - hydroxyl, mercapto; - alkoxy, alkylthio; - Alkyl and (O)2S(O -),M + optionally substituted aryloxy or arylthio, which are preferentially substituted by one or more groups selected from + is as defined above); - Alkyl and (O)2S(O-)-, M + (In the formula, M + is as defined above); - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino; - (O)2S(O - )-,M + (In the formula, M + is as defined above) represents a group selected from: Z' is a hydrogen atom or a group NR 28 R 29 (wherein R 28 and R 29 may be the same or different and are a hydrogen atom, or - alkyl; - polyhydroxyalkyl, such as hydroxyethyl; one or more groups, in particular i) alkyl, such as methyl, n-dodecyl, n-butyl; ii) (O)S(O - )-, M + (In the formula, M + is as defined above; iii) aryl optionally substituted with R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above and preferentially R° represents an alkyl group); - cycloalkyl, in particular cyclohexyl; represents a group selected from: - Z is hydroxyl and NR' 28 R' 29 (wherein R' represents a group selected from 28 and R' 29 may be the same or different and are R as defined above. 28 and R29 represents the same atom or group as Formulas (XXI) and (XXI') contain at least one sulfonate group (O)S(O - )-,M + or one carboxylate group C(O)O - ,M + ; it is understood that it preferentially comprises sodium sulfonate.

[0148] Examples of dyes of formula (XXI) include Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2; and an example of a dye of formula (XXI') is Acid Black 48.

[0149] d) Nitro dyes of formula (XXII) and (XXII'): [ka] In formulas (XII) and (XII'), -R 30 , R 31 and R 32 may be the same or different and represent a hydrogen or halogen atom, or - alkyl; - alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups; - hydroxyl, mercapto; - Nitro, nitroso; - polyhaloalkyl; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above); - (O)2S(O- )-,M + (In the formula, M + is as defined above); - (O)CO - -,M + (In the formula, M + is as defined above); - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino; heterocycloalkyl, such as piperidino, piperazino or morpholino In particular, R 30 , R 31 and R 32 represents a hydrogen atom; Rc and Rd may be identical or different and represent a hydrogen atom or an alkyl group; - W is as defined above; W represents, in particular, an -NH- group; - ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group; - n is 1 or 2; - p represents an integer between 1 and 5 (inclusive); - q represents an integer between 1 and 4 (inclusive); - u is 0 or 1; - when n is 1, J represents a nitro or nitroso group; in particular nitro; - when n is 2, J is an oxygen or sulfur atom or a divalent -S(O) m - group, where m represents an integer of 1 or 2; preferentially, J represents a -SO2- group; M' represents a hydrogen atom or a cationic counterion; - [ka] is optionally present and may be one or more R 30 represents a benzo group optionally substituted with a group; Formulas (XXII) and (XXII') contain at least one sulfonate group (O)S(O - )-,M + or one carboxylate group -C(O)O - ,M + ; it is understood that it preferentially comprises sodium sulfonate.

[0150] Examples of dyes of formula (XXII) include Acid Brown 13 and Acid Orange 3; examples of dyes of formula (XXII') include Acid Yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4'-N,N-2''-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; and EXT D&C Yellow 7.

[0151] e) Triarylmethane dyes of formula (XXIII): [ka] In formula (XXIII), -R 33 , R 34 , R 35 and R 36 may be identical or different and represent a hydrogen atom or a group selected from alkyl, optionally substituted aryl and optionally substituted arylalkyl; in particular alkyl groups and optionally (O) m S(O - )-, M + group (in the formula, M + and m represents a benzyl group substituted with (as defined above); -R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 may be the same or different and are a hydrogen atom, or - alkyl; - alkoxy, alkylthio; - (di)(alkyl)amino; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be identical or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); or - Alternatively, two adjacent groups R 41 and R 42 or R 42 and R 43 or R 43 and R 44 together form a fused benzo group: I'; I' is i) nitro; ii) nitroso; iii) (O)S(O - )-,M + iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; and ix) R°-X'-C(X)-X''-, where M + , R°, X, X' and X'' are as defined above). and optionally substituted with one or more groups selected from: 37 ~R 40 represents a hydrogen atom, and R 41 ~R 44 may be the same or different and are hydroxyl groups or (O)S(O - )-,M + represents;R 43 and R 44together form a benzo group, this is preferentially (O)S(O - )-group; At least one of the rings G, H, I, or I′ contains at least one sulfonate group (O)S(O - )- or one carboxylate group -C(O)O - ; it is understood that it preferentially comprises sulfonates.

[0152] Examples of dyes of formula (XXIII) include Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid Green 3, Acid Green 5 and Acid Green 50.

[0153] f) Xanthene dyes of formula (XXIV): [ka] In formula (XXIV), -R 45 , R 46 , R 47 and R 48 may be the same or different and represent a hydrogen or halogen atom; -R 49 , R 50 , R 51 and R 52 may be the same or different and represent a hydrogen or halogen atom, or - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above) In particular, R 49 , R 50 , R 51 and R 52 represents a hydrogen or halogen atom; G represents an oxygen or sulfur atom or an NRe group, where Re is as defined above; in particular, G represents an oxygen atom; - L is alkoxide O - , M + ; Thioalkoxide S - , M + or an NRf group (wherein Rf represents a hydrogen atom or an alkyl group, and M + is as defined above; M + is in particular sodium or potassium); L' is an oxygen or sulfur atom or an ammonium group: N + RfRg, where Rf and Rg may be the same or different and represent a hydrogen atom or an optionally substituted alkyl or aryl group; L' represents, in particular, an oxygen atom or one or more alkyl or (O) m S(O - )-, M + Groups (wherein m and M + represents a phenylamino group optionally substituted with (as defined above); Q and Q', which may be identical or different, represent an oxygen or sulfur atom; in particular, Q and Q' represent an oxygen atom; -M + is as defined above.

[0154] Examples of dyes of formula (XXIV) include Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; and Acid Violet 9.

[0155] g) Indole dyes of formula (XXV): [ka] In formula (XXV), -R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 may be the same or different and are a hydrogen atom, or - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be identical or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); represents a group selected from G represents an oxygen or sulfur atom or an NRe group, where Re is as defined above; in particular, G represents an oxygen atom; Ri and Rh may be identical or different and represent a hydrogen atom or an alkyl group; Formula (XXV) contains at least one sulfonate group (O)S(O - )-, M + or one carboxylate group -C(O)O - , M + ; it is understood that it preferentially comprises sodium sulfonate.

[0156] An example of a dye of formula (XXV) is Acid Blue 74.

[0157] h) Quinoline dyes of formula (XXVI): [ka] In formula (XXVI), -R 61 represents a hydrogen atom, a halogen atom, or an alkyl group; -R 62 , R 63 and R 64 may be the same or different and are a hydrogen atom or (O)S(O - )-, M + group (in the formula, M + represents a hydrogen atom or a cationic counterion; or Instead, R 61 and R 62 or R 61 and R 64 together form one or more (O)S(O - )-, M + group (in the formula, M + represents a hydrogen atom or a cationic counterion), forming a benzo group optionally substituted with It is understood that formula (XXVI) contains at least one sulfonate group (O)2S(O-)-,M+, preferentially sodium sulfonate.

[0158] Examples of dyes of formula (XXVI) include Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0159] Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, apigenidin, orcein. Extracts or decoctions containing these natural dyes can also be used, in particular henna-based poultices or extracts.

[0160] Preferably, the direct dye is selected from anionic direct dyes.

[0161] The colorants may be present in a total content ranging from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight relative to the total weight of the dye composition; preferably, the colorants are chosen from pigments.

[0162] The pigments may be present in a total amount of 0.05% to 20% by weight, preferably 0.1% to 15% by weight, and even better still 0.5% to 10% by weight, relative to the total weight of the composition for coloring hair keratin fibers.

[0163] The direct dyes may be present in a total content ranging from 0.001% to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition for coloring hair keratin fibers.

[0164] Non-carboxylate anionic thickener The composition for coloring hair keratin fibers may also contain a non-carboxylate anionic thickener.

[0165] For purposes of the present invention, the term "non-carboxylic acid agent" refers to an agent that does not contain a carboxylic acid functional group (-COOH) or a carboxylate functional group (-COO - ) means a drug that does not contain

[0166] For the purposes of the present invention, the term "thickener" means a thickener that, when present at a concentration of 0.05% by weight relative to the total weight of the composition, thickens the composition into which it is incorporated at room temperature (25°C) and atmospheric pressure at a shear rate of 1 s -1 (Viscosity can be measured using a cone and plate viscometer such as a Haake R600 rheometer).

[0167] Preferably, the non-carboxylic acid anionic thickener is chosen from non-carboxylic acid anionic polymers, more preferentially from anionic polymers containing sulfonic groups.

[0168] For purposes of the present invention, the term "anionic polymer" means a polymer that contains one or more anionic groups or anionic groups and no cationic groups or cationic groups.

[0169] Advantageously, the non-carboxylic acid anionic thickener is chosen from anionic polymers comprising at least one ethylenically unsaturated monomer bearing a sulfonic group, in free form or in partially or completely neutralized form.

[0170] The polymers may be crosslinked or not, they are preferably crosslinked.

[0171] These polymers can be associative or non-associative, preferably non-associative.

[0172] Recall that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0173] Its chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0174] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon chain containing at least 8 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms, more preferentially 18 to 30 carbon atoms.

[0175] Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also represent a hydrocarbon-based polymer (for example, polybutadiene).

[0176] The ethylenically unsaturated monomer having a sulfonic acid group is, in particular, vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylamide (C1-C 22) Alkyl sulfonic acid, N-(C1-C 22 ) Alkyl (meth)acrylamide (C1-C 22 ) alkyl sulfonic acids (such as undecylacrylamido methane sulfonic acid) and also partially or fully neutralized forms thereof.

[0177] (Meth)acrylamide (C1-C 22 ) Alkyl sulfonic acids, such as acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also their partially or completely neutralized forms, are more preferentially used.

[0178] More particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and also its partially or fully neutralized forms are used.

[0179] Among the 2-acrylamido-2-methylpropanesulfonic acid copolymers, mention may be made of partially or completely neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide; particular mention may be made of the products described in Example 1 of EP 503853, to which reference may be made with regard to these polymers.

[0180] Mention may also be made of copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts and hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT 10 by the company SEPPIC (INCI name: Hydroxyethyl acrylate / Sodium acryloyldimethyltaurate copolymer).

[0181] Associative AMPS polymers are particularly suitable for C6-C 22 They can be selected from statistical associative AMPS polymers modified by reaction with n-mono- or di-n-alkylamines, such as those described in patent application WO 00 / 31154, the content of which forms an integral part. These polymers can also contain other ethylenically unsaturated hydrophilic monomers, such as (meth)acrylic acid derivatives, for example their esters with monohydric alcohols, or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidones or mixtures of these compounds.

[0182] Preferred polymers of this family are selected from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0183] These same copolymers may also contain one or more ethylenically unsaturated monomers not containing a fatty chain, such as (meth)acrylic acid derivatives, in particular their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.

[0184] These copolymers are described in particular in EP-A-750899, U.S. Pat. No. 5,089,578 and the following publications from Yotaro Morishima: - Self-assembling amphiphilic polyelectrolytes and their nanostructures,Chinese Journal of Polymer Science,Vol.18,No.40,(2000),323-336; - Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering-Macromolecules,Vol.33,No.10(2000),3694-3704; - Solution properties of micelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte:salt effects on rheological behavior - Langmuir,Vol.16,No.12,(2000)5324-5332; - Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers-Polym.Preprint, Div. Polym. Chem., 40(2), (1999), 220-221.

[0185] Among these polymers, mention may be made of: - 15% to 60% by mass of AMPS units and 40% to 85% by mass of (C8 to C9 16 ) alkyl (meth) acrylamide or (C8-C 16 ) alkyl (meth)acrylate units, crosslinked or non-crosslinked, neutralized or non-neutralized copolymers, such as those described in EP-A-750899; - 10 mol% to 90 mol% of acrylamide units, 0.1 mol% to 10 mol% of AMPS units, and 5 mol% to 80 mol% of n-(C6 to C 18) terpolymers containing alkylacrylamide units, such as those described in U.S. Pat. No. 5,089,578.

[0186] Mention may also be made of fully neutralized copolymers of AMPS and dodecyl methacrylate and also crosslinked and non-crosslinked copolymers of AMPS and n-dodecyl methacrylamide, such as those described in the Morishima paper mentioned above.

