Method for removing color from previously dyed keratin hair fibers

Abstract

The present invention relates to a method for removing color from keratin hair fibres previously dyed by at least one composition for dyeing keratin hair fibres, the composition comprising: at least one (poly) carbodiimide compound; and at least one colorant selected from the group consisting of pigments, direct dyes, and mixtures thereof. The invention relates to a method for dyeing keratin hair fibres, said method comprising the steps of: i) applying to these keratin hair fibres previously dyed by said dyeing composition at least one decolorizing composition comprising at least one alkyl carbonate or alkylene carbonate; and ii) applying to the keratin hair fibres a clamp (1) comprising two arms A and B, the keratin hair fibres passing between the arms.

Description

Technical Field

[0001] The present invention relates to a method for removing color from keratin hair fibers previously dyed by at least one composition for dyeing keratin hair fibers, the composition comprising: at least one (poly)carbodiimide compound; and at least one colorant chosen from pigments, direct dyes and mixtures thereof. The method comprises the steps of: i) applying to these keratin hair fibers previously dyed by said dyeing composition at least one color removing composition comprising at least one alkyl carbonate or alkylene carbonate; and ii) applying to said keratin hair fibers a fixture comprising two arms A and B, between which said keratin hair fibers pass, as described below. Background Art

[0002] In the field of dyeing keratin hair fibres, in particular human keratin hair fibres, it is a known practice to colour keratin hair fibres by various techniques using direct dyes or pigments for non-permanent colouring, or dye precursors for permanent colouring.

[0003] There are basically three types of methods for dyeing hair:

[0004] a) "permanent" coloring, the function of which is to provide a substantial change in the natural color and which uses oxidative dyes which penetrate into the hair fiber and form the coloration by a process of oxidative condensation;

[0005] b) non-permanent, semi-permanent or direct dyeing which does not use an oxidative condensation process and which withstands four or five shampooing operations; it comprises dyeing keratin fibers with a dye composition containing direct dyes;

[0006] c) Temporary coloring, which causes a change in the natural color of the hair that is preserved from one shampooing operation to the next and serves to enhance or correct an already acquired hue. It can also be likened to a "make-up" process.

[0007] For this last type of dyeing, it is known practice to use colored polymers formed by grafting onto the polymer chain one or more dyes of an azo, triphenylmethane, azine, indoleamine or anthraquinone nature. These colored polymers are not entirely satisfactory, in particular as regards the homogeneity of the coloration obtained and its resistance, not to mention the problems associated with their manufacture and, in particular, with their reproducibility.

[0008] Another dyeing method involves the use of pigments. In particular, the use of pigments on the surface of keratin hair fibers generally enables visible coloring to be obtained on dark hair, since the surface pigments mask the natural color of the fibers.

[0009] This dyeing process also makes it possible to provide dye compositions which have the advantage of producing a uniform colored coating on keratinous hair fibers, in particular the hair, while forming a coating which withstands shampooing operations and various aggressors to which the hair may be subjected, such as brushing and / or friction, without deteriorating the hair.

[0010] However, there are no methods for removing color from keratin hair fibers previously dyed with pigments which effectively implement color removal compositions that withstand shampooing operations and implements with temporary dye compositions of this type.

[0011] Therefore, there remains a need for a method for effectively removing color from keratinous hair fibers, such as hair, which have been previously dyed by such shampoo-resistant dye compositions.

[0012] It was therefore an object of the present invention to develop a method for effectively removing colour from keratinous hair fibres, such as hair. Summary of the invention

[0013] The subject of the present invention is therefore a method for removing color from keratinous hair fibers that have previously been dyed by at least one composition for dyeing keratinous hair fibers, comprising:

[0014] - at least one (poly)carbodiimide compound; and

[0015] - at least one colorant selected from pigments, direct dyes and mixtures thereof;

[0016] The method comprises the following steps:

[0017] i) applying to these keratin hair fibers previously dyed by said dyeing composition at least one color-removing composition comprising:

[0018] - at least one alkyl carbonate or alkylene carbonate; and

[0019] ii) applying a clamp comprising two arms A and B to the keratin hair fiber, the keratin hair fiber passing between the arms,

[0020] Each arm A and B comprises a supporting part and a movable part.

[0021] The arms A and B are movable between a spaced-apart position in which the movable parts are at a distance from each other and a brought-together position in which the movable parts are brought towards each other.

[0022] The movable portion comprises an active surface and an opposite surface, wherein the active surface has bristles,

[0023] Therein, in the closed position of the movable parts, the bristles of the arms A and B are interlaced with one another so as to clamp the keratin hair fibers without blocking them.

[0024] The combination of a composition for removing color as described above, comprising at least one alkyl carbonate or alkylene carbonate, and a clamp enables effective removal of color from keratin hair fibers previously dyed by a dyeing composition, as previously described.

[0025] "Keratin hair fibers" means hair. In other words, the expressions "keratin hair fibers" and "hair" are equivalent in the rest of the description.

[0026] For the purposes of the present invention, "hair" means the entire head of hair. This term does not correspond to body hair, eyebrows or eyelashes.

[0027] The expression "at least one" means one or more than one.

[0028] Unless otherwise indicated, the limits of a range of values ​​are included in that range, particularly in the expressions "between" and "ranging from to".

[0029] The invention is not limited to the examples shown. Features of the different examples can in particular be combined in variants not shown.

[0030] For the purposes of the present invention and unless otherwise indicated:

[0031] - "Alkyl" indicates a straight-chain or branched saturated group containing, for example, from 1 to 20 carbon atoms;

[0032] - "aminoalkyl" indicates an alkyl group as defined previously, said alkyl group comprising an NH2 group;

[0033] - "Hydroxyalkyl" indicates an alkyl group as defined previously, said alkyl group comprising an OH group;

[0034] - "Alkylene" indicates a straight or branched divalent saturated C2-C4 hydrocarbon-based group, such as methylene, ethylene or propylene;

[0035] - "cycloalkyl" or "alicyclic alkyl" indicates a cyclic saturated monocyclic or polycyclic, preferably monocyclic hydrocarbon-based group containing 1 to 3 rings, preferably 2 rings and containing 3 to 24 carbon atoms, particularly containing 3 to 20 carbon atoms, more particularly 3 to 13 carbon atoms, even more particularly 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, particularly cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl may be substituted by one or more (C1-C4)alkyl groups such as methyl; preferably, the cycloalkyl is then isobornyl;

[0036] - "Cycloalkylene" refers to a divalent cycloalkyl group, wherein "cycloalkyl" is as defined above, preferably C3-C 12 ;

[0037] - "aryl" is a monocyclic, bicyclic or tricyclic, fused or non-fused, unsaturated and aromatic hydrocarbon-based cyclic group containing from 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms; preferably, aryl contains 1 ring with 6 carbon atoms, such as phenyl, naphthyl, anthracenyl, phenanthrenyl and biphenyl, it being understood that aryl may be substituted by one or more (C1-C4)alkyl groups such as methyl, preferably tolyl, xylyl or methylnaphthyl; preferably, aryl represents phenyl;

[0038] - "arylene" is a divalent aromatic radical, wherein "aryl" is as previously defined; preferably, arylene represents phenylene;

[0039] - a "heterocyclic" group indicates a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based group containing one or more heteroatoms, preferably from 1 to 5 atoms selected from O, S or N, comprising from 3 to 20 ring members, preferably between 5 and 10 ring members, such as imidazolyl, pyrrolyl and furanyl;

[0040] - "Heterocycloalkylene" is a divalent heterocyclic radical, wherein "heterocycle" is as previously defined;

[0041] - "Aryloxy" indicates an aryl-oxy group, wherein "aryl" is as previously defined;

[0042] - "alkoxy" indicates an alkyl-oxy group, wherein "alkyl" is as previously defined;

[0043] - "Acyloxy" denotes an ester group RC(O)-O-, wherein R is alkyl as defined above;

[0044] - A "reactive" group is a group that is capable of forming a covalent bond with another identical or different group by a chemical reaction.

[0045] Unless otherwise indicated, when a compound is mentioned in the present patent application, it also includes its optical isomers, its geometric isomers, its tautomers or its salts, either alone or as a mixture.

[0046] "Keratin hair fibers" means hair. In other words, the expressions "keratin hair fibers" and "hair" are equivalent in the rest of the description.

[0047] For the purposes of the present invention, "hair" means the entire head of hair. This term does not correspond to body hair, eyebrows or eyelashes. DETAILED DESCRIPTION

[0048] Staining composition:

[0049] Polycarbodiimide compounds

[0050] As indicated previously, the composition for dyeing keratin hair fibres used in the context of the method according to the invention comprises at least one (poly)carbodiimide compound.

[0051] The composition may comprise at least two different (poly)carbodiimide compounds, present as a mixture in the composition.

[0052] The term "(poly)carbodiimide compound" means a compound comprising one or more carbodiimide groups, preferably at least two carbodiimide groups, more preferably at least three carbodiimide groups; in particular, the number of carbodiimide groups does not exceed 200, preferably 150, more preferably 100.

[0053] The term "carbodiimide group" means a divalent straight-chain three-atom moiety of the general formula -(N=C=N)-.

[0054] The (poly)carbodiimide compound according to the present invention may optionally contain in its structure one or more reactive groups other than the carbodiimide group, the reactive groups being selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacryloylalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonylalkyl, alkylepoxides such as propylepoxide or butylepoxide and aziridine groups.

[0055] The reactive groups other than the carbodiimide groups may be side groups or terminal groups. Preferably, the (poly)carbodiimide compound comprises one or more terminal groups other than the carbodiimide groups, preferably one or more terminal groups selected from the group consisting of alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxides such as propylepoxide or butylepoxide and aziridine groups.

[0056] According to a specific embodiment, the (poly)carbodiimide compound is selected from the compounds of the following formula (I):

[0057]

[0058] in:

[0059] -X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0060] - R1 and R2 independently represent: a group selected from a hydrocarbon-based group, preferably an alkyl group, optionally interrupted by one or more heteroatoms; selected from an alkoxysilyl group, a hydroxysilyl group, an acetoxysilyl group, a vinylsilyl group, an acryloylalkylsilyl group, a methacryloylalkylsilyl group, a crotonylalkylsilyl group, a carboxyanhydridealkylsilyl group, a carboxyalkylsilyl group, a hydroxyalkylsilyl group, an aldehydealkylsilyl group, a mercaptoalkylsilyl group, a norbornenylsilyl group, an acylpentadienylalkylsilyl group, a maleimidoalkylsilyl group, a sulfonylalkylsilyl group, a (meth)acryloylalkyl group, a crotonylalkyl group, an alkylepoxide such as a propylepoxide or a butylepoxide and an aziridine group and hydrocarbon-based groups, preferably alkyl groups, which are optionally interrupted by one or more heteroatoms and one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacryloylalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonylalkyl, alkylepoxides such as propylepoxide or butylepoxide and aziridine groups;

[0061] -n indicates an integer ranging from 1 to 1000; and

[0062] -A is a monomer selected from the following compounds:

[0063]

[0064]

[0065] According to another embodiment, the (poly)carbodiimide compound is selected from the compounds of the following formula (I'):

[0066]

[0067] in:

[0068] -X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0069] -Y1 and Y2 independently represent a saturated C1 to C 36 Aliphatic group or C6 to C 24 a divalent organic group of an aromatic or alkyl aromatic group, the aliphatic or aromatic group optionally containing one or more non-pendent heteroatoms, such as a nitrogen atom, an oxygen atom, a sulfur atom, or a combination thereof;

[0070] - Z1 and Z2 independently represent a reactive terminal group or an inert terminal group;

[0071] - As inert terminal groups, Z1 and Z2 can independently represent saturated linear or branched or cyclic C1 to C 50 Aliphatic group, or C6 to C 18 an aromatic group, the aliphatic and aromatic groups optionally containing from 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 variant, Z1 and Z2 contain a bonding group CG connecting Z1 to Y1 and Z2 to Y2, which group CG may be 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 carbamate group, a thiocarbamate group or a urea group;

[0072] - as reactive terminal groups, Z1 and Z2 may be selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonylalkyl, alkylepoxides such as propylepoxide or butylepoxide and aziridine groups;

[0073] -Q represents an organic polymer or organic oligomer comprising repeating units of saturated linear or branched or alicyclic groups, or aromatic groups or alkyl aromatic groups, which repeating units are coupled via carbonate, ester, ether, amide, carbamate or urea repeating bonds or a combination thereof;

[0074] -A represents a divalent aliphatic, aromatic, alkylaromatic or linear, saturated, branched or cyclic group having from 2 to 30 carbon atoms, which may optionally contain one or more non-pendent heteroatoms in the aliphatic or aromatic chain, such as nitrogen atoms, oxygen atoms, sulfur atoms, or combinations thereof;

[0075] -r indicates an integer equal to 0 or 1;

[0076] - m indicates an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0077] - m' indicates an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0078] -n indicates an integer ranging from 0 to 1000, preferably equal to 0 or 1, where m+(m'*n)≥2.

[0079] Preferably, Z1 and Z2 independently represent reactive terminal groups; more preferably, Z1 and Z2 independently represent groups selected from the following: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacryloylalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and aziridine group.

[0080] Such (poly)carbodiimide compounds are sold, for example, by Stahl BV under the name Permutex XR, or under the name RelcaLink 10, or under the name Picassian XL and by Nisshinbo under the name Carbodilite and the series V-02, V-02-L2, SV-02, E-02, V-10, SW-12G, E-03A, E-04DG-T, E-05, V-04, V-02B, V-04PF, V-05.