[0187] Preferably, the non-carboxylic anionic thickener is chosen from sodium 2-acrylamido-2-methylpropanesulfonate / hydroxyethyl acrylate copolymers sold by the company SEPPIC (INCI name Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer).

[0188] Advantageously, the total amount of non-carboxylate anionic thickeners ranges from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even better from 0.1% to 5% by weight, and even better still from 0.1% to 2% by weight relative to the total weight of the hair colouring composition.

[0189] silicone The composition for coloring hair keratin fibers may also contain at least one silicone.

[0190] Silicones are distinct from compounds containing at least one carboxylic acid group as defined below.

[0191] Preferably, the hair coloring composition comprises at least one silicone selected from non-aminosilicones, aminosilicones and mixtures thereof.

[0192] Silicone is a material that is resistant to atmospheric pressure (1.013 x 10 5 It may be solid or liquid and may be volatile or non-volatile.

[0193] The silicones that can be used may be soluble or insoluble in the compositions according to the invention and they may be in the form of oils, waxes, resins or gums, with silicone oils being preferred.

[0194] Silicones are particularly well-described in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press.

[0195] Preferably, the hair colouring composition is applied at atmospheric pressure (1.013 x 10 5 The silicone composition contains one or more silicones that are liquid at temperatures below 100°C (Pa).

[0196] Volatile silicones can be selected from those having a boiling point between 60°C and 260°C (at atmospheric pressure), more particularly from: i) cyclic polydialkylsiloxanes containing 3 to 7, preferably 4 to 5, silicon atoms, such as: - Octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. Products sold under the name Volatile Silicone 7207 by Union Carbide or Silbione 70045 V 2 by Rhodia, Volatile Silicone 7158 by Union Carbide or Silbione 70045 V 5 by Rhodia; - cyclic copolymers of the dimethylsiloxane / methylalkylsiloxane type having the following chemical structure: [ka] Preferably, cyclomethylsiloxane can be mentioned. Volatile Silicone FZ 3109, available from Union Carbide; - mixtures of cyclic silicones with silicon-based organic compounds, such as octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50 / 50) and octamethylcyclotetrasiloxane and 1,1'-oxy(2,2,2',2',3,3'-hexatrimethylsilyloxy)bisneopentane; ii) Generally, the viscosity at 25°C is 5 x 10 -6 m 2 / s or less, such as decamethyltetrasiloxane, containing 2 to 9 silicon atoms.

[0197] Other silicones belonging to this category are described in the article published in Cosmetics and Toiletries, Vol. 91, January 76, pp. 27-32, Todd & Byers Volatile silicone fluids for cosmetics, and mention may be made of the product sold under the name SH 200 by the company Toray Silicone.

[0198] Among non-volatile silicones, mention may be made of polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, either alone or in mixtures, as well as organopolysiloxanes (or organomodified polysiloxanes or alternatively organomodified silicones) that contain one or more organic functional groups, preferably selected from aryl groups, amine groups, alkoxy groups, and polyoxyethylene or polyoxypropylene groups, generally bonded via hydrocarbon-based groups in their structure. Preferably, the non-volatile silicones are selected from optionally oxyethylenated and oxypropylenated polydimethyl / methylsiloxanes.

[0199] The organomodified silicone may be a polydiarylsiloxane, in particular a polydiphenylsiloxane and a polyalkylarylsiloxane modified with the organofunctional groups mentioned above, the latter being chosen in particular from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes.

[0200] Among the organically modified silicones, mention may be made of organopolysiloxanes, including: - Optionally C6~C 24 polyoxyethylene and / or polyoxypropylene groups containing alkyl groups; for example, dimethicone copolyols, in particular those sold under the name DC 1248 by Dow Corning or the oils Silwet® L722, L7500, L77 and L711 by Union Carbide; or (C12) alkylmethicone copolyols, in particular those sold under the name Q2 5200 by Dow Corning; substituted or unsubstituted amine groups, in particular C1-C4 aminoalkyl groups; mention may be made of the products sold under the names GP4 Silicone Fluid and GP7100 by Genesee or Q2-8220, DC929 or DC939 by Dow Corning; - thiol groups; for example, the products sold by Genesee under the names GP72A and GP71; alkoxylated groups, such as the products sold under the name Silicone Copolymer F-755 by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by Goldschmidt; - hydroxylated groups; for example, polyorganosiloxanes with hydroxyalkyl groups; acyloxyalkyl groups, such as the polyorganosiloxanes described in US Pat. No. 4,957,732; anionic groups of the carboxylic acid type, such as those described in EP 186507 or anionic groups of the alkylcarboxylic acid type, such as the product X-22-3701E from Shin-Etsu Chemical Co., Ltd., or anionic groups of the 2-hydroxyalkylsulfonate or 2-hydroxyalkylthiosulfate type, such as the products sold under the names Abil® S201 and Abil® S255 by Goldschmidt; hydroxyacylamino groups; for example, polyorganosiloxanes as described in EP-A-342834; for example, the product Q2-8413 from Dow Corning.

[0201] The silicone may also be chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes with trimethylsilyl end groups. Among these polydialkylsiloxanes, mention may be made of the following commercially available products: Silbione® oils of the 47 and 70 047 series or Mirasil® oils sold by Rhodia, such as 70 047 V 500 000 oil; - oils of the Mirasil® series sold by the company Rhodia; - Dow Corning 200 series oils, e.g., with a viscosity of 60,000 mm 2 DC200, viscosity in / s; - Viscasil® oils from General Electric and certain oils of the SF series from General Electric (SF 96, SF 18).

[0202] Mention may also be made of polydimethylsiloxanes with dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the 48 series oils from the company Rhodia.

[0203] Polydialkylsiloxanes in this category also include products sold by Goldschmidt under the names Abil Wax® 9800 and 9801, which are poly(C1-C20) dialkylsiloxanes.

[0204] More specific products that can be used in accordance with the present invention are mixtures such as: - mixtures produced from polydimethylsiloxanes with hydroxyl groups at the chain ends, i.e. dimethiconol (CTFA) and from cyclic polydimethylsiloxanes, also known as cyclomethicone (CTFA), such as the product Q2-1401 sold by Dow Corning; - mixtures made from polydimethylsiloxanes with hydroxyl groups at the chain ends, i.e. polydimethylsiloxanes also known as dimethiconol (CTFA) and dimethicone (CTFA), such as Xiameter® PMX-1503 Fluid, a product sold by Dow Corning.

[0205] Polyalkylarylsiloxanes, in particular, have a viscosity of 1 x 10 at 25°C. -5 ~5×10 -2 m 2 The siloxanes are selected from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes, with a molecular weight in the range of 1 / s.

[0206] Among these polyalkylarylsiloxanes, mention may be made of products sold under the following names: - Silbione® oils of the 70 641 series from Rhodia; - Rhodorsil® oils 70633 and 763 series from Rhodia; - Dow Corning Oil Dow Corning 556 Cosmetic Grade Fluid; - Silicones of the PK series from Bayer, for example product PK20; - PN and PH series silicones from Bayer, for example products PN1000 and PH1000; - Certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

[0207] Preferably, the hair coloring composition comprises at least one aminosilicone. The term "aminosilicone" refers to any silicone that contains at least one primary, secondary or tertiary amine or quaternary ammonium group.

[0208] The weight average molecular weight of these aminosilicones can be measured by gel permeation chromatography (GPC) at room temperature (25°C) in terms of polystyrene. A μ-styragel column is used. The eluent is THF, and the flow rate is 1 ml / min. 200 μl of a solution containing 0.5% by weight of silicone in THF is injected. Detection is performed by refractive index measurement and UV measurement.

[0209] Preferably, the aminosilicones that can be used in connection with the present invention are selected from: a) Formula (A): [ka] (wherein x' and y' are integers that result in a mass average molecular weight (Mw) of approximately 5,000 to 500,000) Polysiloxanes corresponding to: b) Formula (B): R'aG3-a-Si(OSiG2)n-(OSiGbR'2-b)mO-SiG3-a-R'a(B) (In the formula, G, which may be identical or different, represent a hydrogen atom or a radical from phenyl, OH, C1-C8 alkyl, such as methyl, or C1-C8 alkoxy, such as methoxy; a, which may be identical or different, represents 0 or an integer from 1 to 3, in particular 0, b represents 0 or 1, in particular 1; - m and n are numbers whose sum (n+m) ranges from 1 to 2000, in particular from 50 to 150, where n can represent a number from 0 to 1999, in particular from 49 to 149, and m can represent a number from 1 to 2000, in particular from 1 to 10; - R' may be the same or different and have the formula -CqH2qL, where q is a number ranging from 2 to 8, and L is one of the following groups: -N(R'')2; -N+(R'')3A-; -NR''-QN(R'')2; and -NR''-Q-N+(R'')3A-, where R'' may be the same or different and are hydrogen, phenyl, benzyl or a monovalent saturated hydrocarbon-based group, such as C1-C 20 represents an alkyl group; Q represents a group of formula C r H 2r (r is an integer ranging from 2 to 6, preferably from 2 to 4), represents a linear or branched group; A- is an optionally quaternized amine group selected from the group consisting of a cosmetically acceptable anion, in particular a halide anion, such as fluoride, chloride, bromide or iodide. The corresponding amino silicone.

[0210] Preferably, the aminosilicone is selected from aminosilicones of formula (B): Preferably, the aminosilicones of formula (B) are selected from aminosilicones corresponding to the following formulae (C), (D), (E), (F) and / or (G):

[0211] According to a first embodiment, the aminosilicone corresponding to formula (B) is of formula (C): [ka] (wherein m and n are numbers such that the sum (n+m) is in the range of 1 to 2000, particularly 50 to 150, n optionally representing a number of 0 to 1999, particularly 49 to 149, and m optionally representing a number of 1 to 2000, particularly 1 to 10). The silicone is selected from the group known as "trimethylsilylamodimethicone", which corresponds to

[0212] According to a second embodiment, the aminosilicone corresponding to formula (B) has the following formula (D): [ka] (In the formula, - m and n are numbers whose sum (n+m) is in the range of 1 to 1000, in particular in the range of 50 to 250, more particularly in the range of 100 to 200; n can represent a number from 0 to 999, in particular from 49 to 249, more particularly from 125 to 175, and m can represent a number from 1 to 1000, in particular from 1 to 10, more particularly from 1 to 5; - R1, R2 and R3 may be identical or different and represent a hydroxyl or a C1-C4 alkoxy group, and at least one of the R1-R3 groups represents an alkoxy group. The silicones are selected from the group consisting of:

[0213] Preferably, the alkoxy group is a methoxy group.

[0214] The hydroxy / alkoxy molar ratio is preferably in the range of 0.2:1 to 0.4:1, preferably 0.25:1 to 0.35:1, more particularly 0.3:1.

[0215] The mass average molecular weight (Mw) of these silicones is preferably in the range of 2,000 to 1,000,000, more particularly in the range of 3,500 to 200,000.

[0216] According to a third embodiment, the aminosilicone corresponding to formula (B) has the following formula (E): [ka] (In the formula, - p and q are numbers whose sum (p+q) is in the range of 1 to 1000, in particular in the range of 50 to 350, more particularly in the range of 150 to 250; p can represent a number from 0 to 999, in particular from 49 to 349, more particularly from 159 to 239, and q can represent a number from 1 to 1000, in particular from 1 to 10, more particularly from 1 to 5; - R1 and R2 are different and represent a hydroxyl or a C1-C4 alkoxy group, and at least one of the R1 or R2 groups represents an alkoxy group. The silicones are selected from the group consisting of:

[0217] Preferably, the alkoxy group is a methoxy group.

[0218] The hydroxy / alkoxy molar ratio is generally in the range of 1:0.8 to 1:1.1, preferably in the range of 1:0.9 to 1:1, and more particularly 1:0.95.

[0219] The mass average molecular weight (Mw) of the silicone is preferably in the range of 2,000 to 200,000, more particularly 5,000 to 100,000, and even more particularly 10,000 to 50,000.

[0220] Commercially available products containing silicones of structure (D) or (E) may contain in their composition one or more other aminosilicones having a structure different from formula (D) or (E).

[0221] A product containing aminosilicone of structure (D) is sold under the name Belsil® ADM 652 by Wacker.

[0222] Products containing aminosilicones of structure (E) are sold by Wacker under the names Fluid WR 1300® or Belsil® ADM LOG 1.