[0081] Preferably, the (poly)carbodiimide compound is selected from the compounds of the following formula (II):

[0082]

[0083] in:

[0084] -X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0085] - R1 and R2 independently represent a hydrocarbon-based group optionally interrupted by one or more heteroatoms;

[0086] - n and z indicate integers ranging from 1 to 20, wherein n+z≥2 and w indicates an integer ranging from 1 to 3;

[0087] -L1 independently represents C1-C 18 Divalent aliphatic hydrocarbon-based groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocycloalkylene or C6-C 14 Arylene, and mixtures thereof;

[0088] -E independently represents a group selected from the following:

[0089] --O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-;

[0090] wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms;

[0091] - R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms;

[0092] -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms.

[0093] The term "hydrocarbon-based group" means a saturated or unsaturated, linear or branched group having from 1 to 300 carbon atoms, preferably from 1 to 250 carbon atoms, more preferably from 1 to 200 carbon atoms. Preferably, the hydrocarbon-based group is a saturated linear group.

[0094] The hydrocarbon-based group may contain one or more cyclic groups.

[0095] The hydrocarbon-based groups may be interrupted by one or more heteroatoms, in particular selected from O, S or N, and / or be substituted by one or more cations, anions or zwitterions or cationic groups such as ammonium, anionic groups such as carboxylates, or zwitterionic groups, and / or contain metal ions which may be introduced in the form of salts.

[0096] The term "heteroatom" means oxygen O, sulfur S or nitrogen N atoms, and also halogen atoms such as Cl, F, Br and I. If the hydrocarbon-based group contains heteroatoms in the chain, the heteroatoms are preferably selected from oxygen O, sulfur S or nitrogen N atoms.

[0097] Preferably, X1 and X2 independently represent an oxygen atom.

[0098] Preferably, 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.

[0099] In a preferred embodiment, R1 and R2 are independently selected from the following groups (i) to (iv):

[0100] (i) a compound of the following formula (III):

[0101] R7-OC(O)-C(R8)(H)- (III),

[0102] wherein R7 represents a C1-C3 alkyl group, and R8 represents a hydrogen atom or a C1-C3 alkyl group; preferably, R7 is a methyl group, and R8 is a hydrogen atom or a methyl group.

[0103] (ii) a compound of the following formula (IV):

[0104] R9-[O-CH2-C(H)(R 10 )] p - (IV),

[0105] Wherein R9 represents C1-C4 alkyl, R 10 represents a hydrogen atom or a C1-C4 alkyl group and p indicates an integer ranging from 1 to 3; preferably, R9 is a methyl group, an ethyl group or a butyl group, R 10 is a hydrogen atom or a methyl group and p is equal to 1.

[0106] (iii) a compound of the following formula (V):

[0107] (R 11 )2N-CH2-C(H)(R 12 )- (V),

[0108] Where 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 It is a hydrogen atom or a methyl group.

[0109] (iv) a compound of the following formula (VI):

[0110] R 13 -[O-CH2-C(H)(R 14 )] q - (VI),

[0111] Where R 13 represents a C1-C4 alkyl group or a phenyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group and q indicates an integer ranging from 4 to 30; preferably, R 13 is methyl, ethyl or butyl, and R 14 It is a hydrogen atom or a methyl group.

[0112] Preferably, R1 and R2 independently represent a compound of formula (VI) wherein R 13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30.

[0113] According to an alternative embodiment, R1 and R2 are different and one of the radicals R1 or R2 represents a compound of formula (IV) as described above and the other of the radicals R1 or R2 represents a compound of formula (VI) as described above.

[0114] Preferably, in formula (IV), R9 is methyl, ethyl or butyl, and R 10 is a hydrogen atom or a methyl group and p is equal to 1.

[0115] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or a methyl group and q indicates an integer ranging from 4 to 30.

[0116] According to another alternative embodiment, R1 and R2 are identical and represent a compound of formula (VI) wherein R 13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30.

[0117] Preferably, n indicates an integer ranging from 1-20, more preferably from 2-20.

[0118] Preferably, z indicates an integer ranging from 1 to 20, more preferably from 2 to 20.

[0119] Preferably, w is equal to 1.

[0120] Preferably, w is equal to 1, and n+z indicates an integer ranging from 4 to 10.

[0121] Preferably, L1 is selected from C1-C 18 Divalent aliphatic hydrocarbon-based groups such as methylene, ethylene and propylene, C3-C 15 Cycloalkylene such as cyclopentylene, cycloheptylene and cyclohexylene, C3-C 12 Heterocycloalkylene such as imidazolylene, pyrrolylene and furylene, or C6-C 14 Arylene groups such as phenylene, and mixtures thereof.

[0122] For example, L1 can be selected from groups derived from toluene 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-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate and phenylene diisocyanate, and mixtures thereof.

[0123] Preferably, L1 is selected from C3-C 15 Cycloalkylene or C6-C 14 Arylene, and mixtures thereof, such as compounds of formula (VII) below:

[0124]

[0125] Preferably, L1 is 4,4-dicyclohexylenemethane corresponding to the following formula (VIII):

[0126]

[0127] According to another embodiment, when L1 is C6-C 14 When L1 is an arylene group, L1 is not a meta-tetramethylxylylene group represented by the following formula (IX):

[0128]

[0129] As previously indicated, E independently represents a group selected from:

[0130] --O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-;

[0131] wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms;

[0132] - R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; and

[0133] -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms.

[0134] Preferably, R3 and R4 are independently selected from C6-C 14 Arylene such as phenylene, C3-C 12 Cycloalkylene such as cyclopropylene and cyclobutylene, straight or branched C1-C 18 Alkylene groups such as methylene and ethylene, and mixtures thereof.

[0135] More preferably, R3 and R4 are independently selected from a linear or branched C1-C 18 Alkylene groups, such as methylene, butylene, propylene, and ethylene.

[0136] Preferably, when R5 is not a covalent bond, R5 is selected from C6-C 14 Arylene such as phenylene, C3-C 12 Cycloalkylene such as cyclopropylene and cyclobutylene, straight or branched C1-C 18 Alkylene groups such as methylene and ethylene, and mixtures thereof.

[0137] Preferably, R6 is selected from C6-C 14 Arylene such as phenylene, C3-C 12 Cycloalkylene such as cyclopropylene and cyclobutylene, straight or branched C1-C 18 Alkylene groups such as methylene and ethylene, and mixtures thereof.

[0138] Preferably, E represents a group -O-R3-O-, wherein R3 is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof.

[0139] More preferably, E represents a group -O-R3-O-, wherein R3 represents a straight or branched C1-C ... 18 Alkylene groups, such as methylene, butylene, propylene, and ethylene.

[0140] According to a specific embodiment, the (poly)carbodiimide compound is a copolymer derived from α-methylstyryl isocyanate of the following formula (X):

[0141]

[0142] wherein R independently represents an alkyl group having from 1 to 24 carbon atoms, a cycloalkyl group having from 3 to 24 carbon atoms or an aryl group having from 6 to 24 carbon atoms, and

[0143] n indicates an integer ranging from 2 to 100.

[0144] In this embodiment, the term "alkyl" is as previously defined.

[0145] In this embodiment, the term "cycloalkyl" is as previously defined.

[0146] In this embodiment, n may indicate an integer ranging from 2 to 50, preferably from 3 to 30 and even more preferably from 5 to 10.

[0147] According to another specific embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI):

[0148]

[0149] wherein R independently represents an alkyl group having from 1 to 24 carbon atoms, a cycloalkyl group having from 3 to 24 carbon atoms or an aryl group having from 6 to 24 carbon atoms.

[0150] "Alkyl," "cycloalkyl," and "aryl" are as previously defined.

[0151] According to a preferred embodiment, the (poly)carbodiimide compound is selected from the compounds of formula (I) or formula (II), wherein:

[0152] -X1 and X2 independently represent an oxygen atom;

[0153] - 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, more preferably compounds of formula (VI) as described above, wherein R 13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30;

[0154] - n and z (when they are present) indicate integers ranging from 1 to 20, where n+z≥2 and w is equal to 1;

[0155] -L1 (when present) is selected from C1-C 18 Divalent aliphatic hydrocarbon-based groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocycloalkylene or C6-C 14 Arylene, and mixtures thereof, preferably C3-C 15 Cycloalkylene;

[0156] -A (when present) is selected from C1-C 18 Divalent aliphatic hydrocarbon-based groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocycloalkylene or C6-C 14 Arylene, and mixtures thereof, preferably C3-C 15 Cycloalkylene;

[0157] -E (when present) independently represents a group selected from:

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

[0159] wherein R3 and R4 are independently selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene and mixtures thereof;

[0160] - When R5 is not a covalent bond, R5 (when present) is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof; and

[0161] -R6 (when present) is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof.

[0162] Preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein:

[0163] -X1 and X2 independently represent an oxygen atom;

[0164] - 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;

[0165] - n and z indicate integers ranging from 1 to 20, where n+z≥2 and w is equal to 1;

[0166] -L1 is selected from C1-C 18 Divalent aliphatic hydrocarbon-based groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocycloalkylene or C6-C 14 Arylene, and mixtures thereof;

[0167] -E independently represents a group selected from the following:

[0168] --O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-;

[0169] wherein R3 and R4 are independently selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene and mixtures thereof;

[0170] - When R5 is not a covalent bond, R5 is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof; and

[0171] -R6 is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof.

[0172] More preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein:

[0173] -X1 and X2 independently represent an oxygen atom;

[0174] - R1 and R2 are independently monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed;

[0175] - n and z indicate integers ranging from 1 to 20, where n+z≥2 and w is equal to 1;

[0176] -L1 is C3-C 15 Cycloalkylene;

[0177] -E independently represents a group selected from the following:

[0178] --O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-;

[0179] wherein R3 and R4 are independently selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene and mixtures thereof;

[0180] - When R5 is not a covalent bond, R5 is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof; and

[0181] -R6 is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof.

[0182] Even more preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein:

[0183] -X1 and X2 independently represent an oxygen atom;

[0184] - R1 and R2 independently represent a compound of the following formula (VI):

[0185] R 13 -[O-CH2-C(H)(R 14 )] q - (VI),

[0186] Where R13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30;

[0187] - n and z indicate integers ranging from 2 to 20, wherein n+z ranges from 4 to 10 and w is equal to 1;

[0188] -L1 is C3-C 15 Cycloalkylene, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane; and

[0189] -E represents a group -O-R3-O-, wherein R3 is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof.

[0190] Even more preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein:

[0191] -X1 and X2 independently represent an oxygen atom;

[0192] - R1 and R2 independently represent a compound of the following formula (VI):

[0193] R 13 -[O-CH2-C(H)(R 14 )] q - (VI)

[0194] Where R 13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30;

[0195] - n and z indicate integers ranging from 2 to 20, wherein n+z ranges from 4 to 10 and w is equal to 1;

[0196] -L1 is C3-C 15 Cycloalkylene, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and

[0197] -E represents a group -O-R3-O-, wherein R3 represents a straight or branched C1-C 18 Alkylene groups, such as methylene, propylene, butylene, and ethylene.

[0198] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of the following formula (XII):

[0199]

[0200] wherein L1 is 4,4-dicyclohexylene methane, n and z indicate integers ranging from 2 to 20, wherein n+z ranges from 4 to 10, and E represents a group -O-R3-O-, wherein R3 represents a straight or branched C1-C ... 18 Alkylene groups such as methylene, propylene, butylene, ethylene, and r and s indicate integers ranging from 4 to 30.

[0201] The total amount of (poly)carbodiimide compounds present in the dyeing composition preferably ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferably from 0.2% to 10% by weight, even more preferably from 0.5% to 8%, better still from 1% to 6% by weight relative to the total weight of the dyeing composition.

[0202] Colorants

[0203] As previously indicated, the composition for dyeing keratin hair fibres used in the context of the method according to the invention comprises one or more coloring agents chosen from pigments, direct dyes and mixtures thereof.

[0204] Preferably, the composition for dyeing keratin hair fibres comprises one or more pigments.

[0205] The term "pigment" means any pigment which imparts colour to keratin materials. Their solubility in water at 25°C and atmospheric pressure (760 mmHg) is less than 0.05% by weight and preferably less than 0.01%.

[0206] The pigments that may be used are chosen in particular from the organic and / or mineral pigments known in the art, in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and Ullmann's Encyclopedia of Industrial Chemistry.

[0207] They may be natural, of natural origin, or non-natural.

[0208] These pigments may be in the form of pigment powders or pastes. They may be coated or uncoated.

[0209] The pigments may, for example, be chosen from mineral pigments, organic pigments, lakes, pigments with special effects such as mother-of-pearl or glitter flakes, and mixtures thereof.

[0210] The pigment may be a mineral pigment. "Mineral pigment" means any pigment that meets the definition in the chapter on inorganic pigments in Ullmann's Encyclopedia. Among the mineral pigments that can be used in the present invention, mention may be made of iron oxide, chromium oxide, manganese violet, ultramarine, chromium hydrate, iron blue and titanium oxide.

[0211] The pigment may be an organic pigment. "Organic pigment" means any pigment that meets the definition in the chapter on organic pigments in Ullmann's Encyclopedia.

[0212] The organic pigments may in particular be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal complexes, isoindolinone, isoindoline, quinacridone, peronone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

[0213] In particular, the white or colored organic pigment can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments numbered in the Color Index with the index numbers CI 42090, 69800, 69825, 74100, 74160, yellow pigments numbered in the Color Index with the index numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, green pigments numbered in the Color Index with the index numbers CI 61565, 61570, 74260, Orange pigments numbered 11725, 45370, 71105, red pigments numbered in the color index with index numbers CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, as obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.