[0223] When these aminosilicones are used, a particularly advantageous embodiment involves their use in the form of an oil-in-water emulsion. The oil-in-water emulsion may contain one or more surfactants. The surfactants may be of any nature, but are preferably cationic and / or nonionic. The number-average particle size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nm. Preferably, microemulsions having an average particle size in the range of 5 nm to 60 nm (inclusive), more particularly in the range of 10 nm to 50 nm (inclusive), are used, especially for aminosilicones of formula (E). Thus, in accordance with the present invention, aminosilicone microemulsions of formula (E) sold by Wacker under the names Finish CT 96 E (registered trademark) or SLM 28020 (registered trademark) can be used.

[0224] According to a fourth embodiment, the aminosilicone corresponding to formula (B) has the following formula (F): [ka] (In the formula, - m and n are numbers whose sum (n+m) ranges from 1 to 2000, in particular from 50 to 150, where n can represent a number from 0 to 1999, in particular from 49 to 149, and m can represent a number from 1 to 2000, in particular from 1 to 10; - A represents a linear or branched alkylene group containing 4 to 8 carbon atoms, preferably 4 carbon atoms. The group is preferably linear.

[0225] The weight average molecular weight (Mw) of these aminosilicones is preferably in the range of 2,000 to 1,000,000, more specifically 3,500 to 200,000.

[0226] Other silicones corresponding to formula (B) are, for example, Xiameter MEM 8299 Emulsion from Dow Corning (INCI name: Amodimethicone and Trideceth-6 and Cetrimonium Chloride).

[0227] According to a fifth embodiment, the aminosilicone corresponding to formula (B) has the following formula (G): [ka] (In the formula, - m and n are numbers whose sum (n+m) ranges from 1 to 2000, in particular from 50 to 150, where n can represent a number from 0 to 1999, in particular from 49 to 149, and m can represent a number from 1 to 2000, in particular from 1 to 10; - A represents a linear or branched alkylene group containing 4 to 8 carbon atoms, preferably 4 carbon atoms. This group is preferably branched.

[0228] The weight average molecular weight (Mw) of these aminosilicones is preferably in the range of 500 to 1,000,000, and even more particularly 1,000 to 200,000.

[0229] A silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning.

[0230] c) Formula (H): [ka] (In the formula, R5 is a monovalent hydrocarbon-based radical containing 1 to 18 carbon atoms, in particular C1-C 18 Alkyl or C2-C 18 represents an alkenyl group, for example methyl; - R6 is a divalent hydrocarbon group, especially C1-C, bonded to Si via a SiC bond. 18 Alkylene group or divalent C1-C 18 For example, a C1-C8 alkyleneoxy group; - Q - is an anion, for example a halide ion, especially chloride, or an organic acid salt, especially acetate; - r represents a statistical mean value ranging from 2 to 20, especially from 2 to 8; - s represents a statistical mean value ranging from 20 to 200, especially 20 to 50) The corresponding amino silicone.

[0231] Aminosilicones of this type are described in particular in US Pat. No. 4,185,087.

[0232] - d) Formula (I): [ka] (In the formula, R7 may be identical or different and are monovalent hydrocarbon-based radicals containing 1 to 18 carbon atoms, in particular C1-C 18 Alkyl groups, C2-C 18 represents an alkenyl group or a ring containing 5 or 6 carbon atoms, for example methyl; - R6 is a divalent hydrocarbon group, especially C1-C, bonded to Si via a SiC bond. 18 Alkylene group or divalent C1-C 18 For example, a C1-C8 alkyleneoxy group; R8 may be identical or different and are a hydrogen atom, a monovalent hydrocarbon-based radical having 1 to 18 carbon atoms, in particular C1-C 18 Alkyl groups, C2-C 18 represents an alkenyl group or a -R6-NHCOR7 group; - X - is an anion, such as a halide ion, especially chloride, or an organic acid salt, especially acetate; - r represents a statistical mean value ranging from 2 to 200, especially from 5 to 100) Quaternary ammonium silicone.

[0233] These silicones are described, for example, in patent application EP-A-0 530 974.

[0234] e) Formula (J): [ka] (In the formula, R1, R2, R3 and R4 may be identical or different and represent a C1-C4 alkyl group or a phenyl group; R5 represents a C1-C4 alkyl group or a hydroxyl group; n is an integer ranging from 1 to 5; m is an integer ranging from 1 to 5; - x is selected so that the amine number is in the range of 0.01 to 1 meq / g) of amino silicone; f)(AB) n Multiblock polyoxyalkylenated aminosilicones of the type (A is a polysiloxane block and B is a polyoxyalkylene block containing at least one amine group).

[0235] The silicone preferably has the following general formula: [-(SiMeO) x SiMe2-RN(R'')-R'-O(C2H4O) a (C3H6O) b -R'-N(H)-R-], or Instead, [-(SiMe2O)xSiMe2-RN(R'')-R'-O(C2H4O) a (C3H6O) b -] (In the formula, a is an integer greater than or equal to 1, preferably ranging from 5 to 200, more particularly from 10 to 100; - b is an integer ranging from 0 to 200, preferably from 4 to 100, more particularly from 5 to 30; - x is an integer ranging from 1 to 10000, more particularly from 10 to 5000; R″ is a hydrogen atom or methyl; R is a linear or branched divalent C-C alkyl group which may be the same or different and optionally contains one or more heteroatoms such as oxygen. 12represents a hydrocarbon-based group; preferably, R represents an ethylene group, a linear or branched propylene group, a linear or branched butylene group or a CH2CH2CH2OCH2CH(OH)CH2- group; preferentially, R represents a -CH2CH2CH2OCH2CH(OH)CH2- group; R' is a linear or branched divalent C-C alkyl group which may be identical or different and optionally contains one or more heteroatoms such as oxygen. 12 represents a hydrocarbon-based group; preferably, R' represents an ethylene group, a linear or branched propylene group, a linear or branched butylene group or a -CH2CH2CH2OCH2CH(OH)CH2- group; preferentially, R' represents -CH(CH3)-CH2- It is formed from repeating units represented by the following formula:

[0236] The siloxane blocks preferably represent from 50 mol % to 95 mol %, more particularly from 70 mol % to 85 mol %, relative to the total mass of silicones.

[0237] The amine content is preferably between 0.02 and 0.5 meq / g, more particularly between 0.05 and 0.2, in a solution containing 30% of the copolymer in dipropylene glycol.

[0238] The mass average molecular weight (Mw) of the silicone is preferably 5,000 to 1,000,000, and more specifically 10,000 to 200,000.

[0239] Mention may be made, inter alia, of the silicones sold by Momentive under the names Silsoft A-843 or Silsoft A+.

[0240] g) and mixtures thereof.

[0241] Preferably, the aminosilicone of formula (B) is chosen from the aminosilicones corresponding to formula (E):

[0242] Preferably, the hair coloring composition comprises at least one aminosilicone with the INCI name Amodimethicone, preferably introduced in the form of an emulsion or microemulsion together with a surfactant.

[0243] Preferably, the hair coloring composition comprises at least one aminosilicone having the INCI name Amodimethicone as an emulsion or microemulsion together with surfactants having the INCI names Trideceth-5 and Trideceth-10.

[0244] The silicones may be present in a total amount ranging from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight, and even more preferentially from 0.5% to 5% by weight, relative to the total weight of the hair colouring composition.

[0245] The aminosilicones may be present in a total amount ranging from 0.01% to 20%, preferably from 0.05% to 15%, more preferentially from 0.1% to 10%, and even more preferentially from 0.5% to 5% by weight relative to the total weight of the hair colouring composition.

[0246] Associative Polymers The composition for coloring hair keratin fibers used in connection with the color removal method according to the invention may also comprise at least one associative polymer different from the non-carboxylic acid anionic thickeners described above.

[0247] Recall that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0248] Its chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0249] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon chain containing at least 10 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms, more preferentially 18 to 30 carbon atoms.

[0250] Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also represent a hydrocarbon-based polymer (for example, polybutadiene).

[0251] Associative polymers can be nonionic, anionic, cationic, or amphoteric.

[0252] Preferably, the associative polymer is selected from anionic associative polymers.

[0253] Among the anionic associative polymers that may be mentioned are the following: (a) those comprising at least one hydrophilic unit and at least one fatty chain allyl ether unit, more particularly those in which the hydrophilic unit is formed from an anionic ethylenically unsaturated monomer, more particularly those formed from a vinyl carboxylic acid, most particularly those formed from acrylic acid or methacrylic acid or a mixture thereof.

[0254] Among these anionic associative polymers, those particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and / or methacrylic acid, 5% to 60% by weight of lower alkyl (meth)acrylate, 2% to 50% by weight of aliphatic allyl ether, and 0 to 1% by weight of a crosslinker (a well-known copolymerizable unsaturated polyethylenic monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, or methylbisacrylamide).

[0255] Among the latter polymers, the most preferred are crosslinked terpolymers of methacrylic acid, ethyl acrylate and polyethylene glycol (10EO) stearyl alcohol ether (Steareth-10), in particular the aqueous 30% emulsion of crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10 allyl ether (40 / 50 / 10) sold by Ciba under the names Salcare SC 80® and Salcare SC 90®.

[0256] - (b) i) at least one hydrophilic unit of unsaturated olefinic carboxylic acid type and ii) at least one hydrophobic unit such as a (C10-C30) alkyl ester of unsaturated carboxylic acid type.

[0257] The unsaturated carboxylic acids useful in the present invention (C 10 ~C 30 ) Alkyl esters include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, and dodecyl acrylate and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

[0258] Anionic polymers of this type are described and prepared, for example, by US Pat. No. 3,915,921 and US Pat. No. 4,509,949.

[0259] Among this type of anionic associative polymer, 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C 10 ~C 30 alkyl acrylate (hydrophobic unit) and 0 to 6% by mass of a cross-linkable polymerizable monomer, or the above-mentioned, 98% to 96% by mass of acrylic acid (hydrophilic unit), 1% to 4% by mass of C 10 ~C 30 More particularly, one consisting of alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of a cross-linking polymerizable monomer will be used.

[0260] Among the above-mentioned polymers, those most particularly preferred according to the invention are Pemulen TR1®, Pemulen TR2®, Carbopol 1382®, and even more preferentially the product sold by Goodrich under the trade name Pemulen TR1® and the product sold by SEPPIC under the name Coatex SX®.

[0261] Mention may also be made of the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer sold by ISP under the name Acrylidone LM.

[0262] - (c) Maleic anhydride / C 30 ~C 38 α-olefin / alkyl maleate terpolymers, such as those sold under the trade name Performa V 1608® by Newphase Technologies (maleic anhydride / C 30 ~C 38 α-olefin / isopropyl maleate copolymer); (d) Acrylic terpolymers, including: i) approximately 20% by mass to 70% by mass of an α,β-monoethylenically unsaturated carboxylic acid [A]; ii) about 20% to 80% by weight of an α,β-monoethylenically unsaturated non-surfactant monomer other than [A]; iii) about 0.5% to 60% by weight of a nonionic monourethane that is the reaction product of a surfactant having one hydroxyl group and a monoethylenically unsaturated monoisocyanate; For example, the terpolymer described in EP 0 173 109, more specifically in Example 3, namely an aqueous 25% dispersion of terpolymer of methacrylic acid / methyl acrylate / behenyl alcohol dimethyl-meta-isopropenyl benzyl isocyanate ethoxylate (40EO). (e) Copolymers comprising as monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkylenated fatty alcohol.

[0263] Preferentially, these compounds also contain, as monomers, esters of α,β-monoethylenically unsaturated carboxylic acids and C1-C4 alcohols.

[0264] Examples of this type of compound include Aculyn 22®, sold by Roehm & Haas, which is a terpolymer of methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate, and Aculyn 88, also sold by Roehm & Haas.

[0265] Advantageously, the associative polymer different from the non-carboxylic anionic thickener is chosen from acrylic associative polymers, more preferentially carboxylic acrylic associative polymers.

[0266] Particularly preferably, the associative polymers are chosen from copolymers which contain among their monomers α,β-monoethylenically unsaturated carboxylic acids and esters of α,β-monoethylenically unsaturated carboxylic acids with oxyalkylenated fatty alcohols.

[0267] Advantageously, the total amount of associative polymer ranges from 0.05% to 15% by weight, preferably from 0.05% to 10% by weight, more preferentially from 0.1% to 5% by weight and even more preferentially from 0.1% to 1% by weight relative to the total weight of the hair colouring composition.

[0268] Compounds containing at least one carboxylic acid group The composition for coloring hair keratin fibers used in connection with the color removal method according to the invention comprises at least one associative polymer, and also at least one compound different from the associative polymer.