[0214] Examples that may also be mentioned include pigment pastes of organic pigments, such as the products sold under the following names by the company Hoechst:

[0215] - Cosmenyl Yellow 10G: Yellow 3 pigment (CI 11710);

[0216] - Cosmenyl Yellow G: Yellow 1 pigment (CI 11680);

[0217] - Cosmenyl Orange GR: Orange 43 pigment (CI 71105);

[0218] - Cosmenyl Red R: Red 4 pigment (CI 12085);

[0219] - Cosmenyl Carmine FB: Red 5 pigment (CI 12490);

[0220] - Cosmenyl Violet RL: Violet 23 pigment (CI 51319);

[0221] - Cosmenyl Blue A2R: blue 15.1 pigment (CI 74160);

[0222] - Cosmenyl Green GG: Green 7 pigment (CI 74260);

[0223] - Cosmenyl Black R: Black 7 Pigment (CI 77266).

[0224] The pigments according to the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may in particular consist of particles comprising an inorganic core, at least one binder for attaching an organic pigment to the core and at least one organic pigment at least partially covering the core.

[0225] The organic pigment may also be a lake. "Lake" means a dye adsorbed on insoluble particles, the assembly thus obtained remaining insoluble during use.

[0226] The inorganic substrate onto which the dye is adsorbed is, for example, alumina, silica, sodium calcium borosilicate or calcium aluminum borosilicate and aluminum.

[0227] Among these dyes, mention may be made of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42090).

[0228] Examples of lakes that may be mentioned are the products known under the following names: D&C Red 7 (CI 15 850:1).

[0229] Pigments may also be special effect pigments. "Special effect pigments" means pigments that generally produce a colored appearance (characterized by a certain chromaticity, a certain vivacity and a certain brightness level) that is not uniform and varies based on viewing conditions (light, temperature, viewing angle, etc.). Thus, they differ from colored pigments that provide a standard uniform opaque, translucent or transparent hue.

[0230] There are several types of special effect pigments: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.

[0231] Examples of special effect pigments that may be mentioned include pearlescent pigments, such as mica coated with titanium or coated with bismuth oxychloride, colored pearlescent pigments, such as mica coated with titanium and iron oxides, mica coated with iron oxides, mica coated with titanium and in particular with iron blue or with chromium oxides, mica coated with titanium and an organic pigment as defined previously, and also pearlescent pigments based on bismuth oxychloride. Pearlescent pigments that may be mentioned include the nacres Cellini (mica-TiO2-lake) sold by BASF, Prestige (mica-TiO2) sold by Eckart, Prestige Bronze (mica-Fe2O3) sold by Eckart and Colorona (mica-TiO2-Fe2O3) sold by Merck.

[0232] Mention may also be made of the gold mother-of-pearl sold, in particular, by BASF under the names Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); bronze mother-of-pearl sold, in particular, by Merck under the names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super bronze (Cloisonne); orange mother-of-pearl sold, in particular, by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion orange (Colorona) and Matteorange (17449) (Microna); and Nu-antiquecopper 340XB (Cloisonne) and Brown by BASF. brown mother-of-pearl sold under the name CL4509 (Chromalite); brown mother-of-pearl with a copper hue, sold in particular by BASF under the name Copper 340A (Timica); mother-of-pearl with a red hue, sold in particular by Merck under the name Sienna fine (17386) (Colorona); mother-of-pearl with a yellow hue, sold in particular by BASF under the name Yellow (4502) (Chromalite); red mother-of-pearl with a golden hue, sold in particular by BASF under the name Sunstone G012 (Gemtone); pink mother-of-pearl sold in particular by BASF under the name Tan opale G005 (Gemtone); black mother-of-pearl with a golden hue, sold in particular by BASF under the name Nuantique bronze 240AB (Timica); blue nacres sold under the name Blue (17433) (Microna); white nacres with a silvery hue sold in particular under the name Xirona Silver by Merck; and golden green pink-orange nacres sold in particular under the name Indian summer (Xirona) by Merck; and mixtures thereof.

[0233] Still by way of example of nacres, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

[0234] Particles comprising a glass substrate coated with titanium oxide are sold in particular by the company Toyal under the name Metashine MC1080RY.

[0235] Finally, examples of nacres that may also be mentioned include polyethylene terephthalate glitter flakes, in particular those sold under the name Silver 1P 0.004X0.004 (silver glitter flakes) by the company Meadowbrook Inventions. Multilayer pigments based on synthetic substrates such as alumina, silica, sodium calcium borosilicate, calcium aluminum borosilicate and aluminum are also conceivable.

[0236] The special effect pigments may also be chosen from reflective particles, that is to say in particular from particles whose size, structure, in particular the thickness of the layer in which they are made, and their physical and chemical properties as well as the surface state allow them to reflect incident light. If appropriate, when applied to the support to be made up, this reflection may be of sufficient intensity to produce, on the surface of the composition or mixture, visible highlights (i.e. points that are brighter in contrast to their environment by the appearance of sparkles), visible to the naked eye.

[0237] The reflective particles may be selected so as not to significantly alter the coloring effect produced by the colorant with which they are combined, and more particularly so as to optimize this effect in terms of color reproduction. They may more particularly have a yellow, pink, red, bronze, orange-like, brown, gold and / or copper tint or shade.

[0238] The particles may have different forms and may in particular be in platelet-like or spherical form, in particular in spherical form.

[0239] Regardless of their form, the reflective particles may or may not have a multilayer structure and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, in particular of a reflective material.

[0240] When the reflective particles do not have a multilayer structure, they can consist, for example, of metal oxides, in particular synthetically obtained titanium or iron oxides.

[0241] When the reflective particles have a multilayer structure, they can include, for example, a natural or synthetic substrate, in particular a synthetic substrate at least partially coated with at least one layer of reflective material, in particular at least one metal or metallic material. The substrate can be made of one or more organic and / or inorganic materials.

[0242] More particularly, it may be chosen from glass, ceramics, graphite, metal oxides, alumina, silica, silicates (especially aluminosilicates and borosilicates), and synthetic mica, and mixtures thereof, this list not being limiting.

[0243] The reflective material may include a metal layer or a layer of metallic material.

[0244] The reflective particles are described in particular in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0245] Furthermore, as examples of reflective particles comprising a mineral substrate coated with a metal layer, mention may also be made of particles comprising a silver-coated borosilicate substrate.

[0246] Particles with a silver-coated glass substrate in the form of flakes are sold under the name Microglass Metashine REFSX 2025PS by Toyo Corporation. Particles with a glass substrate coated with a nickel / chromium / molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by the same company.

[0247] It is also possible to use particles comprising a metal substrate, such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, which 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.

[0248] Examples that may be mentioned include aluminum powders, bronze powders or copper powders coated with SiO 2 , which are sold under the name Visionaire by the company Eckart.

[0249] Mention may also be made of interference pigments which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectraf / x from Spectratek). Special effect pigments also include fluorescent pigments (whether these are substances that fluoresce in daylight or produce UV fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, such as sold by QuantumDots Corporation.

[0250] The various pigments which can be used in the invention make it possible to obtain a wide range of colors, and also specific optical effects, such as metallic effects or interference effects.

[0251] 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 preferably between 30 nm and 50 μm.

[0252] The pigment may be dispersed in the composition by a dispersant.

[0253] Dispersants are used to protect the dispersed particles from agglomeration or flocculation. The dispersants can be surfactants, oligomers, polymers or mixtures of several thereof with one or more functional groups having a strong affinity for the surface of the particles to be dispersed. In particular, they can become physically or chemically attached to the surface of the pigment. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, use is made of esters of, in particular, 12-hydroxystearic acid and of C8 to C20 fatty acids and of polyols such as glycerol or diglycerol, for example poly(12-hydroxystearic acid)stearate having a molecular weight of about 750 g / mol, such as the product sold under the name Solsperse 21 000 by Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by Henkel, or polyhydroxystearic acids such as the product sold under the reference Arlacel P100 by Uniqema, and mixtures thereof.

[0254] As other dispersants that can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, such as Solsperse 17 000 sold by Avicia, and polydimethylsiloxane / propylene oxide mixtures, such as those sold under the references DC2-5185 and DC2-5225 C by Dow Corning.

[0255] The pigments used in the composition may be surface treated with an organic agent.

[0256] Thus, pigments which have previously been surface-treated and which are usable 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 an organic agent, such as those described in particular in Cosmetics and Toiletries, February 1990, volume 105, pages 53-64, and which are then dispersed in the composition according to the invention. These organic agents can, for example, be chosen from waxes, such as carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and its derivatives; anionic surfactants; lecithin; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, such as aluminum stearate or aluminum laurate; metal alkoxides; polyethylene; (meth)acrylic acid polymers, such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; polysiloxane compounds, such as polysiloxanes, in particular polydimethylsiloxanes; organic fluorine compounds, such as perfluoroalkyl ethers; fluorosilicone compounds.

[0257] The surface-treated pigments that can be used in the composition may also have been treated with mixtures of these compounds and / or may have undergone several surface treatments.

[0258] The surface-treated pigments useful in the context of the present invention can be prepared according to surface treatment techniques well known to those skilled in the art, or can be purchased commercially as such.

[0259] Preferably, the surface treated pigment is coated with an organic layer.

[0260] The organic agent for treating the pigment may be attached to the pigment by evaporation of the solvent, chemical reaction between molecules of the surfactant, or formation of a covalent bond between the surfactant and the pigment.

[0261] The surface treatment can thus be carried out, for example, by chemical reaction of the surfactant with the pigment surface and formation of covalent bonds between the surfactant and the pigment or filler. This method is described in particular in patent US Pat. No. 4,578,266.

[0262] Preference is given to using organic agents which are covalently bonded to the pigment.

[0263] The agent for surface treatment may account for 0.1 to 50% by weight, preferably 0.5 to 30% by weight and even more preferably 1 to 20% by weight of the total weight of the surface-treated pigment.

[0264] Preferably, the surface treatment agent of the pigment is selected from the following treatment agents:

[0265] - PEG-silicone treatments, such as AQ surface treatment sold by LCW;

[0266] - polymethylsiloxane treatments, such as SI surface treatments sold by LCW;

[0267] - polydimethylsiloxane treatments, such as Covasil 3.05 surface treatment sold by LCW;

[0268] - polydimethylsiloxane / trimethylsiloxysilicate treatment agents, such as Covasil 4.05 surface treatment agent sold by LCW;

[0269] - magnesium myristate treatments, such as the MM surface treatment sold by LCW;

[0270] - Aluminium dimyristate treatment agents, such as the MI surface treatment agent sold by Miyoshi;

[0271] - perfluoropolymethylisopropyl ether treatment agents, such as the FHC surface treatment agent sold by LCW;

[0272] - isostearyl sebacate treatment agents, such as HS surface treatment agent sold by Miyoshi Chemicals;

[0273] - perfluoroalkyl phosphate treatment agents, such as the PF surface treatment agents sold by Daito;

[0274] - acrylate / polydimethylsiloxane copolymers and perfluoroalkyl phosphate treatments, such as the FSA surface treatment sold by Daito Corporation;

[0275] - polymethylhydrogensiloxane / perfluoroalkyl phosphate treatment agent, such as FS01 surface treatment agent sold by Dadong Company;

[0276] - acrylate / polydimethylsiloxane copolymer treatment agents, such as ASC surface treatment agent sold by Dadong Company;

[0277] - isopropyl titanate triisostearate treatment agents, such as the ITT surface treatment agent sold by Dadong Company;

[0278] - Acrylate copolymer treatment agents, such as APD surface treatment agents sold by Dadong Company;

[0279] - Perfluoroalkyl phosphate / isopropyl titanate triisostearate treatment agent, such as PF+ITT surface treatment agent sold by Daito Corporation.

[0280] According to a particular embodiment of the invention, the dispersant is present together with the organic or inorganic pigment in composition B in the form of particles of submicron size.

[0281] “Submicron sized” or “submicron” means a pigment having a particle size that has been micronized by a micronization process and having an average particle size less than microns (μm), in particular between 0.1 and 0.9 μm and preferably between 0.2 and 0.6 μm.

[0282] According to one embodiment, the dispersant and the pigment are present in an amount according to a weight ratio (dispersant:pigment) between 1:4 and 4:1, in particular between 1.5:3.5 and 3.5:1 or better still between 1.75:3 and 3:1.

[0283] Thus, the dispersants may have a silicone backbone, such as silicone polyethers and dispersants of the aminosilicone type other than the aminosilicones mentioned below. Among suitable dispersants, mention may be made of:

[0284] aminosilicones, i.e. silicones comprising one or more amino groups, such as those sold under the following names and reference numbers: BYK LPX 21879 from BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1 sold by Genesee Polymers,

[0285] - Silicone acrylates, such as those sold by Evonik RC 902, RC 922, RC 1041 and RC 1043,

[0286] - Polydimethylsiloxane (PDMS) silicones with carboxyl groups such as Shin-Etsu's X-22162 and X-22370, epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695, or Evonik's RC 1401, RC 1403, RC 1412.

[0287] According to one particular embodiment, the dispersant is of the aminosilicone type other than the aminosilicone mentioned below and is cationic.

[0288] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments or organic pigments.

[0289] In one variant of the invention, the pigment is an organic pigment, preferably an organic pigment surface-treated with an organic agent selected from silicone compounds. In another variant of the invention, the pigment is a mineral pigment.

[0290] Preferably, the pigment is chosen from: iron oxide, in particular red, brown or black iron oxide; nacres, in particular mica coated with titanium or bismuth oxychloride, mica coated with titanium and iron oxide, mica coated with iron oxide, mica coated with titanium; and mixtures thereof.