[0269] Preferably, the compound different from the associative polymer containing at least one carboxylic acid group is selected from silicone compounds, polyurethanes, acrylic polymers and mixtures thereof containing at least one carboxyl group.

[0270] Polyurethane and acrylic polymers According to a preferred embodiment, the composition for coloring hair keratin fibers comprises one or more compounds, different from the associative polymer, containing at least one carboxylic acid group selected from polyurethanes, acrylic polymers and mixtures thereof.

[0271] Preferably, the compound different from the associative polymer containing at least one carboxylic acid group is in the form of an aqueous dispersion of particles of a polymer chosen from polyurethanes, acrylic polymers and mixtures thereof.

[0272] Preferably, the composition for coloring hair keratin fibers comprises one or more compounds different from the associative polymer, containing at least one carboxylic acid group, in the form of an aqueous dispersion of particles of a polymer chosen from polyurethanes, acrylic polymers and mixtures thereof.

[0273] Thus, in this embodiment, the polymer used in the aqueous dispersion of polymer particles is different from the associative polymer.

[0274] The dispersion may be a simple dispersion of the cosmetic composition in an aqueous medium. A specific example of a dispersion is a latex.

[0275] The aqueous dispersion of polymer particles may be selected from aqueous dispersions of polyurethane particles.

[0276] More particularly, the polyurethane present in the aqueous dispersion used in the present invention is - the following formula (A): [ka] (In the formula, R1 represents a divalent radical of a dihydroxylated compound, R2 represents the radical of an aliphatic or cycloaliphatic polyisocyanate, R3 represents a radical of a low molecular weight diol optionally substituted with one or more ionic groups, n represents an integer ranging from 1 to 5, and - m is greater than 1) and a prepolymer of; - the following formula (B): H2N-R4-NH2(B) wherein R4 represents an alkylene or alkylene oxide group that is not substituted with one or more ionic or potentially ionic groups. with at least one chain extender according to the formula: - the following formula (C): H2N-R5-NH2(C) wherein R5 represents an alkylene group substituted with one or more ionic or potentially ionic groups. and at least one chain extender according to It is obtained by the reaction:

[0277] Among the dihydroxylated compounds that can be used according to the present invention, mention may be made in particular of compounds containing two hydroxyl groups and having a number average molecular weight of about 700 to about 16,000, preferably about 750 to about 5,000. Examples of high molecular weight dihydroxylated compounds include polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadiene, polyhydroxylated polythioethers, and mixtures thereof. Preferably, the hydroxylated compound is selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0278] The polyisocyanates that can be used according to the invention are chosen in particular from organic diisocyanates having a molecular weight of about 112 to 1000, preferably about 140 to 400.

[0279] Preferably, the polyisocyanate is selected from diisocyanates, more particularly from those represented by the general formula R2(NCO)2, where R2 represents a divalent aliphatic hydrocarbon group containing 4 to 18 carbon atoms, a divalent alicyclic hydrocarbon group containing 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group containing 7 to 15 carbon atoms, or a divalent aromatic hydrocarbon group containing 6 to 15 carbon atoms.

[0280] Preferably, R2 represents an organic diisocyanate. Examples of organic diisocyanates may be selected in particular from: tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)methane, isomers of toluene diisocyanate (TDI), such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, diphenylmethane 4,4'-diisocyanate and mixtures thereof with its diphenylmethane 2,4-diisocyanate isomer, optionally with diphenylmethane 2,2'-diisocyanate isomer, naphthalene 1,5-diisocyanate and mixtures thereof.

[0281] Preferably, the diisocyanates are aliphatic and cycloaliphatic diisocyanates, more preferentially chosen from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate and mixtures thereof.

[0282] The term "low molecular weight diols" according to the present invention refers to diols having a molecular weight of about 62 to 700, preferably 62 to 200. These diols may contain aliphatic, alicyclic or aromatic groups. Preferably, they contain only aliphatic groups.

[0283] Preferably, R3 represents a low molecular weight diol containing more than 20 carbon atoms and is more preferentially selected from ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, neopentyl glycol, butylethylpropanediol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane) and mixtures thereof.

[0284] The low molecular weight diols may optionally contain ionic or potentially ionic groups. Examples of low molecular weight diols containing ionic or potentially ionic groups are described, inter alia, in patent US 3,412,054. Compounds of this type are preferably selected from dimethylol butanoic acid, dimethylol propionic acid, polycaprolactone diols containing carboxyl groups, and mixtures thereof.

[0285] When low molecular weight diols containing ionic or potentially ionic groups are used, they are preferably used in an amount such that less than 0.30 meq of COOH per gram of polyurethane is present in the polyurethane dispersion.

[0286] The prepolymer is chain extended by using chain extenders belonging to two groups: The first group of chain extenders corresponds to compounds of general formula (B):

[0287] The chain extender of formula (B) is preferably an alkylene diamine, such as hydrazine, ethylene diamine, propylene diamine, 1,4-butylene diamine, piperazine; an alkylene oxide diamine, such as 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine (also known as dipropylamine diethylene glycol or DPA-DEG, available from Tomah Products, Milton, Wis.), 2-methyl-1,5-pentanediamine (Dytec A from DuPont), hexane diamine, isophorone diamine, 4,4-methylenedi(cyclohexylamine), Tomah and mixtures thereof.

[0288] The second group of chain extenders corresponds to compounds of general formula (C). Compounds of this type preferably have an ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Compounds of this type can optionally contain two groups that react with isocyanate groups and one group that is ionic or capable of forming an ionic group.

[0289] The ionic or potentially ionic groups may preferably be selected from tertiary or quaternary ammonium groups or groups that can be converted into such groups, carboxyl groups, carboxylate groups, sulfonic acid groups and sulfonate groups. The conversion of at least a portion of the groups that can be converted into salts of tertiary or quaternary ammonium groups can be carried out before or during mixing with water.

[0290] The chain extender of formula (C) is preferably selected from diaminosulfonates, such as the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid, and mixtures thereof.

[0291] The polyurethanes that can be used according to the invention can also optionally contain compounds (chain terminators) located at the respective chain ends that terminate the chains, such compounds being described in particular in US Pat. No. 7,445,770 and / or US Pat. No. 7,452,770.

[0292] Preferably, the viscosity of the aqueous dispersion of polyurethane particles is less than 2000 mPa.s at 23°C, more preferentially less than 1500, and even better still less than 1000. Even more preferably, the glass transition temperature of the aqueous dispersion of polyurethane particles is less than 0°C.

[0293] Also preferably, the polyurethane (or active substance or solids) content of the aqueous polyurethane dispersion is from 20% to 60% by weight, more preferentially from 25% to 55% by weight, and even better still from 30% to 50% by weight, based on the weight of the dispersion. This is intended to mean that the polyurethane content (dry matter) of the aqueous dispersion is preferably from 20% to 60% by weight, more preferentially from 25% to 55% by weight, and even better still from 30% to 50% by weight, relative to the total weight of the dispersion.

[0294] Also preferably, the glass transition temperature (Tg) of the aqueous dispersion of polyurethane particles is lower than or equal to -25°C, preferably lower than -35°C and more preferentially lower than -40°C.

[0295] The average size of the polyurethane particles can be up to about 1000 nm, for example, in the range of about 50 nm to about 800 nm, and even better, about 100 nm to about 500 nm. These particle sizes can be measured using a laser particle size distribution analyzer (e.g., Brookhaven BI90).

[0296] Non-limiting examples of aqueous polyurethane dispersions include those sold by Bayer under the name Baycusan®, such as Baycusan® C1000 (INCI name: Polyurethane-34), Baycusan® C1001 (INCI name: Polyurethane-34), Baycusan® C1003 (INCI name: Polyurethane-32), Baycusan® C1004 (INCI name: Polyurethane-35) and Baycusan® C1008 (INCI name: Polyurethane-48).

[0297] Mention may also be made of aqueous polyurethane dispersions of isophthalic acid / adipic acid copolymer / hexylene glycol / neopentyl glycol / dimethylol acid / isophorone diisocyanate (INCI name: Polyurethane-1, for example Luviset® PUR from BASF), polyurethanes of polycarbonate, polyurethanes of aliphatic polyesters and aliphatic polyurethanes (for example the Neorez® series from DSM, such as Neorez® R989, Neorez® and R-2202).

[0298] According to a preferred embodiment, the aqueous dispersion of polyurethane particles may be chosen from aqueous dispersions of particles of a compound having the INCI name Polyurethane-35 or of a compound having the INCI name Polyurethane-34.

[0299] Preferably, the compound different from the associative polymer containing at least one carboxylic acid group is in the form of an aqueous dispersion of particles of an acrylic polymer, more preferentially in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0300] For the purposes of the present invention, the term "polymer" means a compound corresponding to the repetition of one or more units, which are derived from compounds known as monomers, where this or these units are repeated at least twice, preferably at least three times.

[0301] The term "film-forming polymer" refers to a polymer that is capable of forming a macroscopically continuous, preferably a coherent, film on a substrate, in particular a keratinous material, either alone or in the presence of an auxiliary film-forming agent.

[0302] For the purposes of the present invention, the term "acrylic polymer" means a polymer synthesized from at least one monomer selected from (meth)acrylic acid and / or (meth)acrylic acid esters and / or (meth)acrylic acid amides.

[0303] The units of the polymer derived from (meth)acrylic acid monomers may optionally be in the form of a salt, in particular an alkali metal salt, an alkaline earth metal salt or an ammonium salt, or an organic base salt.

[0304] The (meth)acrylic acid esters (also known as (meth)acrylates) are advantageously alkyl (meth)acrylates, in particular C1-C 30 , preferably C1 to C 20 , and even better C1 to C 10 Alkyl (meth)acrylates, aryl (meth)acrylates, especially C6-C 10 It is selected from aryl (meth)acrylates and hydroxyalkyl (meth)acrylates, in particular C2 to C6 hydroxyalkyl (meth)acrylates.

[0305] Among the alkyl (meth)acrylates, mention may be made of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and cyclohexyl (meth)acrylate.

[0306] Among the hydroxyalkyl(meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0307] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0308] Particularly preferred (meth)acrylic acid esters are alkyl, preferably C1-C 30 , and more preferentially C1~C 20 , and even better still C1 to C 10 and even more particularly C1 to C4 alkyl (meth)acrylates.

[0309] According to the present invention, the alkyl group of the ester may be fluorinated or even perfluorinated, ie some or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms.

[0310] Examples of (meth)acrylic acid amides include (meth)acrylamides as well as N-alkyl(meth)acrylamides, particularly N-(C-C 12 Mention may also be made of N-alkyl(meth)acrylamides. Among the N-alkyl(meth)acrylamides, mention may be made of N-ethylacrylamide, Nt-butylacrylamide, Nt-octylacrylamide and N-undecylacrylamide.

[0311] The acrylic polymer according to the invention may be a homopolymer or a copolymer, advantageously a copolymer, and even better a copolymer of (meth)acrylic acid and of a (meth)acrylic acid ester.

[0312] Preferably, the acrylic polymer according to the present invention comprises the following monomers: a) (meth)acrylic acid; and b) C1~C 30 , and more preferentially C1~C 20 , and even better C1 to C 10 , more particularly C1-C4 alkyl (meth)acrylate Contains one or more units derived from

[0313] Preferably, the aqueous dispersion of acrylic polymer particles is surfactant-free.

[0314] The term "surfactant" refers to any agent that can modify the surface tension between two surfaces.

[0315] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and ethyl acrylate, such as the compound sold by BASF under the trade name Luvimer MAE, or the compound sold by Lubrizol under the trade name Fixate Superhold Polymer, such as polyacrylate-2 crosspolymer, or the compound sold by Daito Kasei Kogyo under the trade name Daitosol 3000VP3, or the compound sold by Daito Kasei Kogyo under the trade name Daitosol 3000 SLPN-PE1, such as acrylate copolymer.

[0316] The acrylic polymer may optionally contain one or more additional monomers other than (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide monomers.

[0317] Additional monomers may include, for example, styrene monomers, particularly styrene and alpha-methylstyrene, preferably styrene.

[0318] In particular, the acrylic polymer is a styrene / (meth)acrylate copolymer, in particular a copolymer of at least one styrene monomer and at least one C1-C6 (meth)acrylate copolymer. 20 , preferably C1 to C 10 The polymer may be a copolymer selected from copolymers obtained by polymerizing alkyl (meth)acrylate monomers.

[0319] C1~C 10 The alkyl (meth)acrylate monomer may be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate.

[0320] Among the acrylic polymers, mention may be made of styrene / (meth)acrylate copolymers sold under the names Joncryl 77 by BASF, Yodosol GH41F by Akzo Nobel and Syntran 5760 CG by Interpolymer.

[0321] Preferably, the hair coloring composition comprises at least one aqueous dispersion of acrylic polymer particles.

[0322] More preferentially, the hair coloring composition comprises the following monomers: a) (meth)acrylic acid; and b) C1~C 30 , and more preferentially C1~C 20 , and even better C1 to C 10 , more particularly C1-C4 alkyl (meth)acrylate and at least one aqueous dispersion of acrylic polymer particles comprising one or more units derived from

[0323] Preferably, the acrylic polymer (or active substance or solids) content of the aqueous dispersion of acrylic polymer particles is between 20% and 60% by weight, more preferentially between 22% and 55% by weight, and even better still between 25% and 50% by weight, based on the weight of the dispersion.

[0324] The total amount of compounds different from the associative polymer and containing at least one carboxylic acid group preferably ranges from 0.1% to 35% by weight, more preferentially from 0.5% to 30% by weight, even better from 1% to 25% by weight and even more preferentially from 3% to 25% by weight relative to the total weight of the hair colorant composition.

[0325] The total amount of aqueous dispersion of polymer particles different from the aforementioned associative polymers, selected from polyurethanes, acrylic polymers and mixtures thereof, preferably ranges from 0.1% to 35% by weight, more preferentially from 0.5% to 30% by weight, even more preferably from 1% to 25% by weight and even more preferentially from 3% to 25% by weight, relative to the total weight of the hair colorant composition.

[0326] According to a particular embodiment, the total amount of aqueous dispersion of acrylic polymer particles different from the associative polymers described above preferably ranges from 0.1% to 35% by weight, more preferentially from 0.5% to 30% by weight, better still from 1% to 25% by weight and even more preferentially from 3% to 25% by weight relative to the total weight of the hair colorant composition.

[0327] organic solvents The dye composition used in connection with the method according to the present invention may contain one or more organic solvents.

[0328] Examples of organic solvents include lower C1-C4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether and diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0329] Preferably, the hair colouring composition comprises one or more organic solvents selected from C1 to C4 lower alkanols, more preferentially ethanol.

[0330] The organic solvent may be present in a total amount of from about 0.01% to 60% by weight (inclusive) relative to the total weight of the hair colorant composition, preferably from 0.05% to 50% by weight, and more preferentially from 0.1% to 45% by weight (inclusive) relative to the total weight of the hair colorant composition.

[0331] The hair coloring compositions used in connection with the method according to the invention are preferably aqueous: the water content may range from 20% to 99% by weight, preferably from 50% to 98% by weight, and more preferentially from 60% to 95% by weight, relative to the total weight of the hair coloring composition.

[0332] additives The composition for coloring hair keratin fibers used in connection with the method according to the invention may contain any adjuvant or additive normally used.

[0333] Among the additives that may be included in the hair coloring composition may be mentioned reducing agents, emollients, antifoaming agents, moisturizing agents, UV screening agents, deflocculants, solubilizing agents, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, preservatives, oils, waxes and mixtures thereof.

[0334] The composition for coloring hair keratin fibers may in particular be in the form of a suspension, dispersion, gel, emulsion, in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion or a multiphase emulsion (W / O / W or polyol / O / W or O / W / O), a cream, a mousse, a stick, a vesicle, in particular a dispersion of ionic or nonionic lipids or a two-phase or multiphase lotion.

[0335] A person skilled in the art will be able, based on his general knowledge, to select a suitable presentation form as well as a method for preparing it, taking into account first the properties of the components used, in particular their solubility in the carrier, and then the intended use of the composition.

[0336] Optional Application of Composition D The method for removing color from hair keratin fibers, such as hair, according to the present invention may also comprise the step of applying to the hair keratin fibers a composition D comprising at least one silicone compound containing at least one carboxyl group, said application of composition D being carried out before the application of the color removing composition.

[0337] The term "carboxyl group" refers to COOH or COO - It means functional group, COO - The counterions of the groups can be selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0338] The silicones that can be used may be soluble or insoluble in composition D and may be in the form of oils, waxes, resins or gums, with silicone oils and gums being preferred.

[0339] Silicones are particularly well-described in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press.

[0340] Preferably, the silicone compound containing at least one carboxyl group has the following formula (XXVII): [ka] (In the formula, R1 independently represents an alkyl group containing 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; a hydroxyl group; an alkoxy group containing 1 to 20 carbon atoms; or an aryl group containing 6 to 12 carbon atoms; R2 independently represent a group R4-COOM, where R4 represents a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur, nitrogen, oxygen and mixtures thereof, and M represents a hydrogen atom; an alkali metal or alkaline earth metal or quaternary ammonium NR'3, where R' may be identical or different and represent H or an alkyl group containing 1 to 4 carbon atoms; a carboxyl group COOH or a pyrrolidine group containing the group Ra-(ORb)x-COOM, where Ra represents a linear or branched alkylene group containing 1 to 4 carbon atoms, Rb represents an alkyl group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; M represents a hydrogen atom, an alkali metal or alkaline earth metal or quaternary ammonium NR'3, where R' may be identical or different and represent H or an alkyl group containing 1 to 4 carbon atoms; - R3 independently represents an alkyl group containing 1 to 20 carbon atoms; a hydroxyl group; an R4-COOM group (R4 represents a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof, and M represents a hydrogen atom); an alkali metal or alkaline earth metal or quaternary ammonium NR'3 (R' may be the same or different and represents H or an alkyl group containing 1 to 4 carbon atoms); an alkoxy group containing 1 to 20 carbon atoms; an aryl group containing 6 to 12 carbon atoms or an R a -(OR b ) x -COOM group (in the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, and R brepresents an alkyl group containing 1 to 4 carbon atoms, x is an integer ranging from 1 to 200; M represents a hydrogen atom, an alkali metal or alkaline earth metal, or a quaternary ammonium NR'3 (wherein R' may be the same or different and represents H or an alkyl group containing 1 to 4 carbon atoms); - n represents an integer ranging from 1 to 1000; - p represents an integer ranging from 0 to 1000; It is understood that at least one of the R2 and / or R3 groups comprises a carboxyl group COOH or COOM, where M represents an alkali metal or alkaline earth metal or a quaternary ammonium NR'3, where R' may be the same or different and represents H or an alkyl containing 1 to 4 carbon atoms. The organosiloxanes are selected from the following:

[0341] In particular, the silicone compound containing at least one carboxyl group can be chosen from: Formula (XXVIII): [ka] (In the formula, R1 independently represent a linear or branched alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and even better from 1 to 6 carbon atoms, preferentially methyl; R4 independently represents a linear or branched alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof; or a divalent group R a -(OR b ) x -(In the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, and R b represents an alkylene group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; M independently represents a hydrogen atom, an alkali metal or alkaline earth metal, or a quaternary ammonium NR'3, where R' may be identical or different and represents H or alkyl containing 1 to 4 carbon atoms; - n represents an integer ranging from 1 to 1000 of organosiloxanes; of the following formula (XXIX): [ka] (In the formula, R1 independently represent an alkyl group containing 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferentially methyl; R4 is a linear or branched, saturated or unsaturated alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof; or a divalent group R a -(OR b ) x -(In the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, and R b represents an alkylene group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; M represents a hydrogen atom, an alkali metal or alkaline earth metal or a quaternary ammonium NR'3, where R' may be identical or different and represent H or alkyl containing 1 to 4 carbon atoms; - p represents an integer ranging from 1 to 1000; - n represents an integer ranging from 1 to 1000 of organosiloxanes; - the following formula (XXX): [ka] (In the formula, R1 independently represent an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and even better from 1 to 6 carbon atoms, preferentially methyl; R4 is a linear or branched alkylene group containing from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof; or a divalent group R a -(OR b ) x -(In the formula, R a represents a linear or branched alkylene group containing 1 to 4 carbon atoms, and R b represents an alkylene group containing 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; R3 represents an alkyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms, or an aryl group containing 6 to 12 carbon atoms; M independently represents a hydrogen atom, an alkali metal or alkaline earth metal, or a quaternary ammonium NR'3, where R' may be identical or different and represents H or alkyl containing 1 to 4 carbon atoms; - n represents an integer ranging from 1 to 1000 of organosiloxanes; of the following formula (XXXI): [ka] (In the formula, R8 represents an alkyl group containing 1 to 6 carbon atoms, preferably methyl; - m represents an integer ranging from 1 to 1000; - n represents an integer ranging from 1 to 1000 Organosiloxanes of the formula: - A mixture of them.

[0342] Among the organosiloxanes of formula (XXVIII), mention may be made of polydimethylsiloxanes (PDMS) having carboxyl end groups, such as the compound sold by the company Momentive under the trade name Silform INX (INCI name: Biscarboxydecyldimethicone).

[0343] Among the organosiloxanes of formula (XXIX), mention may be made of polydimethylsiloxanes (PDMS) having pendant carboxyl groups, such as the compound sold by Shin-Etsu Chemical Co., Ltd. under the trade name X-22-3701E.

[0344] Among the organosiloxanes of formula (XXX), mention may be made of polydimethylsiloxanes (PDMS) having carboxyl end groups, such as the compound sold by Shin-Etsu Chemical Co., Ltd. under the trade name X-22-3710.

[0345] Among the organosiloxanes of formula (XXXI), mention may be made of the compound sold by Grant Industries under the trade name Grandsil SiW-PCA-10 (INCI name: dimethicone and PCA dimethicone and butylene glycol and decyl glucoside).

[0346] The silicone compounds containing carboxyl groups may correspond, for example, to the compounds described in EP 186507 in the name of Chisso Corporation, which is incorporated herein by reference.

[0347] Preferably, the silicone compound containing at least one carboxyl group is selected from organosiloxanes of formula (XXVIII), organopolysiloxanes of formula (XXIX), and mixtures thereof.

[0348] More preferentially, the silicone compound containing at least one carboxyl group has the following formula (XXIXa): [ka] (In the formula, R4 represents a linear or branched, saturated or unsaturated alkylene group containing 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms and mixtures thereof or by 8 to 12 carbon atoms; - p represents an integer ranging from 1 to 1000; - n represents an integer ranging from 1 to 1000 The organosiloxanes are selected from the following:

[0349] The total amount of silicone compounds containing at least one carboxyl group present in composition D preferably ranges from 0.01% to 20% by weight, more preferentially from 0.1% to 15% by weight, and even better still from 0.5% to 10% by weight, relative to the total weight of composition D.

[0350] oil Composition D may also include one or more oils.

[0351] Preferably, composition D comprises one or more oils. More preferentially, composition D comprises one or more oils chosen from alkanes.

[0352] The term "oil" refers to oil at room temperature (25°C) and atmospheric pressure (760 mmHg, i.e., 1.013 x 10 5 "Liquid" refers to a fatty substance that is liquid at temperatures below 100°C (Pa).

[0353] The oil may be volatile or non-volatile.

[0354] The term "volatile oil" refers to an oil that can evaporate in less than one hour upon contact with the skin at room temperature and atmospheric pressure. Volatile oils are cosmetic volatile oils that are liquid at room temperature. More specifically, the evaporation rate of volatile oils is between 0.01 and 200 mg / cm. 2 / min inclusive (see evaporation rate measurement procedure later in the text).

[0355] The term "non-volatile oil" refers to an oil that remains on the skin or keratinous fibers at room temperature and atmospheric pressure. More specifically, the evaporation rate of a non-volatile oil is exactly 0.01 mg / cm 2 / min (see procedure for measuring evaporation rate later in the text).

[0356] Preferably, the composition contains C6 to C 16 It comprises one or more oils selected from alkanes and / or mixtures thereof.

[0357] C6~C 16 With respect to alkanes, these may be straight-chain or branched, and optionally cyclic.

[0358] In particular, branches C8 to C 16 Alkanes, e.g., C8-C 16 Mention may be made of isoalkanes (also known as isoparaffins), isododecane, isodecane or isohexadecane, for example the oils sold under the trade names Isopar or Permethyl, and mixtures thereof.

[0359] Mention may also be made of linear alkanes, preferably of plant origin, containing 7 to 15 carbon atoms, in particular 9 to 14 carbon atoms, more particularly 11 to 13 carbon atoms.

[0360] Examples of linear alkanes suitable for use in the present invention include n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14) and n-pentadecane (C15) and mixtures thereof, in particular the mixture of n-undecane (C11) and n-tridecane (C13) described in Example 1 of Cognis patent application WO 2008 / 155059.