[0291] As an example of iron oxide, mention may be made of the product sold by Sun Chemical under the trade name Iron oxide sold by Red Iron Oxide.

[0292] As examples of nacres, mention may be made of mica and iron oxide sold under the name Pearlescent Pigment Prestige soft bronze by Sudarshan Chemical.

[0293] According to a preferred embodiment, the dyeing composition according to the invention comprises a mixture of pigments, in particular iron oxide, and nacres, in particular mica coated with titanium or bismuth oxychloride, mica coated with titanium and iron oxide, mica coated with iron oxide, mica coated with titanium.

[0294] Direct dyes

[0295] The composition for dyeing keratin hair fibres used in the context of the process according to the invention may comprise one or more direct dyes.

[0296] "Direct dyes" means natural and / or synthetic dyes, except oxidation dyes. These are dyes that will spread superficially on the fiber.

[0297] They may be ionic or nonionic, preferably cationic or nonionic.

[0298] Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes, such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, either alone or in mixtures.

[0299] The direct dye is preferably a cationic direct dye. Mention may be made of the following hydrazono cationic dyes of formula (XIII) and (XIV) and azo cationic dyes of formula (XV) and (XVI):

[0300] Het +-N(Ra)-N=C(Rb)-Ar,Q- (XIII),

[0301] Het + -C(Ra)=NN(Rb)-Ar,Q (XIV),

[0302] Het + -N=N-Ar,Q- (XV),

[0303] Ar + -N=N-Ar”,Q-

[0304] (XVI),

[0305] In formulae (XIII) to (XVI):

[0306] -Het+ represents a cationic heteroaryl group, preferably with an intracyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally, preferably, substituted by at least one (C1-C8)alkyl group, such as methyl;

[0307] -Ar+ represents an aromatic group with an exocyclic cationic charge, preferably ammonium, in particular tri(C1-C8)alkylammonium such as trimethylammonium, such as phenyl or naphthyl;

[0308] - Ar represents an aryl group, in particular a phenyl group, which is optionally substituted preferably by 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, optionally substituted on the alkyl by hydroxy, iv) aryl(C1-C8)alkylamino, v) optionally substituted N-(C1-C8)alkyl-N-aryl(C1-C8)alkylamino, or alternatively, Ar represents a julolidine group;

[0309] -Ar" represents optionally substituted (hetero)aryl, such as phenyl or pyrazolyl, which is optionally substituted, preferably by one or more (C1-C8)alkyl, hydroxy, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl;

[0310] - Ra and Rb are the same or different and represent a hydrogen atom or a (C1-C8)alkyl group which is optionally substituted preferably by a hydroxyl group;

[0311] or in addition the substituents Ra and Het+ and / or Rb and Ar together with the atoms carrying them form a (hetero)cycloalkyl group; in particular, Ra and Rb represent a hydrogen atom or a (C1-C4)alkyl group which is optionally substituted by a hydroxyl group;

[0312] -Q- represents an organic or inorganic anionic counterion, such as a halide or an alkyl sulfate.

[0313] In particular, mention may be made of azo and hydrazono direct dyes with an intracyclic cationic charge of formulae (XIII) to (XVI) as defined previously; more particularly, cationic direct dyes with an intracyclic cationic charge are described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954; preference is given to the following direct dyes:

[0314]

[0315] In formulae (XVII) and (XVIII):

[0316] -R 1 represents a (C1-C4)alkyl group such as methyl;

[0317] -R 2 and R 3 are the same or different and represent a hydrogen atom or a (C1-C4) alkyl group, such as a methyl group; and

[0318] -R 4 represents a hydrogen atom or an electron-donating group, such as optionally substituted (C1-C8)alkyl, optionally substituted (C1-C8)alkoxy, or (di)(C1-C8)(alkyl)amino optionally substituted by hydroxy on the alkyl; in particular, R 4 It is a hydrogen atom;

[0319] -Z represents a CH group or a nitrogen atom, preferably CH;

[0320] -Q- is an anionic counterion as defined previously, in particular a halide such as chloride, or an alkyl sulfate such as methyl sulfate or mesityl.

[0321] In particular, the dyes of formula (XVII) and (XVIII) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof, wherein Q' is an anionic counterion as previously defined, in particular a halide such as chloride, or an alkyl sulfate such as methyl sulfate or mesityl.

[0322] Direct dye can be selected from anionic direct dye.Anionic direct dye of the present invention is the dyestuff that is usually called "acidic" direct dye due to their affinity to alkaline substances."anionic direct dye" means any direct dye comprising at least one CO2R or SO3R substituent in its structure, wherein R represents a hydrogen atom or a cation or an ammonium ion derived from a metal or amine.Anionic dye can be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indigo amine (indoamine) acid dyes, anthraquinone acid dyes, indigo dyes and natural acid dyes.

[0323] As acid dyes which can be used in the present invention, mention may be made of the dyes of the following formulae (XIX), (XIX'), (XX), (XX'), (XXI), (XXI'), (XXII), (XXII'), (XXIII), (XXIV), (XXV) and (XXVI):

[0324] a) Diaryl anionic azo dyes of formula (XIX) or (XIX'):

[0325]

[0326] In formulas (XIX) and (XIX'):

[0327] -R7, R8, R9, R 10 , R'7, R'8, R'9 and R' 10 The same or different, represents a hydrogen atom or a group selected from the following:

[0328] -alkyl;

[0329] - alkoxy, alkylthio;

[0330] -Hydroxy, thiol;

[0331] -Nitro, nitroso;

[0332] -R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"-, wherein R° represents a hydrogen atom or an alkyl group or an aryl group; X, X' and X" are the same or different and represent an oxygen or sulfur atom, or NR, wherein R represents a hydrogen atom or an alkyl group;

[0333] -(O)2S(O-)-,M+, where M+ represents a hydrogen atom or a cationic counterion;

[0334] -(O)CO--,M+, wherein M+ is as previously defined;

[0335] -R"-S(O)2-, wherein R" represents a hydrogen atom or an alkyl group, an aryl group, a (di)(alkyl)amino group or an aryl(alkyl)amino group; preferably a phenylamino group or a phenyl group;

[0336] -R"'-S(O)2-X'-, wherein R"' represents an optionally substituted alkyl or aryl group and X' is as previously defined;

[0337] -(di)(alkyl)amino;

[0338] - aryl(alkyl)amino, optionally substituted by one or more groups selected from: i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+ and iv) alkoxy, wherein M+ is as previously defined;

[0339] - optionally substituted heteroaryl; preferably benzothiazolyl;

[0340] - cycloalkyl, especially cyclohexyl;

[0341] -Ar-N=N-, wherein Ar represents an optionally substituted aryl group; preferably a phenyl group optionally substituted by one or more alkyl groups, (O)2S(O-)-, M+ or phenylamino groups;

[0342] - or alternatively, two adjacent groups R7 and R8 or R8 and R9 or R9 and R 10 together form a fused benzo group A'; and R'7 and R'8 or R'8 and R'9 or R'9 and R' 10 together to form a fused benzo group B'; wherein A' and B' are optionally substituted by one or more groups selected from the following: i) nitro; ii) nitroso; iii) (O) 2S (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; wherein M + , R°, X, X', X" and Ar are as previously defined;

[0343] -W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent radical i) -NR-, wherein R is as previously defined, or ii) a methylene group -C(Ra)(Rb)-, wherein Ra and Rb are identical or different, represent a hydrogen atom or an aryl group, or alternatively, Ra and Rb together with the carbon atom carrying them form a spirocycloalkyl group; preferably, W represents a sulfur atom or Ra and Rb together form a cyclohexyl group;

[0344] It is understood that formula (XIX) and (XIX') contain at least one sulfonate group (O)2S(O-)-, M+ or one carboxylate group (O)CO--, M+ on one of the rings A, A', B, B' or C; preferably sodium sulfonate.

[0345] As examples of dyes of formula (XIX), mention may be made of 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 18 4, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or Sunset Yellow;

[0346] Also, as examples of dyes of formula (XIX'), there may be mentioned: Acid Red 111, Acid Red 134, Acid Yellow 38;

[0347] b) Pyrazolone anionic azo dyes of formula (XX) and (XX'):

[0348]

[0349] In formula (XX) and (XX'):

[0350] -R 11 , R 12 and R 13 are the same or different and represent a hydrogen or halogen atom, an alkyl group or -(O)2S(O-), M+, wherein M+ is as defined previously;

[0351] -R 14 represents a hydrogen atom, an alkyl group or a group -C(O)O - ,M + , where M + As previously defined;

[0352] -R 15 represents a hydrogen atom;

[0353] -R 16 represents an oxo group, in which case R' 16 does not exist, or alternatively, R 15 With R 16 together to form a double bond;

[0354] -R 17 and R 18 The same or different, represents a hydrogen atom or a group selected from the following:

[0355] -(O)2S(O-)-,M+, wherein M+ is as previously defined;

[0356] -Ar-OS(O)2-, wherein Ar represents an optionally substituted aryl group; preferably a phenyl group optionally substituted by one or more alkyl groups;

[0357] -R 19 and R 20 together forming a double bond, or an optionally substituted benzo group D';

[0358] -R' 16 , R' 19 and R' 20 The same or different, represents a hydrogen atom or an alkyl group or a hydroxyl group;

[0359] -R 21 represents a hydrogen atom or an alkyl group or an alkoxy group;

[0360] - Ra and Rb are identical or different and as previously defined; preferably, Ra represents a hydrogen atom and Rb represents an aryl group;

[0361] -Y represents a hydroxyl group or an oxo group;

[0362] - represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;

[0363] It is understood that formula (XX) and (XX') contain at least one sulfonate group (O)2S(O-)-, M+ or one carboxylate group -C(O)O-, M+ on one of the rings D or E; preferably sodium sulfonate;

[0364] As examples of dyes of formula (XX), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (XX′), mention may be made of: Acid Yellow 17;

[0365] c) Anthraquinone dyes of formula (XXI) and (XXI'):

[0366]

[0367] In formula (XXI) and (XXI'):

[0368] -R 22 , R 23 , R 24 , R 25 , R 26 and R 27 The same or different, represents a hydrogen atom or a halogen atom, or a group selected from the following:

[0369] -alkyl;

[0370] -Hydroxy, thiol;

[0371] - alkoxy, alkylthio;

[0372] - optionally substituted aryloxy or arylthio, which is preferably selected from alkyl and (O)2S(O - )-,M + One or more groups are substituted, wherein M + As previously defined;

[0373] - aryl(alkyl)amino, which may be optionally substituted with one or more selected from alkyl and (O)2S(O - )-,M + The group substituted, where M + As previously defined;

[0374] -(di)(alkyl)amino;

[0375] -(di)(hydroxyalkyl)amino;

[0376] -(O)2S(O-)-,M+, wherein M+ is as previously defined;

[0377] -Z' represents a hydrogen atom or a group NR 28 R 29 , where R 28 and R 29 The same or different, represents a hydrogen atom or a group selected from the following:

[0378] -alkyl;

[0379] - polyhydroxyalkyl, such as hydroxyethyl;

[0380] - aryl, optionally substituted by one or more groups, in particular: i) alkyl, such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O - )-,M + , where M + as previously defined; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"-, wherein R°, X, X' and X" are as previously defined, preferably R° represents an alkyl group;

[0381] - cycloalkyl, especially cyclohexyl;

[0382] -Z represents a group consisting of hydroxyl and NR' 28 R' 29 A group in which R' 28 and R' 29 Same or different, meaning R as defined previously 28 and R29 The same atoms or groups;

[0383] It is understood that formula (XXI) and (XXI') contain at least one sulfonate group (O)2S(O-)-, M+ or one carboxylate group -C(O)O-, M+; preferably sodium sulfonate;

[0384] As examples of dyes of formula (XXI), there may be mentioned: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2; and, as examples of dyes of formula (XXI'), there may be mentioned: Acid Black 48;

[0385] d) Nitro dyes of formula (XXII) and (XXII'):

[0386]

[0387] In formula (XXII) and (XXII'):

[0388] -R 30 , R 31 and R 32 The same or different, represents a hydrogen atom or a halogen atom, or a group selected from the following:

[0389] -alkyl;

[0390] - alkoxy optionally substituted by one or more hydroxyl groups, alkylthio optionally substituted by one or more hydroxyl groups;

[0391] -Hydroxy, thiol;

[0392] -Nitro, nitroso;

[0393] -polyhaloalkyl;

[0394] -R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"-, wherein R°, X, X' and X" are as previously defined;

[0395] -(O)2S(O-)-,M+, wherein M+ is as previously defined;

[0396] -(O)CO--,M+, wherein M+ is as previously defined;

[0397] -(di)(alkyl)amino;

[0398] -(di)(hydroxyalkyl)amino;

[0399] -heterocycloalkyl, such as piperidino, piperazino or morpholino; in particular, R 30 , R 31 and R 32 represents a hydrogen atom;

[0400] -Rc and Rd are the same or different and represent a hydrogen atom or an alkyl group;

[0401] -W is as defined previously; W in particular represents a -NH- group;

[0402] -ALK represents a linear or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group;

[0403] -n is 1 or 2;

[0404] -p represents an integer between 1 and 5, inclusive;

[0405] -q represents an integer between 1 and 4, including the end value;

[0406] -u is 0 or 1;

[0407] - when n is 1, J represents nitro or nitroso; in particular nitro;

[0408] -When n is 2, J represents an oxygen or sulfur atom, or a divalent group -S(O) m -, wherein m represents an integer of 1 or 2; preferably, J represents a -SO2- group;

[0409] -M' represents a hydrogen atom or a cationic counterion;

[0410] - may be present or absent, indicating that it is optionally replaced by one or more groups R as defined previously 30 Substituted benzo groups;

[0411] It is to be understood that formula (XXII) and (XXII') contain at least one sulfonate group (O)2S(O-)-, M+ or one carboxylate group -C(O)O-, M+; preferably sodium sulfonate.

[0412] As examples of dyes of formula (XXII), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XXII'), mention may be made of: Acid Yellow 1,2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidinyl-5-nitrobenzenesulfonic acid, 2-(4'-N,N-(2"-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, the sodium salt of 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; External D&C Yellow 7 (EXT D&C Yellow 7);

[0413] e) Triarylmethane dyes of formula (XXIII):

[0414]

[0415] In formula (XXIII):

[0416] -R 33 , R 34 , R 35 and R 36 are identical or different and represent a hydrogen atom or a group selected from the group consisting of alkyl, optionally substituted aryl and optionally substituted aralkyl; in particular alkyl and benzyl optionally substituted by a group (O)mS(O-)-, M+, wherein M+ and m are as previously defined;

[0417] -R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 The same or different, represents a hydrogen atom or a group selected from the following:

[0418] -alkyl;

[0419] - alkoxy, alkylthio;

[0420] -(di)(alkyl)amino;

[0421] -Hydroxy, thiol;

[0422] -Nitro, nitroso;

[0423] -R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"-, wherein R° represents a hydrogen atom or an alkyl group or an aryl group; X, X' and X" are the same or different and represent an oxygen or sulfur atom, or NR, wherein R represents a hydrogen atom or an alkyl group;

[0424] -(O)2S(O-)-,M+, where M+ represents a hydrogen atom or a cationic counterion;

[0425] -(O)CO--,M+, wherein M+ is as previously defined;

[0426] - or alternatively, two adjacent groups R 41 With R 42 or R 42 With R 43 or R 43 With R 44together to form a fused benzo group: I'; wherein I' is optionally substituted with one or more groups selected from the group consisting of: i) nitro; ii) nitroso; iii) (O)2S(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"-; wherein M+, R°, X, X', X" are as defined above; in particular, R 37 To R 40 represents a hydrogen atom, and R 41 To R 44 are the same or different, representing a hydroxyl group or a (O)2S(O-)-, M+ group; and when R 43 With R 44 When together they form a benzo group, they are preferably substituted with a (O)2S(O-)- group;

[0427] It is understood that at least one of the rings G, H, I or I' comprises at least one sulfonate group (O)2S(O-)- or one carboxylate group -C(O)O-; preferably a sulfonate group.

[0428] As examples of dyes of formula (XXIII), mention may be made of: 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.

[0429] f) Xanthene-based dyes of formula (XXIV):

[0430]

[0431] In formula (XXIV):

[0432] -R 45 , R 46 , R 47 and R 48 the same or different, representing hydrogen or halogen atoms;

[0433] -R 49 , R 50 , R 51 and R 52 are the same or different and represent a hydrogen or halogen atom, or a group selected from the following:

[0434] -alkyl;

[0435] - alkoxy, alkylthio;

[0436] -Hydroxy, thiol;

[0437] -Nitro, nitroso;

[0438] -(O)2S(O-)-,M+, where M+ represents a hydrogen atom or a cationic counterion;

[0439] -(O)CO--,M+, wherein M+ is as previously defined;

[0440] In particular, R 49 , R 50 , R 51 and R 52 represents a hydrogen or halogen atom;

[0441] -G represents an oxygen or sulfur atom or a group NRe, wherein Re is as defined previously; in particular, G represents an oxygen atom;

[0442] -L represents alkoxide O - ,M + ; Thiol salt S - ,M + or a group NRf, wherein Rf represents a hydrogen atom or an alkyl group, and M + As defined above; M + especially sodium or potassium;

[0443] -L' represents an oxygen or sulfur atom or an ammonium group: N+RfRg, wherein Rf and Rg are identical or different and represent a hydrogen atom or an optionally substituted alkyl or aryl group; L' represents in particular an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (O)mS(O-)-,M+ groups, wherein m and M+ are as previously defined;

[0444] - Q and Q' are the same or different and represent an oxygen or sulfur atom; in particular, Q and Q' represent an oxygen atom;

[0445] -M + As defined previously.

[0446] As examples of dyes of formula (XXIV), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[0447] g) Indole-based dyes of formula (XXV):

[0448]

[0449] In formula (XXV):

[0450] -R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60The same or different, represents a hydrogen atom or a group selected from the following:

[0451] -alkyl;

[0452] - alkoxy, alkylthio;

[0453] -Hydroxy, thiol;

[0454] -Nitro, nitroso;

[0455] -R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"-, wherein R° represents a hydrogen atom or an alkyl group or an aryl group; X, X' and X" are the same or different and represent an oxygen or sulfur atom, or NR, wherein R represents a hydrogen atom or an alkyl group;

[0456] -(O)2S(O-)-,M+, where M+ represents a hydrogen atom or a cationic counterion;

[0457] -(O)CO--,M+, wherein M+ is as previously defined;

[0458] -G represents an oxygen or sulfur atom or a group NRe, wherein Re is as defined previously; in particular, G represents an oxygen atom;

[0459] -Ri and Rh are the same or different and represent a hydrogen atom or an alkyl group;

[0460] It is to be understood that formula (XXV) comprises at least one sulfonate group (O)2S(O-)-, M+ or one carboxylate group -C(O)O-, M+; preferably sodium sulfonate.

[0461] As examples of dyes of formula (XXV), mention may be made of: Acid Blue 74;

[0462] h) Quinoline-based dyes of formula (XXVI):

[0463]

[0464] In formula (XXVI):

[0465] -R 61 represents a hydrogen or halogen atom or an alkyl group;

[0466] -R 62 , R 63 and R 64 The same or different, represents a hydrogen atom or a group (O)2S(O-)-, M+, wherein M+ represents a hydrogen atom or a cationic counterion;

[0467] Or alternatively, R 61 With R 62 , or R 61 With R64 Together they form a benzo group, which is optionally substituted by one or more groups (O)2S(O-)-, M+, wherein M+ represents a hydrogen atom or a cationic counterion;

[0468] It will be appreciated that formula (XXVI) comprises at least one sulfonate group (O)2S(O-)-, M+, preferably sodium sulfate.

[0469] As examples of dyes of formula (XXVI) there may be mentioned: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0470] Among the natural direct dyes that can be used according to the invention, mention may be made of hennaquinone, juglone, alizarin, purpurin, carminic acid, carminic acid, erythrogallol, protocatechaldehyde, indigo, isatin, curcumin, arachidin, apigenin and orcein. It is also possible to use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

[0471] Preferably, the direct dyes are selected from anionic direct dyes.

[0472] The coloring agents may be present in a total amount ranging from 0.001% to 20% by weight and preferably from 0.005% to 15% by weight relative to the total weight of the dyeing composition; preferably, the coloring agents are chosen from pigments.

[0473] The pigments may be present in a total amount ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight and better still from 0.5% to 10% by weight relative to the total weight of the dyeing composition.

[0474] The direct dyes may be present in a total amount ranging from 0.001% to 10% by weight relative to the total weight of the composition, preferably from 0.005% to 5% by weight relative to the total weight of the dyeing composition.

[0475] Non-carboxylic acid anionic thickener

[0476] The compositions for dyeing keratin hair fibres may also comprise a non-carboxylic acid anionic thickener.

[0477] For the purposes of the present invention, a "non-carboxylic acid reagent" means a reagent that does not contain any carboxylic acid functional group (-COOH) or carboxylate functional group (-COO - ) reagents.

[0478] For the purposes of the present invention, "thickener" means a compound which has a viscosity at room temperature (25° C.), at atmospheric pressure and at 1 s -1The viscosity of the composition into which the compound is introduced at a concentration of 0.05% by weight relative to the total weight of the composition is increased by at least 20 cps, preferably at least 50 cps at a shear rate of 1.5 %.

[0479] Preferably, the non-carboxylic acid anionic thickener is selected from non-carboxylic acid anionic polymers, more preferably from anionic polymers carrying one or more sulfonic acid groups.

[0480] For the purposes of the present invention, "anionic polymer" means a polymer that contains one or more anionic or anionizable groups and does not contain any cationic or cationizable groups.

[0481] Advantageously, the non-carboxylic anionic thickener is chosen from anionic polymers comprising at least one ethylenically unsaturated monomer carrying sulfonic acid groups, in free form or in partially or completely neutralized form.

[0482] These polymers may be cross-linked or non-cross-linked. They are preferably cross-linked.

[0483] These polymers may be associative or non-associative, preferably non-associative.

[0484] It is contemplated that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0485] Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.

[0486] "Hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon-based chain containing at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms, and more preferably from 18 to 30 carbon atoms.

[0487] Preferably, 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, dodecanol or decanol. It may also indicate a hydrocarbon-based polymer, such as polybutadiene.

[0488] The ethylenically unsaturated monomers carrying sulfonic acid groups are selected in particular from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamide (C1-C 22 ) alkylsulfonic acid, N-(C1-C 22 )alkyl(meth)acrylamide(C1-C 22 ) alkylsulfonic acids such as undecylacrylamidomethanesulfonic acid and also partially or completely neutralized forms thereof.

[0489] More preferably, the (meth)acrylamide group (C1-C 22 ) alkylsulfonic acids, for example acrylamido methanesulfonic acid, acrylamido ethanesulfonic acid, acrylamido propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and also partially or completely neutralized forms thereof.

[0490] Use is made more particularly of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and also its partially or completely neutralized forms.

[0491] 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; mention may in particular be made of the products described in Example 1 of EP 503 853, and reference may be made to said document with regard to these polymers.

[0492] 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 SEPPIC (INCI name: hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer).

[0493] The associative AMPS polymers can be selected in particular from 22 Randomly associative AMPS polymers modified by reaction with n-mono- or di-n-alkylamines, and as described in patent application WO 00 / 31154, forming an integral part of the content of the specification. These polymers may also contain other ethylenically unsaturated hydrophilic monomers selected, for example, from (meth)acrylic acid derivatives, such as their esters with monohydric alcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, or mixtures of these compounds.

[0494] Preferred polymers of this family are selected from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0495] These same copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acid derivatives, in particular their esters with monohydric alcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, or mixtures of these compounds.

[0496] These copolymers are described in particular in patent application EP-A 750 899, patent US 5 089 578 and in the following publication by Yotaro Morishima:

[0497] -Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40, (2000), 323-336;

[0498] -Micelle formation of random copolymers of sodium2-(acrylamido)-2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water asstudied by fluorescence and dynamic light scattering, Macromolecules, Vol. 33, No. 10, (2000), 3694-3704;

[0499] -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;

[0500] -Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers, Polym. Preprint, Div. Polym. Chem. 40(2), (1999), 220-221.

[0501] Among these polymers, mention may be made of:

[0502] - a crosslinked or non-crosslinked, neutralized or unneutralized copolymer comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C8-C 16 ) alkyl (meth) acrylamide or (meth) acrylic acid (C8-C 16 ) alkyl ester units, such as those described in patent application EP-A 750 899;

[0503] - a terpolymer comprising from 10 mol % to 90 mol % of acrylamide units, from 0.1 mol % to 10 mol % of AMPS units and from 5 mol % to 80 mol % of n-(C6-C 18 ) alkylacrylamide units, such as those described in patent US-5 089 578.

[0504] Mention may also be made of completely neutralized copolymers of AMPS and dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and n-dodecylmethacrylamide, such as those described in the abovementioned Morishima article.

[0505] Preferably, the non-carboxylic acid anionic thickener is chosen from the group consisting of sodium 2-acrylamido-2-methylpropane sulfonate / hydroxyethyl acrylate copolymer (INCI name: hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer) sold by the company Cypic.

[0506] Advantageously, the total amount of non-carboxylic acid anionic thickener may range from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, better still from 0.1% to 5% by weight and even better still from 0.1% to 3% by weight relative to the total weight of the dyeing composition.

[0507] Silicone

[0508] The composition for dyeing keratin hair fibres may also comprise at least one silicone.

[0509] Silicones are distinguished from compounds having at least one carboxylic acid group as defined below.

[0510] Preferably, the dyeing composition comprises at least one silicone selected from non-amino silicones, amino silicones and mixtures thereof.

[0511] Silicone at 25°C and atmospheric pressure (1.013×10 5 Pa) can be solid or liquid and volatile or non-volatile.

[0512] The silicones that can be used may be soluble or insoluble in the compositions according to the invention; they may be in the form of oils, waxes, resins or gums; silicone oils are preferred.

[0513] Silicones are described in particular detail in "Chemistry and Technology of Silicones" by Walter Noll (1968), Academic Press.

[0514] Preferably, the dyeing composition contains one or more 5 Pa) is liquid silicone.

[0515] The volatile silicones may be chosen from those having a boiling point between 60° C. and 260° C. (at atmospheric pressure), and more particularly from:

[0516] i) Cyclic polydialkylsiloxanes containing 3 to 7 and preferably 4 to 5 silicon atoms, such as

[0517] -Octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

[0518] Mention may be made of the products sold under the name Volatile Silicone 7207 by Union Carbide or under the name Silbione 70045V 2 by Rhodia, Volatile Silicone 7158 by Union Carbide or under the name Silbione 70045V 5 by Rhodia;

[0519] - Cyclic copolymers of dimethylsiloxane / methylalkylsiloxane type having the following chemical structure:

[0520]

[0521] Cyclomethicone is preferred.