[0361] Mention may also be made of n-dodecane (C12) and n-tetradecane (C14), sold under the trade designations Parafol 12-97 and Parafol 14-97, respectively, by Sasol, as well as mixtures thereof.

[0362] Examples of alkanes suitable for use in the present invention include those described in patent applications WO 2007 / 068371 and WO 2008 / 155059. These alkanes are obtained from fatty alcohols, which themselves are obtained from coconut kernel oil or palm oil.

[0363] According to a particular embodiment, the composition comprises isododecane. A compound of this type is, for example, isododecane sold by Ineos under the trade designation Isododecane.

[0364] Preferably, composition D is C8 to C 16 It comprises one or more oils chosen from alkanes, more preferentially from isododecane, isohexadecane, tetradecane and / or mixtures thereof.

[0365] More preferentially, composition D comprises isododecane.

[0366] Composition D may comprise one or more oils present in a total amount of from 30% to 99% by weight, preferably from 50% to 99% by weight and even better still from 70% to 99% by weight relative to the total weight of the composition.

[0367] Composition D may contain at least one colorant selected from the pigments, direct dyes and mixtures thereof previously described.

[0368] color removing composition As indicated above, the method for removing color from hair keratinous fibers, in particular hair, comprises applying at least one color removing composition to said hair keratinous fibers that have been previously colored using at least one composition for coloring hair keratinous fibers as defined above, said color removing composition comprising at least one glycol ether and, optionally, at least one alkyl or alkylene carbonate.

[0369] Glycol Ether The term "glycol ether" refers to one or more glycol ethers, which may or may not contain hydroxyl groups.

[0370] Preferably, the glycol ether is of the formula R 11 (-O-CH(CH3)-CH2) n OH (in the formula, R 11 is C1~C 30 , preferably a C1 to C6, more preferentially a C1 to C4 alkyl group, and n is 1 to 50, preferably 2 to 50, more preferably 2 to 10, preferentially 2 to 5).

[0371] Advantageously, the glycol ether has the formula CH3(-O-CH(CH3)-CH2) n OH (wherein n is 2 to 50, preferably 2 to 10, more preferentially 2 to 5).

[0372] Particularly preferably, the glycol ether is selected from tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol propyl ether, tripropylene glycol butyl ether and mixtures thereof, preferably tripropylene glycol methyl ether.

[0373] The total content of glycol ethers is preferably at least 5% by weight, more preferentially at least 10% by weight, relative to the total weight of the colour removal composition.

[0374] The total content of glycol ethers may range from 5% to 100% by weight, preferably from 5 to 80% by weight, more preferentially from 5 to 60% by weight, even more preferentially from 5 to 50% by weight, more preferably from 5 to 40% by weight, even more preferably from 10 to 40% by weight, and even more preferably from 20 to 40% by weight, relative to the total weight of the colour removal composition.

[0375] Alkyl or alkylene carbonate The color removal composition used in connection with the method according to the present invention may comprise at least one alkyl or alkylene carbonate.

[0376] The term "alkyl carbonate" means an alkyl or dialkyl carbonate.

[0377] Preferably, the alkyl or alkylene carbonate is a C1-C 30 , preferably C1 to C6 alkyl or C1 to C 30 More preferentially, the alkyl or alkylene carbonate is chosen from alkylene carbonates, and even better from propylene carbonate, butylene carbonate, pentylene carbonate and mixtures thereof.

[0378] Particularly preferably, the alkyl or alkylene carbonate is selected from propylene carbonate.

[0379] Advantageously, the total content of alkyl or alkyl carbonates ranges from 10% to 60% by weight, preferably from 15% to 50% by weight, relative to the total weight of the colour removal composition.

[0380] polyol The color removal composition used in connection with the method according to the present invention may comprise at least one polyol different from the glycol ethers mentioned above.

[0381] For the purposes of the present invention, the term "polyol" means an organic compound composed of a hydrocarbon-based chain optionally interrupted by one or more oxygen atoms and having at least two free hydroxyl groups (-OH) carried by different carbon atoms, which compound may be cyclic or acyclic, linear or branched, and saturated or unsaturated.

[0382] More particularly, the polyol contains from 2 to 30 hydroxyl groups, more preferentially from 2 to 10 hydroxyl groups, and even more preferentially from 2 to 3 hydroxyl groups.

[0383] The color removal composition may preferably comprise one or more polyols selected from diglycerol, glycerol, propylene glycol, propane-1,3-diol, 1,3-butylene glycol, pentane-1,2-diol, octane-1,2-diol, dipropylene glycol, hexylene glycol, ethylene glycol, polyethylene glycol, sorbitol, sugars such as glucose, and mixtures thereof.

[0384] Particularly preferably, the polyol is selected from dipropylene glycol.

[0385] The polyol content advantageously ranges from 1% to 50% by weight, preferably from 5% to 30% by weight and more preferentially from 5% to 20% by weight relative to the total weight of the colour removal composition.

[0386] Alkaline agent The color removal composition used in connection with the method according to the present invention may also include at least one alkaline agent.

[0387] Preferably, the alkaline agent may be selected from organic alkaline agents and inorganic alkaline agents, more preferentially organic alkaline agents.

[0388] Preferably, the organic alkaline agent is selected from organic amines having a pKb at 25°C of less than 12, more preferably less than 10, and even more preferentially less than 6. It should be noted that this is the pKb corresponding to the most basic functional group. In addition, the organic amine does not contain alkyl or alkenyl fatty chains containing more than 10 carbon atoms.

[0389] The organic alkaline agent is preferably selected from alkanolamines, in particular mono-, di- or tri-hydroxy(C1-C6)alkylamines, such as 2-amino-2-methylpropanol, monoethanolamine, oxyethylenated and / or oxypropylenated ethylenediamines, amino acids, polyamines of formula (I) below and mixtures thereof. [ka] In formula (I), W is a divalent C1-C6 alkylene group optionally substituted with one or more hydroxyl groups or C1-C6 alkyl groups and / or optionally interrupted with one or more heteroatoms such as O, or -NR u and;R x , R y , R z , R t and R u (which may be the same or different) represent a hydrogen atom, a C1 to C6 alkyl group, a C1 to C6 hydroxyalkyl group, or a C1 to C6 aminoalkyl group.

[0390] Examples of amines of formula (I) include 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

[0391] The term "alkanolamine" means an organic amine containing a primary, secondary, or tertiary amine functional group and one or more linear or branched C1-C8 alkyl groups bearing one or more hydroxyl groups.

[0392] Organic amines selected from alkanolamines, such as monoalkanolamines, dialkanolamines or trialkanolamines, containing 1 to 3 identical or different C1 to C4 hydroxyalkyl groups are particularly suitable for carrying out the present invention.

[0393] Among compounds of this type, mention may be made of monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol and tris(hydroxymethylamino)methane.

[0394] More particularly, the amino acids that can be used are of natural or synthetic origin, in L-, D- or racemic form, and more particularly contain at least one acid function selected from carboxylic acid, sulfonic acid, phosphonic acid and phosphoric acid functions. The amino acids can be in neutral or ionic form.

[0395] Amino acids that may be used in the present invention may include, inter alia, aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine.

[0396] Advantageously, the amino acid is a basic amino acid containing an additional amine function, optionally in the ring or in the ureido group.

[0397] Such basic amino acids preferably have the following formula (II): R-CH2-CH(NH2)-C(O)-OH (II) (In formula (II), R represents a group selected from imidazolyl, preferably imidazolyl-4-yl; aminopropyl; aminoethyl; —(CH)N(H)—C(O)—NH; and —(CH)—N(H)—C(NH)—NH). and also salts thereof.

[0398] The organic amines can also be chosen from organic amines of the heterocyclic type. In addition to histidine, which has already been mentioned with respect to the amino acids, mention may in particular also be made of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.

[0399] The organic amine can also be selected from amino acid dipeptides, including carnosine, anserine and balenine, among others, that can be used in the present invention.

[0400] The organic amine can also be selected from compounds containing a guanidine functional group. In addition to arginine, which has already been mentioned as an amino acid, amines of this type that can be used in the present invention include, in particular, creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid 2-([amino(imino)methyl]amino)ethane-1-sulfonic acid, and guanidine carbonate.

[0401] Preferably, the alkaline agent is selected from alkanolamines, more preferentially from monoethanolamines.

[0402] When present, the content of alkaline agent advantageously ranges from 0.01% to 10% by weight, preferably from 0.1% to 5% by weight and more preferentially from 0.1% to 2% by weight relative to the total weight of the colour removal composition.

[0403] Water-soluble organic solvent The color removal composition used in connection with the method according to the present invention may comprise at least one water-soluble organic solvent selected from monoalcohols containing from 1 to 5 carbon atoms, such as ethanol, isopropanol, and butanol.

[0404] The color removal composition used in connection with the method according to the present invention may comprise water.

[0405] According to another particular embodiment, the color removal composition is water-free.

[0406] Additionally, the additives described above may be included in the color removal composition used in connection with the method according to the present invention.

[0407] protocol The hair keratin fiber coloring composition and optional composition D can be used on wet or dry hair keratin fibers, and on any type of hair keratin fiber, whether light or dark, natural or colored, permanently waved, bleached or straightened.

[0408] According to a preferred embodiment, the hair coloring composition and composition D are applied simultaneously to the hair keratinous fibers.

[0409] According to another preferred embodiment, composition D is applied to the hair keratinous fibers after the hair coloring composition has been applied to the hair keratinous fibers.

[0410] According to another preferred embodiment, composition D is applied to the hair keratinous fibers before applying the composition for coloring hair keratinous fibers.

[0411] According to a particular embodiment of the present invention, the hair keratin fibers, for example the hair, are washed before applying the composition for coloring hair keratin fibers and optional composition D.

[0412] Preferably, a washing, rinsing, dewatering or drying step is carried out after applying the hair coloring composition to the hair keratinous fibers and before applying composition D to the keratinous fibers.

[0413] More preferentially, a drying step is carried out after applying the hair coloring composition to the hair keratinous fibers and before applying composition D to the hair keratinous fibers.

[0414] Application to the hair keratin fibers can be carried out by any standard means, in particular with a comb, a fine-toothed brush, a wide-toothed brush, a sponge or the fingers.

[0415] The application of the composition for coloring hair keratinous fibers and the optional composition D to the keratinous fibers is generally carried out at room temperature (15 to 25° C.).

[0416] After application of the hair coloring composition to the hair keratinous fibers, it can be left for 1 minute to 6 hours, in particular 1 minute to 2 hours, more particularly 1 minute to 1 hour, and more preferentially 1 minute to 30 minutes, before applying, for example, composition D to the hair keratinous fibers or before, for example, a washing, rinsing, dewatering or drying step.

[0417] Preferably, after the hair coloring composition has been applied to the hair keratinous fibers, no standing time is allowed before composition D is applied to the hair keratinous fibers.

[0418] After applying the hair colouring composition and optional composition D, the fibres may be allowed to dry naturally or may be dried at a temperature of, for example, 30°C or higher.

[0419] Thus, the method according to the invention may comprise the step of applying heat to the hair keratin fibres using a heating appliance.

[0420] The heat application step of the method of the present invention can be carried out using a hood dryer, a hair dryer, a straightener, a Climazon, or the like.

[0421] Preferably, the step of applying heat of the method of the present invention is carried out using a hair dryer.

[0422] When the method of the present invention includes a step of applying heat to the hair keratinous fibers, the step of applying heat to the hair keratinous fibers is carried out after applying the hair keratinous fiber coloring composition and / or optional composition D to the hair keratinous fibers.

[0423] During the step of applying heat to the hair keratin fibers, the hair strands can be subjected to mechanical action such as combing, brushing or hand combing.

[0424] If the step of applying heat to the hair keratin fibers is carried out using a hood dryer or a hair dryer, the temperature is preferably between 30°C and 110°C, preferentially between 50°C and 90°C.

[0425] If the step of applying heat to the hair keratin fibers is carried out using a straightening iron, the temperature is preferably between 110°C and 220°C, preferably between 140°C and 200°C.

[0426] In a particular variant, the method of the present invention comprises a step (b1) of applying heat using a hood dryer, a hair dryer or a crimson, preferably a hair dryer, and a step (b2) of applying heat using a straightening iron or curling iron, preferably a straightening iron.

[0427] Step (b1) can be carried out before step (b2).