[0522] Mention may be made of Volatile Silicone FZ 3109 sold by Union Carbide.

[0523] - mixtures of cyclic silicones with organic compounds derived from silicon, such as a mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50 / 50) and a mixture of octamethylcyclotetrasiloxane and 1,1′-oxy(2,2,2′,2′,3,3′-hexatrimethylsilyloxy)bisneopentane;

[0524] ii) a linear polydialkylsiloxane having 2 to 9 silicon atoms, which generally has a carbon number less than or equal to 5×10 -6 m 2 / s viscosity, such as decamethyltetrasiloxane.

[0525] Other silicones belonging to this category are described in the article Volatile silicone fluids for cosmetics by Todd & Byers, Cosmetics and Toiletries, Vol. 91, January 1976, pp. 27-32; mention may be made of the product sold under the name SH 200 by the company Toray Silicone.

[0526] Among the non-volatile silicones, mention may be made, alone or as a mixture, of polydialkylsiloxanes and in particular polydimethylsiloxanes (PDMS), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and also organopolysiloxanes (or organomodified polysiloxanes, or alternatively organomodified silicones), which are polysiloxanes containing in their structure one or more organic functional groups, generally attached by hydrocarbon groups, and preferably chosen from aryl, amine, alkoxy and polyoxyethylene or polyoxypropylene groups. Preferably, the non-volatile silicones are chosen from polydimethyl / methylsiloxanes, optionally oxyethyleneated and oxypropyleneated.

[0527] The organomodified silicones may be polydiarylsiloxanes (especially polydiphenylsiloxanes) and polyalkylarylsiloxanes functionalized with the previously mentioned organofunctional groups. The polyalkylarylsiloxanes are especially chosen from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes.

[0528] Among the organomodified silicones, mention may be made of organopolysiloxanes comprising:

[0529] - polyoxyethylene and / or polyoxypropylene, which optionally contain C6-C 24 Alkyl groups such as dimethicone copolyols and in particular those sold under the name DC 1248 by Dow Corning or oils from Union Carbide L 722, L 7500, L 77 and L 711; or alternatively (C12) alkyl methicone copolyols, and in particular those sold under the name Q2-5200 by the company Dow Corning;

[0530] - 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 the company Genesee, or the products sold under the names Q2-8220 and DC929 or DC939 by the company Dow Corning;

[0531] - thiol groups, such as the products sold under the names GP 72A and GP 71 by Genesee;

[0532] - alkoxylated groups, such as the product sold under the name Silicone Copolymer F-755 by SWS Silicones and under the name Abil Products sold in 2428, 2434 and 2440;

[0533] - hydroxylated groups, such as polyorganosiloxanes with hydroxyalkyl functional groups;

[0534] - acyloxyalkyl groups, such as polyorganosiloxanes described in US Pat. No. 4,957,732;

[0535] - anionic groups of the carboxylic acid type, as described, for example, in EP 186 507, or of the alkylcarboxylic acid type, such as the product X-22-3701E from Shin-Etsu, or alternatively of the 2-hydroxyalkylsulfonate or 2-hydroxyalkylthiosulfate type, such as those produced by Goschmidt under the name S201 and Products sold by S255;

[0536] - Hydroxyacylamino groups, such as the polyorganosiloxanes described in patent application EP 342 834; mention may be made, by way of example, of the product Q2-8413 from the company Dow Corning.

[0537] Silicones can 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 commercial products:

[0538] - 47 and 70 047 series sold by Rhodia Oil or Oil, for example oil 70047V 500 000;

[0539] - Marketed by Rhodia Series of oils;

[0540] - Oils of the 200 series from Dow Corning, such as those with 60 000 mm 2 / s viscosity DC200;

[0541] - From General Electric oils, and certain oils from the SF series (SF 96, SF 18) from General Electric.

[0542] Mention may also be made of the polydimethylsiloxanes with dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.

[0543] Among this class of polydialkylsiloxanes, mention may also be made of the polysiloxanes marketed under the name Abil Products sold as 9800 and 9801, which are poly (C1-C20) dialkyl siloxanes.

[0544] More particularly, the products that can be used according to the invention are mixtures such as:

[0545] mixtures of polydimethylsiloxanes or dimethiconols (CTFA) with hydroxyl-terminated chains and cyclic dimethicones also known as cyclomethicone (CTFA), such as the product Q2-1401 sold by the company Dow Corning,

[0546] - mixtures of polydimethylsiloxanes or dimethiconol (CTFA) with hydroxyl-terminated chains and polydimethylsiloxanes, also known as dimethicone (CTFA), such as the products sold by Dow Corning PMX-1503 fluid.

[0547] The polyalkylaryl siloxane is particularly selected from those having a carbonyl group ... -5 Up to 5×10 -2 m 2 / s linear and / or branched polydimethyl / methylphenyl siloxane and polydimethyl / diphenyl siloxane having a viscosity of 1.1777 W / s.

[0548] Among these polyalkylaryl siloxanes, mention may be made of the products sold under the following names:

[0549] - Series 70 641 from Rhodia Oil;

[0550] -From Rhodia 70 Oils of the 633 and 763 series;

[0551] - oil from Dow Corning 556 Cosmetic Grade Fluid;

[0552] - Silicones from the PK series from Bayer, such as the product PK20;

[0553] - Silicones from the PN and PH series from Bayer, such as the products PN1000 and PH1000;

[0554] - Certain oils from the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

[0555] Preferably, the dyeing composition comprises at least one aminosilicone. "Aminosilicone" means any silicone comprising at least one primary, secondary, tertiary or quaternary ammonium group.

[0556] The weight average molecular weight of these aminosilicones can be measured by gel permeation chromatography (GPC) at room temperature (25° C.) as polystyrene equivalent. The column used is a μ polystyrene type cross-linked copolymer column. The eluent is THF and the flow rate is 1 ml / min. 200 μl of a 0.5% by weight solution of silicone in THF are injected. Detection is carried out by refractometry and UV determination.

[0557] Preferably, the aminosilicones that can be used in the context of the present invention are selected from:

[0558] a) a polysiloxane corresponding to formula (A):

[0559]

[0560] wherein x' and y' are integers such that the weight average molecular weight (Mw) is approximately between 5000 and 500 000;

[0561] b) aminosilicone corresponding to formula (B):

[0562] R'a G 3-a -Si(OSiG2) n -(OSiG b R' 2-b ) m -O-SiG 3-a -R' a (B)

[0563] in:

[0564] -G are the same or different and indicate a hydrogen atom or a group derived from phenyl, OH, C1-C8 alkyl (e.g., methyl), or C1-C8 alkoxy (e.g., methoxy);

[0565] -a is the same or different and indicates 0 or an integer from 1 to 3, in particular 0,

[0566] -b indicates 0 or 1, especially 1,

[0567] - m and n are numbers such that the sum of (n+m) ranges from 1 to 2000 and in particular from 50 to 150, n may indicate a number from 0 to 1999 and in particular from 49 to 149, and m may indicate a number from 1 to 2000 and in particular from 1 to 10;

[0568] -R' is the same or different, indicating a monovalent group of formula -CqH2qL, wherein q is a number ranging from 2 to 8 and L is an optionally quaternized amine group selected from the following groups:

[0569] -N(R")2; -N+(R")3A-; -NR"-QN(R")2 and -NR"-Q-N+(R")3A-,

[0570] Wherein R" is the same or different and indicates hydrogen, phenyl, benzyl, or a saturated monovalent hydrocarbon-based group, such as C1-C 20 Alkyl; Q indicates formula C r H 2r A linear or branched group, r is an integer ranging from 2 to 6, preferably from 2 to 4; and A - denotes a cosmetically acceptable anion, in particular a halide, such as fluoride, chloride, bromide or iodide.

[0571] Preferably, the aminosilicone is selected from aminosilicones of formula (B). Preferably, the aminosilicone of formula (B) is selected from aminosilicones corresponding to the following formulae (C), (D), (E), (F) and / or (G).

[0572] According to a first embodiment, the aminosilicone corresponding to formula (B) is chosen from the silicones known as “trimethylsilylaminodimethicone” corresponding to formula (C):

[0573]

[0574] Wherein m and n are numbers such that the sum of (n+m) ranges from 1 to 2000 and in particular from 50 to 150, n may indicate a number from 0 to 1999 and in particular from 49 to 149, and m may indicate a number from 1 to 2000 and in particular from 1 to 10.

[0575] According to a second embodiment, the aminosilicone corresponding to formula (B) is chosen from silicones of the following formula (D):

[0576]

[0577] in:

[0578] - m and n are numbers such that the sum of (n+m) ranges from 1 to 1000, in particular from 50 to 250 and more particularly from 100 to 200; n may indicate a number from 0 to 999, in particular from 49 to 249 and more particularly from 125 to 175, and m may indicate a number from 1 to 1000, in particular from 1 to 10 and more particularly from 1 to 5;

[0579] - R1, R2 and R3 are the same or different and represent a hydroxyl group or a C1-C4 alkoxy group, at least one of the groups R1 to R3 represents an alkoxy group.

[0580] Preferably, the alkoxy group is methoxy.

[0581] The hydroxyl / alkoxy molar ratio preferably ranges from 0.2:1 to 0.4:1 and preferably from 0.25:1 to 0.35:1 and more particularly is equal to 0.3:1.

[0582] The weight-average molecular weight (Mw) of these silicones preferably ranges from 2000 to 1 000 000 and more particularly from 3500 to 200 000.

[0583] According to a third embodiment, the aminosilicone corresponding to formula (B) is chosen from silicones of the following formula (E):

[0584]

[0585] in:

[0586] - p and q are numbers such that the sum of (p+q) ranges from 1 to 1000, in particular from 50 to 350, and more particularly from 150 to 250; p may indicate a number from 0 to 999, in particular from 49 to 349, and more particularly from 159 to 239, and q may indicate a number from 1 to 1000, in particular from 1 to 10, and more particularly from 1 to 5;

[0587] - R1 and R2 are different and represent a hydroxyl group or a C1-C4 alkoxy group, and at least one of the groups R1 or R2 represents an alkoxy group.

[0588] Preferably, the alkoxy group is methoxy.

[0589] The hydroxyl / alkoxy molar ratio generally ranges from 1:0.8 to 1:1.1 and preferably from 1:0.9 to 1:1 and is more particularly equal to 1:0.95.

[0590] The weight average molecular weight (Mw) of the silicone preferably ranges from 2000 to 200 000, even more particularly from 5000 to 100 000 and more particularly from 10 000 to 50 000.

[0591] Commercial products comprising silicones of structure (D) or (E) may contain in their composition one or more other aminosilicones having a structure different from that of formula (D) or (E).

[0592] Products containing aminosilicones of structure (D) are marketed by Wacker under the name ADM 652 for sale.

[0593] Products containing aminosilicone with structure (E) are marketed by Wacker under the name Fluid WR Or by name ADM LOG 1 sales.

[0594] When using these aminosilicones, a particularly advantageous embodiment consists in using them in the form of an oil-in-water emulsion. The oil-in-water emulsion may contain one or more surfactants. The surfactant may be of any nature, but is preferably cationic and / or nonionic. The number average size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nm. Preferably, in particular as aminosilicones of formula (E), microemulsions are used with an average particle size ranging from 5 nm to 60 nm (limits included) and more particularly from 10 nm to 50 nm (limits included). Thus, according to the invention, it is possible to use the microemulsions manufactured by Wacker under the name Finish CT 96 or SLM Aminosilicone microemulsion of formula (E) is sold.

[0595] According to a fourth embodiment, the aminosilicone corresponding to formula (B) is chosen from silicones of the following formula (F):

[0596]

[0597] in:

[0598] - m and n are numbers such that the sum of (n+m) ranges from 1 to 2000 and in particular from 50 to 150, n may indicate a number from 0 to 1999 and in particular from 49 to 149, and m may indicate a number from 1 to 2000 and in particular from 1 to 10;

[0599] -A indicates a linear or branched alkylene group having from 4 to 8 carbon atoms and preferably 4 carbon atoms. This group is preferably linear.

[0600] The weight-average molecular weight (Mw) of these aminosilicones preferably ranges from 2000 to 1 000 000 and even more particularly from 3500 to 200 000.

[0601] Another silicone corresponding to formula (B) is, for example, Xiameter MEM 8299 emulsion from Dow Corning (INCI name: Amodimethicone and Trideceth-6 and Cetyltrimonium Chloride).

[0602] According to a fifth embodiment, the aminosilicone corresponding to formula (B) is chosen from silicones of the following formula (G):

[0603]

[0604] in:

[0605] - m and n are numbers such that the sum of (n+m) ranges from 1 to 2000 and in particular from 50 to 150, n may indicate a number from 0 to 1,999 and in particular from 49 to 149, and m may indicate a number from 1 to 2000 and in particular from 1 to 10;

[0606] -A indicates a linear or branched alkylene group having from 4 to 8 carbon atoms and preferably 4 carbon atoms. This group is preferably branched.

[0607] The weight-average molecular weight (Mw) of these aminosilicones preferably ranges from 500 to 1 000 000 and even more particularly from 1000 to 200 000.

[0608] A silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning;

[0609] c) aminosilicone corresponding to formula (H):

[0610]

[0611] in:

[0612] - R5 represents a monovalent hydrocarbon-based group having from 1 to 18 carbon atoms, and in particular C1-C18 Alkyl or C2-C 18 alkenyl, such as methyl;

[0613] -R6 represents a divalent hydrocarbon-based group connected to Si via a SiC bond, in particular a C1-C 18 Alkylene or divalent C1-C 18 For example, C1-C8 alkyleneoxy;

[0614] -Q - is an anion, such as a halide, especially chloride, or an organic acid salt, especially acetate;

[0615] -r represents an average statistical value ranging from 2 to 20 and in particular from 2 to 8;

[0616] -s represents an average statistical value ranging from 20 to 200 and particularly from 20 to 50.

[0617] Such aminosilicones are described in particular in patent US Pat. No. 4,185,087.

[0618] d) Quaternary ammonium silicone of formula (I):

[0619]

[0620] in:

[0621] - R7 are the same or different and represent a monovalent hydrocarbon-based group having from 1 to 18 carbon atoms, and in particular C1-C 18 Alkyl, C2-C 18 alkenyl or a ring containing 5 or 6 carbon atoms, such as methyl;

[0622] -R6 represents a divalent hydrocarbon-based group connected to Si via a SiC bond, in particular a C1-C 18 Alkylene or divalent C1-C 18 For example, C1-C8 alkyleneoxy;

[0623] - R8 are the same or different and represent a hydrogen atom, a monovalent hydrocarbon-based group having from 1 to 18 carbon atoms, and in particular a C1-C 18 Alkyl, C2-C 18 an alkenyl group or a -R6-NHCOR7 group;

[0624] -X - is an anion, such as a halide, especially chloride, or an organic acid salt, especially acetate;

[0625] -r represents an average statistical value ranging from 2 to 200 and particularly 5 to 100.

[0626] These silicones are described, for example, in patent EP-A0 530 974;

[0627] e) Aminosilicone of formula (J):

[0628]

[0629] in:

[0630] - R1, R2, R3 and R4 are the same or different and indicate C1-C4 alkyl or phenyl,

[0631] -R5 indicates a C1-C4 alkyl group or a hydroxyl group,

[0632] -n is an integer ranging from 1 to 5,

[0633] -m is an integer ranging from 1 to 5, and

[0634] - x is selected so that the amine value ranges from 0.01 to 1 meq / g;

[0635] f) Multiblock polyoxyalkylene aminosilicone of (AB)n type, A being a polysiloxane block and B being a polyoxyalkylene block comprising at least one amine group.

[0636] The silicone is preferably formed from repeating units having the following general formula:

[0637] [-(SiMe2O)xSiMe2-RN(R”)-R'-O(C2H4O) a (C3H6O) b -R'-N(H)-R-]

[0638] or alternatively

[0639] [-(SiMe2O)xSiMe2-RN(R")-R'-O(C2H4O)a(C3H6O)b-]

[0640] in:

[0641] - a is an integer greater than or equal to 1, preferably ranging from 5 to 200 and more particularly ranging from 10 to 100;

[0642] - b is an integer between 0 and 200, preferably ranging from 4 to 100 and more particularly between 5 and 30;

[0643] - x is an integer ranging from 1 to 10 000 and more particularly from 10 to 5000;

[0644] -R" is a hydrogen atom or a methyl group;

[0645] -R is the same or different, indicating a straight or branched divalent C2-C 12 A hydrocarbon-based group, which optionally contains one or more heteroatoms such as oxygen; preferably, R indicates an ethylene group, a linear or branched propylene group, a linear or branched butylene group or a CH2CH2CH2OCH2CH(OH)CH2- group; preferably, R indicates a CH2CH2CH2OCH2CH(OH)CH2- group;

[0646] -R' is the same or different, indicating a straight or branched divalent C2-C 12 A hydrocarbon-based group which optionally contains one or more heteroatoms such as oxygen; preferably, R' indicates an ethylene, a linear or branched propylene, a linear or branched butylene or a CH2CH2CH2OCH2CH(OH)CH2- group; preferably, R' indicates -CH(CH3)-CH2-.

[0647] The siloxane blocks preferably represent between 50 and 95 mol %, more particularly from 70 to 85 mol %, of the total weight of the silicone.

[0648] The amine content is preferably between 0.02 and 0.5 meq / g of the copolymer in a 30% solution in dipropylene glycol, more particularly between 0.05 and 0.2.

[0649] The weight-average molecular weight (Mw) of the silicone is preferably between 5,000 and 1,000,000 and more particularly between 10,000 and 200,000.

[0650] Mention may in particular be made of the silicones sold under the name Silsoft A-843 or Silsoft A+ by the company Momentive.

[0651] g) and mixtures thereof.

[0652] Preferably, the aminosilicone of formula (B) is selected from the aminosilicone corresponding to formula (E).

[0653] Preferably, the dyeing composition comprises at least one aminosilicone with the INCI name Amodimethicone, preferably introduced in the form of an emulsion or microemulsion with a surfactant.

[0654] Preferably, the dyeing composition comprises at least one aminosilicone with the INCI name Amodimethicone as emulsion or microemulsion with surfactant, with the INCI names Trideceth-5 and Trideceth-10.

[0655] The silicone may be present in a total amount ranging from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight, more preferably from 0.1% to 10% by weight and even more preferably still from 0.5% to 5% by weight relative to the total weight of the dyeing composition.

[0656] The aminosilicone may be present in a total amount ranging from 0.01% to 20%, preferably from 0.05% to 15%, more preferably from 0.1% to 10% and even more preferably still from 0.5% to 5% relative to the total weight of the dyeing composition.

[0657] Associative polymer

[0658] The composition for dyeing keratin hair fibers used in the context of the color removal process according to the invention may also comprise at least one associative polymer other than the non-carboxylic acid anionic thickener previously described.

[0659] It is contemplated that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0660] Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.

[0661] "Hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon-based chain containing at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms, and more preferably from 18 to 30 carbon atoms.

[0662] Preferably, 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, dodecanol or decanol. It may also indicate a hydrocarbon-based polymer, such as polybutadiene.

[0663] Associative polymers can be nonionic, anionic, cationic or amphoteric in nature.

[0664] Preferably, the associative polymer is chosen from anionic associative polymers.

[0665] Among the associative polymers of anionic type, mention may be made of:

[0666] - (a) those comprising at least one hydrophilic unit and at least one fatty chain allyl ether unit, more particularly those whose hydrophilic units are formed from ethylenically unsaturated anionic monomers, more particularly vinyl carboxylic acids and most particularly acrylic acid or methacrylic acid or mixtures thereof.

[0667] 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, from 5 to 60% by weight of lower alkyl (meth)acrylates, from 2 to 50% by weight of fatty chain allyl ethers and from 0 to 1% by weight of a crosslinking agent, which is a well-known copolymerizable unsaturated polyethylenic monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.

[0668] Among the latter polymers, those most particularly preferred are the crosslinked terpolymers of methacrylic acid, ethyl acrylate and polyethylene glycol (10EO) stearyl ether (steareth-10), especially those marketed by Ciba under the name Salcare SC and Salcare SC Those sold are HYDRADE(R), which is an aqueous 30% emulsion of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10 allyl ether (40 / 50 / 10).

[0669] - (b) comprising i) at least one hydrophilic unit of the unsaturated olefinic carboxylic acid type and ii) at least one (C 10 -C 30 ) alkyl esters and the like.

[0670] The unsaturated carboxylic acid (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.

[0671] Anionic polymers of this type are described and prepared, for example, according to patents US Pat. No. 3,915,921 and US Pat. No. 4,509,949.

[0672] Among anionic associative polymers of this type, use will more particularly be made of from 95 to 60% by weight of acrylic acid (hydrophilic units), from 4 to 40% by weight of acrylic acid C 10 -C 30 alkyl esters (hydrophobic units), and 0 to 6% by weight of a polymerizable crosslinking monomer, or alternatively from 98 to 96% by weight of acrylic acid (hydrophilic units), 1 to 4% by weight of acrylic acid C 10 -C 30Those composed of an alkyl ester (hydrophobic unit), and 0.1 to 0.6% by weight of a crosslinking polymerizable monomer, such as those described above.

[0673] Among the above-mentioned polymers, those which are most particularly preferred according to the invention are those which are produced by Goodrich under the trade name Pemulen Pemulen Carbopol And even more preferably Pemulen Products sold by Seppic under the name Coatex Products for sale.

[0674] Mention may also be made of the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer sold under the name Acrylidone LM by the company ISP.

[0675] - (c) maleic anhydride / C30-C38 alpha-olefin / alkyl maleate terpolymers, such as those marketed by Newphase Technologies under the name Performa V The product sold (maleic anhydride / C30-C38 alpha-olefin / isopropyl maleate copolymer).

[0676] - (d) an acrylic acid terpolymer comprising:

[0677] i) about 20 to 70% by weight of an α,β-monoethylenically unsaturated carboxylic acid [A],

[0678] ii) about 20 to 80% by weight of an α,β-monoethylenically unsaturated non-surfactant monomer other than [A],

[0679] iii) about 0.5% to 60% by weight of a nonionic monocarbamate which is the reaction product of a monobasic surfactant and a monoethylenically unsaturated monoisocyanate,

[0680] Terpolymers such as those described in patent application EP-A-0 173 109, and more particularly those described in Example 3, ie methacrylic acid / methyl acrylate / behenyl dimethyl-m-isopropenyl benzyl isocyanate ethoxylated (40EO) terpolymer, as aqueous 25% dispersion.

[0681] (e) copolymers which comprise, among their monomers, α,β-monoethylenically unsaturated carboxylic acids and esters of α,β-monoethylenically unsaturated carboxylic acids and oxyalkylenated fatty alcohols.

[0682] Preferably, these compounds also contain as monomers esters of α,β-monoethylenically unsaturated carboxylic acids and C1-C4 alcohols.

[0683] An example of a compound of this type that may be mentioned is the Aculyn sold by &Haas It is a methacrylic acid / ethyl acrylate / oxyalkylened stearic methacrylate terpolymer; and also Aculyn 88, also sold by Rohm and Haas Company.

[0684] Advantageously, the associative polymer other than a non-carboxylic acid anionic thickener is chosen from acrylic associative polymers, more preferably carboxylic acid acrylic associative polymers.

[0685] Particularly preferably, the associative polymer is chosen from copolymers which comprise, among their monomers, α,β-monoethylenically unsaturated carboxylic acids and esters of α,β-monoethylenically unsaturated carboxylic acids and of oxyalkylenated fatty alcohols.

[0686] Advantageously, the total amount of associative polymers ranges from 0.05 to 15% by weight, preferably from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight and even more preferably from 0.1 to 1% by weight relative to the total weight of the dyeing composition.

[0687] Compounds having at least one carboxylic acid group

[0688] The composition for dyeing keratin hair fibers used in the context of the dye removal process according to the invention may also comprise, other than the associative polymers described previously, at least one compound having at least one carboxylic acid group.

[0689] "Carboxyl" means a COOH or COO- functional group, the counterion of the COO- group possibly being selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0690] Preferably, the compound other than the associative polymer having at least one carboxylic acid group is selected from polyurethanes, non-silicone acrylic polymers, silicone acrylic copolymers and mixtures thereof.

[0691] Polyurethane and acrylic polymers

[0692] According to a preferred embodiment, the composition for dyeing keratin hair fibers comprises one or more compounds other than associative polymers having at least one carboxylic acid group chosen from polyurethanes, non-silicone acrylic polymers and mixtures thereof.

[0693] Preferably, the compound having at least one carboxylic acid group other than the associative polymer is in the form of an aqueous dispersion of particles of a polymer chosen from polyurethanes, non-silicone acrylic polymers and mixtures thereof.

[0694] Preferably, the composition for dyeing keratin hair fibers comprises one or more compounds having at least one carboxylic acid group other than an associative polymer, in the form of an aqueous dispersion of particles of a polymer chosen from polyurethanes, non-silicone acrylic polymers and mixtures thereof.

[0695] Thus, in this embodiment, the polymer used in the aqueous dispersion of polymer particles is different from the associative polymer.

[0696] The dispersion may be a simple dispersion in the aqueous medium of the cosmetic composition. As a specific case of the dispersion, latex may be mentioned.

[0697] The aqueous dispersion of polymer particles may be selected from aqueous dispersions of polyurethane particles.

[0698] More particularly, the polyurethane present in the aqueous dispersion used in the present invention results from the following reaction:

[0699] - a prepolymer of the following formula (A):

[0700]

[0701] in

[0702] -R1 represents a divalent group of a dihydroxylated compound;

[0703] - R2 represents a group of aliphatic or alicyclic polyisocyanate;

[0704] - R3 represents a low molecular weight diol radical, which is optionally substituted by one or more ionic groups;

[0705] -n represents an integer ranging from 1 to 5, and

[0706] -m is greater than 1;

[0707] - at least one chain extender according to the following formula (B):

[0708] H2N-R4-NH2(B),

[0709] wherein R4 represents an alkylene or alkyleneoxy group which is not substituted by one or more ionic or potentially ionic groups; and

[0710] - at least one chain extender according to the following formula (C):

[0711] H2N-R5-NH2(C),

[0712] wherein R5 represents an alkylene group substituted by one or more ionic or potentially ionic groups.

[0713] Among the dihydroxylated compounds that can be used according to the invention, mention may be made in particular of compounds having two hydroxyl groups and having a number average molecular weight of from about 700 to about 16 000, and preferably from about 750 to about 5000. As examples of dihydroxylated compounds having a high molecular weight, mention may be made of polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polydienes, polyhydroxylated polythioethers, and mixtures thereof.

[0714] Preferably, the hydroxylated compound is selected from the group consisting of polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0715] The polyisocyanates that can be used according to the invention are chosen in particular from organic diisocyanates having a molecular weight of approximately 112 to 1000 and preferably approximately 140 to 400.