[0428] During the implementation of step (b1), also referred to as the drying step, the hair keratin fibers can be dried, for example, at a temperature of at least 30° C. According to a particular embodiment, this temperature is greater than 40° C. According to a particular embodiment, this temperature is greater than 45° C. and less than 110° C.

[0429] Preferably, when drying the hair keratin fibers, they are dried by using an air current in addition to the supply of heat, which makes it possible to improve the separation of the coating of the hair strands.

[0430] During drying, the hair strands can be subjected to mechanical action such as combing, brushing or hand combing.

[0431] The temperature at which the straightening iron or curling iron is slid in the drying step (b2) may preferably be in the range of 110°C to 220°C, more preferably 140°C to 200°C.

[0432] After the drying step is completed, a shaping step can be carried out using, for example, a straightening iron; the temperature in the shaping step is 110 to 220°C, preferably 140 to 200°C.

[0433] Preferably, the present invention is a method for removing color from pre-colored hair keratin fibers, in particular comprising: i) applying the above-described composition for coloring hair keratin fibers to the hair keratin fibers, and then ii) optionally leaving the hair coloring composition on the fiber for a period of from 1 minute to 30 minutes, preferably from 1 to 20 minutes, followed by iii) optionally washing, rinsing, dewatering or drying the fibers, then iv) applying to the hair keratin fibers a composition D comprising at least one silicone compound containing at least one carboxyl group as described above, followed by v) optionally leaving said composition D on the hair keratin fibers for 1 minute to 30 minutes, preferably 1 to 20 minutes, then vi) optionally washing, rinsing, dewatering or drying the hair keratin fibers; The method includes:

[0434] Preferably, the step of applying the hair coloring composition to the hair keratinous fibers is repeated several times.

[0435] According to a preferred embodiment, the color removal method is a method for removing color from hair keratin fibers, in particular when using at least two compositions A and B, which comprise the steps of immediately mixing them to obtain a composition for coloring hair keratin fibers as defined above, and applying the hair coloring composition to the hair keratin fibers, - composition A comprises at least one (poly)carbodiimide compound as previously described; - composition B comprises at least one compound different from said associative polymer, containing said at least one carboxylic acid group; Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof; Composition A and / or Composition B optionally comprise at least one silicone as defined above.

[0436] Preferably, compositions A and B are mixed less than 15 minutes before application to the hair keratinous fibers, more preferentially less than 10 minutes before application, and even better still less than 5 minutes before application.

[0437] The weight ratio of composition A to composition B is preferably in the range of 0.1 to 10, preferentially 0.2 to 5, even better 0.5 to 2, or even 0.6 to 1.5. In a particular embodiment, the weight ratio of composition A to composition B is equal to 1.

[0438] According to a particular embodiment, the method of the invention is a method for removing color from hair keratin fibers, in particular when using at least two compositions A and B, which comprise a step of immediately mixing them to obtain a composition for coloring hair keratin fibers as defined above, and a step of applying the hair coloring composition to the hair keratin fibers, - composition A comprises at least one (poly)carbodiimide compound as previously described; - composition B comprises at least one compound different from said associative polymer, containing said at least one carboxylic acid group; Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof; Composition A and / or Composition B optionally comprise at least one silicone as defined above; and The aforementioned composition D is applied to the hair keratinous fibers before and / or after, preferably after, applying the mixture of compositions A and B to the hair keratinous fibers.

[0439] Then, as indicated above, the method for removing color from hair keratin fibers comprises applying at least one color removing composition as defined above to hair keratin fibers that have been previously colored using at least one composition for coloring hair keratin fibers as defined above.

[0440] Preferably, the color removing composition is then rinsed out after an optional leave-on time, optionally followed by a shampoo wash.

[0441] Preferably, the colour removal composition is left for 30 seconds to 60 minutes, preferentially 1 to 30 minutes, more preferentially 1 to 15 minutes, more preferably 2 to 10 minutes before being rinsed off.

[0442] According to a particular embodiment, the method according to the invention also comprises a step of massaging the hair keratinous fibers after application of the color-removing composition.

[0443] During this massaging process, certain tools such as exfoliating gloves can be used.

[0444] Preferably, the fingers are passed along the tress five times during the massaging step, the total time for the five passes may range, for example, from 30 seconds to 2 minutes per gram of tress.

[0445] The step of massaging the hair keratinous fibers may be repeated several times, for example twice, optionally with an intermediate leave-on time.

[0446] The step of applying the color removal composition may be repeated several times, optionally with intermediate rinsings.

[0447] The time between the step of applying the composition for coloring hair keratin fibers and the step of applying the color-removing composition can range from a few minutes to several days, for example several tens of days. Preferably, the time between the step of applying the hair coloring composition to hair keratin fibers and the step of applying the color-removing composition ranges from 1 hour to 30 days, more preferentially from 1 day to 15 days.

[0448] The optional massaging step may be followed by a step of washing the hair keratinous fibers, for example using a shampoo. The hair keratinous fibers may then be massaged, rinsed and dried.

[0449] color removing composition The present invention relates to a composition for removing color from hair keratin fibers that have been previously colored with a composition for coloring hair keratin fibers, the composition comprising at least one coloring agent selected from pigments, direct dyes and mixtures thereof, - at least 5% by weight, based on the total weight of the color removal composition, of at least one glycol ether; - at least one alkyl or alkylene carbonate; - optionally at least one polyol different from a glycol ether The present invention also relates to a composition comprising:

[0450] Preferably, the composition for coloring hair keratinous fibers is a composition for coloring hair keratinous fibers used in connection with the method according to the invention.

[0451] Preferably, the glycol ether, alkyl carbonate or alkylene carbonate and optional polyol are each as defined above.

[0452] The total content of glycol ethers may advantageously range from 5% to 60% by weight, more preferentially from 5 to 50% by weight, even more preferentially from 5 to 40% by weight, more preferentially from 10 to 40% by weight and even more preferentially from 20 to 40% by weight relative to the total weight of the colour removal composition.

[0453] Advantageously, the total content of alkyl or alkyl carbonates ranges from 10% to 60% by weight, preferably from 15% to 50% by weight, relative to the total weight of the colour removal composition.

[0454] The polyol content advantageously ranges from 1% to 50% by weight, preferably from 5% to 30% by weight and more preferentially from 5% to 20% by weight relative to the total weight of the colour removal composition.

[0455] Preferably, as described above, the ingredients that can be included in the color removal composition used in connection with the method according to the present invention can be included in the color removal composition according to the present invention.

[0456] use The present invention also relates to the use of the composition of the present invention or the composition used in connection with the method of the present invention for removing color from hair keratin fibers, such as hair, that have been previously colored with a composition for coloring hair keratin fibers, the composition comprising at least one coloring agent selected from pigments, direct dyes and mixtures thereof.

[0457] Preferably, the hair colouring composition comprises at least one (poly)carbodiimide compound as defined above.

[0458] Preferably, the composition for coloring hair keratinous fibers is as defined above.

[0459] The invention will now be explained in more detail by means of examples which in no way limit the scope of the invention, but which make it possible to support certain features, variants and preferred embodiments of the invention. [Example]

[0460] The (poly)carbodiimides of the present invention can be obtained via synthesis methods known to those skilled in the art, starting from commercially available products or reagents that can be synthesized according to chemical reactions known to those skilled in the art, such as those described in the book Sciences of Synthesis-Houben-Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag KG, Rüdigerstrasse 14, D-70469 Stuttgart, or in U.S. Pat. No. 4,284,730 or Canadian Patent Application No. 2,509,861.

[0461] More specifically, the method for preparing the (poly)carbodiimide of the present invention comprises, in a first step, reacting a diisocyanate reagent (1): O=C=N-L1-N=C=O (1) (In formula (1), L1 is as defined above.) in the presence of a carbodiimidization catalyst (2) such as those described in U.S. Pat. No. 4,284,730, particularly a phosphorus-based catalyst, particularly one selected from phospholene oxides and phospholene sulfoxides, diaza- and oxaza-phosphoranes, preferably in an inert atmosphere (nitrogen or argon), particularly preferably in an aprotic polar solvent such as THF, glyme, diglyme, 1,4-dioxane or DMF, at a temperature between room temperature and the reflux temperature of the solvent, preferably about 140° C., to obtain a carbodiimide diisocyanate compound (3): O=C=N-L1-(N=C=N-L1) n -N=C=O (3) (In formula (3), L1 and n are as defined above.) A benzoyl halide, such as benzoyl chloride, may be added to deactivate the catalyst.

[0462] In the second step of this preparation process, to obtain a "symmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 eq.) of the nucleophilic reagent R1-X1-H, followed by 0.5 eq. of the reagent HEH (wherein R1, X1 and E are as defined above), to give the "symmetric" compound (4) according to the invention: [R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)]2-E (4) (In formula (4), R1, X1, L1, n, and E are as defined above.) According to one variant to obtain compound (4) from (3), it is possible to first add 0.5 eq. of the reagent HEH, followed by 1 eq. of the reagent R1-X1-H.

[0463] In the second step of this preparation process, to obtain an "unsymmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 eq.) of the nucleophilic reagent R1-X1-H, and then with 1 eq. of the reagent HEH (wherein R1, X1 and E are as defined above), to give compound (5): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EH (5) (In formula (5), R1, X1, L1, n, and E are as defined above.) get.

[0464] According to one variant to obtain compound (5) from (3), it is possible to first add 1 eq. of reagent R1-X1-H, followed by 0.5 eq. of reagent HEH.

[0465] In the third step, compound (5) is reacted with 1 eq. of compound (6): R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O (6) (The compound (6) is a compound (3'): O=C=N-L1-(N=C=N-L1) z -N=C=O(3'), (In formula (3'), L1 and z are as defined above.) with 1 eq. of a nucleophilic reagent R2-X2-H (wherein L1, R2, X2 and z are as defined above). to give the asymmetric compound (7): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EC(O)-NH-L1-(N=C=N-L1) z -NH-C(O)-X2-R2(7) (In formula (7), R1, X1, L1, R2, X2, n, z, and E are as defined above.) get.

[0466] 1 molar equivalent of the compound O=C=N-L1-(N=C=N-L1) z -N=C=O (3') is reacted with 1 / w molar equivalent of HEH, and then with 1 eq. of a nucleophile R2-X2-H to give compound (8): H-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NH-C(O)-X2-R2(8) (In formula (8), L1, R2, X2, z, and E are as defined above, and w is an integer of 1 to 3; more preferentially, w=1.) It is also possible to obtain

[0467] The final compound (8) is then reacted with 1 eq. of compound (4'): R1-X1~C(O)-NH-L1-(N=C=N-L1) n -N=C=O(4') (The compound (4') can be synthesized by reacting 0.5 eq. of a nucleophilic reagent R1-X1-H with 1 eq. of the compound (3).) to obtain the (poly)carbodiimide (9) of the present invention: R1-X1-C(O)-NH-L1-(N=C=N-L1) n-NH-C(O)-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NH-C(O)-X2-R2(9) (In formula (9), L1, R1, X1, R2, X2, n, z, w, and E are as defined above.) can be obtained.

[0468] The (poly)carbodiimide compounds and all reaction intermediates and reagents as well can be purified by conventional methods known to those skilled in the art, such as extraction with water and water-immiscible organic solvents, precipitation, centrifugation, filtration and / or chromatography.

[0469] Example 1: Method for synthesizing (poly)carbodiimide compounds A 500 mL three-necked round-bottom flask equipped with a thermometer, a stirrer, and a reflux condenser is charged with 50 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphole 1-oxide with stirring.

[0470] 2200-2300 cm by infrared spectroscopy -1 The reaction medium is heated under nitrogen at 140°C for 4 hours, and then cooled to 120°C, while the reaction is monitored by the absorption of isocyanate groups.

[0471] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol is introduced into the reaction medium with stirring. -1 The temperature is monitored and maintained at 120°C until the isocyanate groups have completely disappeared, and then cooled to room temperature.

[0472] After cooling to room temperature, the reaction medium is added dropwise, with vigorous stirring, to a 500 mL glass beaker containing 85 g of distilled water, to obtain the desired product in the form of a translucent yellow liquid.

[0473] Example 2 The compositions A1, A2, B1 and B2 described below were prepared, the amounts being expressed as g / 100 g of starting material obtained.

[0474] [Table 1]

[0475] [Table 2]

[0476] Two mixtures are then made.

[0477] Composition A1 is mixed with composition B1 in a 50 / 50 ratio to obtain composition C1.

[0478] Composition A2 is mixed with composition B2 in a 50 / 50 ratio to obtain composition C2.

[0479] Compositions C1 and C2 are therefore hair colouring compositions according to the invention.

[0480] The following composition D was then prepared: Amounts are expressed as g / 100g of starting material obtained.

[0481] [Table 3]

[0482] color removing composition In parallel, several color removal compositions according to the invention were prepared and are set out in the table below, the amounts being expressed as g / 100 g of the starting material obtained.

[0483] [Table 4]

[0484] Protocol for coloring hair: Compositions C1 and C2 are each applied to dry natural hair tresses containing 90% white hair at a rate of 0.5 g of composition per gram of tress.

[0485] The hair tresses are then dried using a hair dryer and then combed.

[0486] Composition D is then applied to the tresses of hair treated with compositions C1 and C2 and dried, at a rate of 0.5 g of composition per gram of tress.

[0487] The hair tresses thus colored are left at room temperature for 24 hours and then subjected to a bleaching treatment.

[0488] The hair tresses coloured with composition C1 are treated with composition E1, and the hair tresses coloured with composition C2 are treated with composition E2.

[0489] Protocol for Removing Color from Pre-Colored Hair Tresses Each of compositions E1 and E2 is applied to a colored hair tress in a ratio of 1 g of composition per 1 g of tress. The tress is first massaged (running fingers along the tress 5 times). Then, after a leave-on time of 10 minutes at room temperature, the tress is massaged again (running fingers along the tress 5 times), and then the tress is rinsed.

[0490] The tresses are then washed using a standard shampoo (Garnier Ultra Doux).

[0491] The hair is then massaged, rinsed and then dried using a hair dryer.

[0492] The color removal is then rated on a scale of 1 to 5. A score of 1 indicates excellent color removal. A score of 5 indicates poor color removal. The results are set forth in the table below.

[0493] [Table 5]

[0494] It is observed that compositions E1 and E2 according to the invention have excellent color removal power.

[0495] The method according to the invention therefore makes it possible to obtain an efficient removal of color from hair tresses that have been previously colored using a hair coloring composition comprising a (poly)carbodiimide compound and a colorant chosen from pigments, direct dyes and mixtures thereof.

[0496] Example 3: In Example 3, hair coloring compositions A1, B1 and D described above in Example 2 are used. Accordingly, in Example 3, hair coloring composition C1 described above in Example 2 is used.

[0497] color removing composition In parallel, several color removal compositions according to the invention were prepared and are set out in the table below, the amounts being expressed as g / 100 g of the starting material obtained.

[0498] [Table 6]

[0499] Protocol for coloring hair: Composition C1 is applied to dry natural hair tresses containing 90% white hair at a rate of 0.5 g of composition per gram of tress.

[0500] The hair tresses are then dried using a hair dryer and then combed.

[0501] Then, after combing, composition D is applied to said tresses of hair treated with composition C1 and dried, at a rate of 0.5 g of composition per gram of tress.

[0502] The hair tresses thus colored are then subjected to a color removal treatment: the hair tresses colored with composition C1 are treated with compositions E3 to E7.

[0503] Protocol for Removing Color from Hair Tresses Each of compositions E3 to E7 is applied to a colored hair tress at a rate of 1 g of composition per gram of tress. The tress is first massaged (running fingers along the tress 5 times). Then, after a 10-minute leave-on time at room temperature, the tress is massaged again (running fingers along the tress 5 times), and then the tress is rinsed.

[0504] The tresses are then washed using a standard shampoo (Garnier Ultra Doux).

[0505] The hair is then massaged, rinsed and then dried using a hair dryer.

[0506] Color removal is then rated on a scale of 1 to 5. A score of 1 indicates excellent color removal (also called bleaching power). A score of 5 indicates poor color removal. The results are set forth in the table below.

[0507] [Table 7]

[0508] It is observed that compositions E3 to E7 according to the invention have excellent color removal power on textiles.

[0509] The method for removing color from hair keratin fibers according to the invention therefore makes it possible to efficiently remove color from hair tresses that have been previously colored using a composition for coloring hair keratin fibers comprising a (poly)carbodiimide compound and a colorant selected from pigments, direct dyes and mixtures thereof.

[0510] Example 4: Compositions A3 and B3 described below were prepared, the amounts being expressed as g / 100g of starting material obtained.

[0511] [Table 8]

[0512] [Table 9]

[0513] Composition A3 is mixed with composition B3 in a 50 / 50 ratio to obtain composition C3.

[0514] Composition D described above in Example 2 is then used.

[0515] color removing composition In parallel, several color removal compositions according to the invention were prepared and are set out in the table below, the amounts being expressed as g / 100 g of the starting material obtained.

[0516] [Table 10]

[0517] Protocol for coloring hair: Composition C3 is applied to dry natural hair tresses containing 90% white hair at a rate of 0.8 g of composition per gram of tress.

[0518] The hair tresses are then dried using a hair dryer and then combed.

[0519] Composition D is then applied to the same tresses of hair that have been treated with composition C3 and dried, at a rate of 0.5 g of composition per gram of tress.

[0520] The hair tresses thus colored are left at room temperature for 24 hours and then subjected to a bleaching treatment.

[0521] The hair tresses coloured with composition C3 are treated with composition E8 or composition E9.

[0522] Protocol for Removing Color from Pre-Colored Hair Tresses Each of compositions E8 and E9 is applied to a colored hair tress at a rate of 0.5 g of composition per gram of tress or 10 g of composition per gram of tress. The tress is first massaged (running fingers along the tress 5 times). Then, after a 10-minute leave-on time at room temperature, the tress is massaged again (running fingers along the tress 5 times), and then the tress is rinsed.

[0523] The tresses are then washed using a standard shampoo (Garnier Ultra Doux).

[0524] The hair is then massaged, rinsed and then dried using a hair dryer.

[0525] result: The color durability of the tresses was evaluated in the CIE L*a*b* system using a Minolta Spectrophotometer CM3600A spectrophotometer (D65 illuminant, 10° angle, including specular reflection component).

[0526] In this L*a*b* system, L* represents the intensity of the color, a* indicates the green / red axis, and b* indicates the blue / yellow axis.

[0527] Color persistence is assessed by the color difference ΔE between colored tresses before removing the color from the tresses and then after undergoing the color removal method from the pre-colored tresses, as described above. The lower the ΔE value, the more color lasting for the color removal composition.

[0528] The ΔE value is calculated according to the following formula:

number

[0529] In this formula, L*a*b* represents the value measured after coloring the hair and after removing the color from the tress, and L0*a0*b0* represents the value measured after coloring the hair but before removing the color from the tress.

[0530] [Table 11]

[0531] It was observed that the composition for removing color E8 according to the present invention had better color removal power compared to the comparative composition for removing color E9.

[0532] Thus, the method for removing color from hair keratin fibers according to the invention makes it possible to efficiently remove color from hair tresses that have been previously colored using a hair coloring composition comprising a (poly)carbodiimide compound and a colorant selected from pigments, direct dyes and mixtures thereof.

Claims

1. 1. A method for removing hair color from pre-colored hair keratin fibers, comprising: The method comprises applying at least one color-removing composition to hair keratinous fibers that have been previously colored using at least one composition for coloring hair keratinous fibers, wherein the at least one composition for coloring hair keratinous fibers comprises: at least one (poly)carbodiimide compound; and at least one colorant chosen from pigments, direct dyes and mixtures thereof; applying, including; applying a composition D to the hair keratinous fibers, the composition D comprising at least one silicone compound containing at least one carboxyl group, the application of the composition D occurring before the application of the color-removing composition, The color removal composition comprises: at least 5% by weight, relative to the total weight of the color removal composition, of at least one glycol ether chosen from glycol ethers of formula R 11 (—O—CH(CH 3 )—CH 2 ) n OH, in which R 11 represents a C 1 -C 6 alkyl group and n is between 2 and 10; A method comprising:

2. The (poly)carbodiimide compound has the following formula (I): 【Chemistry 1】 (In the formula, -X １ and X ２ independently represent an oxygen atom O, a sulfur atom S, or an NH group; -R １ and R ２ are independently selected from hydrocarbon-based groups, alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide, and azacyclopropane groups; n represents an integer ranging from 1 to 1000; and A is the following compound: 【Chemistry 2】 is a monomer selected from 2. The method of claim 1, wherein the compound is selected from the group consisting of:

3. The (poly)carbodiimide compound has the following formula (II): 【Transformation 3】 (In the formula, -X １ and X ２ independently represent an oxygen atom O, a sulfur atom S, or an NH group; -R １ and R ２ independently represent a hydrocarbon group; n and z represent integers ranging from 1 to 20, where n+z≧2, and w represents an integer ranging from 1 to 3; - L １ are independently divalent C １ ~C １８ Aliphatic hydrocarbon group, C ３ ~C １５ Cycloalkylene group, C ３ ~C １２ Heterocycloalkylene group or C ６ ~C １４ represents arylene groups and mixtures thereof; E is independently - -O-R ３ -O-;-S-R ４ -S-;-R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - (In the formula, R ３ and R ４ each independently represents a divalent hydrocarbon group; -R ５ independently represent a covalent bond or a divalent saturated hydrocarbon group; -R ６ each independently represents a hydrogen atom or a hydrocarbon group. represents a group selected from 2. The method of claim 1, wherein the compound is selected from the group consisting of:

4. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ independently represent an oxygen atom; -R １ and R ２ are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, from which the hydroxyl groups have been removed, and mixtures thereof; n and z represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L1 is a divalent C １ ~C １８ Aliphatic hydrocarbon group, C ３ ~C １５ Cycloalkylene group, C ３ ~C １２ Heterocycloalkylene group or C ６ ~C １４ arylene groups and mixtures thereof; E is independently - -O-R ３ -O-;-S-R ４ -S-;-R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - wherein R3 and R4 are independently C ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups and mixtures thereof; -R ５ is not a covalent bond, R ５ is C ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups and mixtures thereof; and -R ６ is C ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups and mixtures thereof) 4. The method of claim 3, wherein the aryl group represents a group selected from:

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

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

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

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

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

9. 9. The method according to claim 1, wherein the total amount of (poly)carbodiimide compounds ranges from 0.01% to 30% by weight relative to the total weight of the composition for coloring hair keratin fibers.

10. 10. The method according to any one of claims 1 to 9, characterized in that the content of coloring agent ranges from 0.001% to 20% by weight relative to the total weight of the composition for coloring hair keratin fibers.

11. 11. The method according to any one of claims 1 to 10, characterized in that the pigment content ranges from 0.05% to 20% by weight relative to the total weight of the composition for coloring hair keratin fibers.

12. 12. The method according to claim 1, wherein the total amount of silicone compounds containing at least one carboxyl group present in composition D ranges from 0.01% to 20% by weight relative to the total weight of composition D.

13. The method according to any one of claims 1 to 12, characterized in that composition D also comprises one or more oils.

14. The glycol ether has the formula CH ３ (-O-CH(CH ３ )-CH ２ ) ｎ 14. The method according to any one of claims 1 to 13, characterized in that the compound is of the formula: OH, wherein n is from 2 to 10.

15. The method of claim 1, wherein the color removal composition further comprises at least one alkyl or alkylene carbonate.

16. The method of claim 15, wherein the alkyl or alkylene carbonate is a C 1 -C 30 alkyl or C 1 -C 30 alkylene carbonate.

17. 17. The method according to claim 15 or 16, characterized in that the total content of alkyl or alkylene carbonates ranges from 10% to 60% by weight relative to the total weight of the color removal composition.

18. 13. A composition for use in a method for removing color from hair keratin fibers previously colored with a hair coloring composition comprising at least one colorant selected from pigments, direct dyes and mixtures thereof and at least one (poly)carbodiimide compound as defined in any one of claims 1 to 9, said method comprising the step of applying to hair keratin fibers a composition D as defined in any one of claims 1, 12 and 13, said application of composition D occurring before said application of a color removing composition, said color removing composition comprising: - at least 5% by weight, relative to the total weight of the color removal composition, of at least one glycol ether as defined in claim 1 or 14; at least one alkylene carbonate chosen from propylene carbonate, butylene carbonate, pentylene carbonate and mixtures thereof; A composition comprising:

19. 19. Use of a composition as defined in any one of claims 1 to 17 or 18 for use in a method for removing color from hair keratin fibers that have been previously colored with a hair coloring composition comprising at least one colorant selected from pigments, direct dyes and mixtures thereof and at least one (poly)carbodiimide compound as defined in any one of claims 1 to 9, said method comprising the step of applying to hair keratin fibers a composition D as defined in any one of claims 1, 12 and 13, said application of composition D occurring before the application of a color removal composition.

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