[0716] Preferably, the polyisocyanate is chosen from diisocyanates and more particularly from those represented by the general formula R2(NCO)2, wherein R2 represents a divalent aliphatic hydrocarbon-based group having from 4 to 18 carbon atoms, a divalent alicyclic hydrocarbon-based group having from 5 to 15 carbon atoms, a divalent aromatic aliphatic hydrocarbon-based group having from 7 to 15 carbon atoms or a divalent aromatic hydrocarbon-based group having from 6 to 15 carbon atoms.

[0717] Preferably, R2 represents an organic diisocyanate. Taking organic diisocyanates as an example, the following items can be particularly selected: 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 diisocyanate, diphenylmethane 4,4'-diisocyanate and mixtures thereof with its diphenylmethane 2,4-diisocyanate isomers and optionally diphenylmethane 2,2'-diisocyanate isomers, naphthalene 1,5-diisocyanate isomers, and mixtures thereof.

[0718] Preferably, the diisocyanate is an aliphatic or cycloaliphatic diisocyanate, and more preferably is selected from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate, and mixtures thereof.

[0719] According to the invention, "low molecular weight diols" are meant diols having a molecular weight of from about 62 to 700, and preferably from 62 to 200. These diols may contain aliphatic, alicyclic or aromatic groups. Preferably, they contain only aliphatic groups.

[0720] Preferably, R3 represents a low molecular weight diol having more than 20 carbon atoms, more preferably selected from ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, neopentyl glycol, butyl ethyl propanediol, 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.

[0721] 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 in particular in patent US 3 412 054. Such compounds are preferably selected from dimethylolbutanoic acid, dimethylolpropionic acid, polycaprolactone diols containing carboxyl groups, and mixtures thereof.

[0722] If 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 milliequivalents of COOH / gram of polyurethane are present in the polyurethane dispersion.

[0723] The prepolymers are chain extended by two families of chain extenders. The first class of chain extenders corresponds to compounds of general formula (B).

[0724] The chain extender of formula (B) is preferably selected from alkylenediamines such as hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine; alkyleneoxydiamines such as 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine (also known as dipropylamine diglycol or DPA-DEG, available from Tomah Products, Milton, Wisconsin), 2-methyl-1,5-pentanediamine (Dytec from DuPont); A), hexamethylenediamine, isophoronediamine, 4,4-methylenebis(cyclohexylamine), ether-amines of the DPA series available from Thomas Products, Milton, Wisconsin, such as dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropylene glycol, dipropylamine poly(propylene glycol), dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propylene glycol, dipropylamine 2-methyl-1,3-propylene glycol, dipropylamine 1,4-butanediol, dipropylamine 1,3-butanediol, dipropylamine 1,6-hexanediol, and dipropylamine cyclohexanedimethanol; and mixtures thereof.

[0725] The second class of chain extenders corresponds to compounds of the general formula (C). Such compounds preferably have an ionic or potentially ionic group and two groups that can react with isocyanate groups. Such compounds may optionally contain two groups that react with isocyanate groups and one group that is an ionic group or is capable of forming an ionic group.

[0726] Ionic or potentially ionic groups can preferably be selected from ternary ammonium or quaternary ammonium groups or groups that can be converted into such groups, carboxyl groups, carboxylate groups, sulfonic acid groups and sulfonate groups. At least partial conversion of groups that can be converted into ternary ammonium or quaternary ammonium group salts can be carried out before or during mixing with water.

[0727] 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.

[0728] The polyurethanes which can be used according to the invention may also optionally contain compounds which are located at the ends of the chains and terminate the chains (chain terminators). Such compounds are described in particular in patents US Pat. No. 7,445,770 and / or US Pat. No. 7,452,770.

[0729] Preferably, the aqueous dispersion of polyurethane particles has a viscosity at 23°C of less than 2000 mPa.s, more preferably less than 1500 and even better still less than 1000. Even more preferably, the aqueous polyurethane dispersion has a glass transition temperature of less than 0°C.

[0730] Also preferably, the aqueous polyurethane dispersion has a polyurethane (or active material, or dry matter) content of from 20% to 60% by weight, more preferably from 25% to 55% by weight and even better still from 30% to 50% by weight, based on the weight of the dispersion. This means that the polyurethane content (dry matter) of the aqueous dispersion is preferably from 20% to 60% by weight, more preferably from 25% to 55% by weight and even better still from 30% to 50% by weight relative to the total weight of the dispersion.

[0731] Also preferably, the aqueous dispersion of polyurethane particles has a glass transition temperature (Tg) less than or equal to -25°C, preferably less than -35°C and more preferably less than -40°C.

[0732] The polyurethane particles may have an average diameter ranging up to about 1000 nm, for example from about 50 nm to about 800 nm, and better still from about 100 nm to about 500 nm. These particle sizes may be measured with a laser particle size analyzer (eg, Brookhaven BI90).

[0733] As non-limiting examples of aqueous polyurethane dispersions, mention may be made of the polyurethane dispersions marketed by Bayer AG under the name Those that are sold, e.g. C1000 (INCI name: Polyurethane-34), C1001 (INCI name: Polyurethane-34), C1003 (INCI name: Polyurethane-32), C1004 (INCI name: Polyurethane-35) and C1008 (INCI name: POLYURETHANE-48).

[0734] Mention may also be made of the following aqueous polyurethane dispersions: isophthalic acid / adipic acid copolymer / hexanediol / neopentyl glycol / dimethylol acid / isophorone diisocyanate (INCI name: Polyurethane-1, e.g. PUR, BASF), polycarbonate polyurethanes, aliphatic polyester polyurethanes and aliphatic polyurethanes (such as series, DSM, such as R989, and R-2202).

[0735] According to a particular embodiment, the aqueous dispersion of polyurethane particles may be chosen from aqueous dispersions of particles of the compound with the INCI name Polyurethane-35 or of the compound with the INCI name Polyurethane-34.

[0736] According to a preferred embodiment, the compound having at least one carboxylic acid group other than the associative polymer is in the form of an aqueous dispersion of particles of a non-silicone acrylic polymer, more preferably in the form of an aqueous dispersion of particles of a film-forming non-silicone acrylic polymer.

[0737] For the purposes of the present invention, "polymer" means a compound corresponding to the repetition of one or more units derived from compounds called monomers. This or these units are repeated at least twice and preferably at least three times.

[0738] "Film-forming polymer" means a polymer that is capable, by itself or in the presence of auxiliary film-forming agents, of forming a macroscopically continuous film on a support, in particular on a keratin material, and preferably an adhesive film.

[0739] For the purpose of the present invention, "acrylic polymer" means a polymer synthesized from at least one monomer selected from (meth)acrylic acid and / or (meth)acrylic ester and / or (meth)acrylamide.

[0740] The units derived from (meth)acrylic acid monomers of the polymer may optionally be in the form of a salt, in particular an alkali metal, alkaline earth metal or ammonium salt, or an organic base salt.

[0741] The (meth)acrylic acid ester (also called (meth)acrylate) is advantageously selected from alkyl (meth)acrylates, in particular C1 to C 4 (meth)acrylates. 30 Alkyl esters, preferably (meth) acrylic acid C1 to C 20 Alkyl esters and also preferably (meth)acrylic acid C1 to C 10 Alkyl esters; (meth) aryl acrylates, especially (meth) acrylates C6 to C 10 Aryl esters; and hydroxyalkyl (meth)acrylates, especially C2 to C6 hydroxyalkyl (meth)acrylates.

[0742] 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.

[0743] Among the hydroxyalkyl (meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0744] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0745] Particularly preferred (meth)acrylates are alkyl groups, preferably C1 to C 30 , more preferably C1 to C 20 , even better C1 to C 10 , and even more particularly C1 to C4 alkyl (meth)acrylates.

[0746] According to the 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.

[0747] As (meth)acrylamides, examples that may be mentioned include (meth)acrylamide and also N-alkyl(meth)acrylamides, in particular N-(C2 to C12 alkyl) (meth)acrylamides. Among the N-alkyl(meth)acrylamides, mention may be made of N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide and N-undecylacrylamide.

[0748] The acrylic polymer according to the invention may be a homopolymer or a copolymer, advantageously a copolymer, even better still a copolymer of (meth)acrylic acid and a (meth)acrylic ester.

[0749] Preferably, the acrylic polymer according to the present invention comprises one or more units derived from the following monomers:

[0750] a) (meth)acrylic acid; and

[0751] b) C1 to C 30 , more preferably C1 to C 20 , and better C1 to C 10 , and even more particularly C1 to C4 alkyl (meth)acrylates.

[0752] Preferably, the aqueous dispersion of non-silicone acrylic polymer particles does not contain any surfactant.

[0753] "Surfactant" means any agent capable of changing the surface tension between two surfaces.

[0754] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and ethyl acrylate, such as the compound sold under the name Luvimer MAE by BASF, or the compound Polyacrylate-2 Crosspolymer sold under the name Fixate Superhold Polymer by Lubrizol, or the compound acrylate copolymer sold under the name Daitosol 3000VP3 by Daito Kasei Kogyo, or the compound acrylate polymer sold under the name Daitosol 3000SLPN-PE1 by Daito Kasei Kogyo.

[0755] The acrylic polymer may optionally comprise one or more additional monomers in addition to the (meth)acrylic acid and / or (meth)acrylate and / or (meth)acrylamide monomers.

[0756] As further monomers, mention will be made, for example, of styrene monomers, in particular styrene and α-methylstyrene, and preferably styrene.

[0757] In particular, the acrylic polymer may be a styrene / (meth)acrylate copolymer, and in particular is selected from at least one styrene monomer and at least one (meth)acrylic acid C1 to C 20 Alkyl esters, preferably (meth) acrylic acid C1 to C 10 The polymerization of alkyl ester monomers produces the copolymer polymer.

[0758] (Meth) acrylic acid C1 to C 10 The alkyl ester monomer may be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate.

[0759] As non-silicone acrylic polymers, mention may be made of the styrene / (meth)acrylate copolymers sold under the names Joncryl 77 by BASF, Yodosol GH41F by Akzo Nobel and Syntran 5760 CG by Interpolymer.

[0760] Silicone Acrylate Copolymer

[0761] According to a preferred embodiment, the compound other than the associative polymer having at least one carboxylic acid group is chosen from silicone acrylic copolymers.

[0762] Preferably, the polysiloxane acrylic copolymer comprises:

[0763] - at least one acrylic acid, methacrylic acid or crotonic acid unit; and

[0764] - at least one polydimethylsiloxane (PDMS) unit.

[0765] For the purposes of the present invention, by "polydimethylsiloxane" (also referred to as PDMS for short), it is intended, according to generally accepted convention, to mean any silicone polymer or oligomer representing a linear structure of variable molecular weight, obtained by polymerization and / or polycondensation of suitably functionalized silanes, and consisting essentially of recurring main units in which silicon atoms are linked together by oxygen atoms (Siloxane-Si-O-Si-bonds), containing methyl groups bonded directly to said silicon atoms via carbon atoms.

[0766] The PDMS chain that can be used to obtain the copolymer used according to the invention comprises at least one polymerizable group, which is preferably located at at least one end of the chain, i.e. the PDMS can, for example, have a polymerizable group at each of the two ends of the chain or have a polymerizable group at one end of the chain and a trimethylsilyl terminal group at the other end of the chain.

[0767] "Polymerizable group" means a group that is capable of polymerizing with other polymerizable groups or monomers. Preferably, the polydimethylsiloxane unit comprises at least one polymerizable group.

[0768] Preferably, the polymerizable group comprises at least one vinyl group.

[0769] Preferably, the polydimethylsiloxane (PDMS) unit comprises at least one polymerizable group comprising at least one vinyl group, preferably at least two polymerizable groups comprising at least one vinyl group, preferably located at at least one end of the chain.

[0770] As previously indicated, the polysiloxane acrylic copolymer comprises at least one acrylic acid, methacrylic acid or crotonic acid unit, ie at least one unit comprising a carboxyl group.

[0771] Preferably, the polysiloxane acrylic copolymer comprises:

[0772] - at least one acrylic acid, methacrylic acid or crotonic acid unit, and at least one acrylate, methacrylate or vinyl ester unit; and

[0773] - at least one polydimethylsiloxane (PDMS) unit.

[0774] More preferably, the dyeing composition comprises one or more silicone acrylic copolymers comprising:

[0775] - at least one crotonic acid unit and at least one unit selected from: a crotonic acid alkyl ester unit, the alkyl group being a linear or branched saturated group containing from 1 to 20 carbon atoms; a vinyl acetate unit; a vinyl alkyl ester unit, the alkyl group being a linear or branched saturated group containing from 2 to 20 carbon atoms; and mixtures thereof; and

[0776] - at least one polydimethylsiloxane (PDMS) unit.

[0777] The "crotonic acid unit" means a unit derived from a crotonic acid monomer or a salt thereof.

[0778] The "alkyl crotonate unit" means a unit derived from a crotonate monomer unit, which has a straight-chain or branched saturated alkyl group containing from 1 to 20 carbon atoms.

[0779] The "vinyl alkyl ester unit" means a unit derived from a vinyl ester monomer unit having a straight-chain or branched saturated alkyl group containing from 2 to 20 carbon atoms.

[0780] "Vinyl acetate units" means units derived from vinyl acetate monomers.

[0781] According to a preferred embodiment, the polysiloxane acrylic copolymer comprises:

[0782] - at least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (the alkyl group is a straight-chain or branched saturated group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms), and

[0783] - at least one polydimethylsiloxane (PDMS) unit.

[0784] According to a particularly preferred embodiment, the polysiloxane acrylic copolymer comprises:

[0785] - at least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (the alkyl group is a straight-chain or branched saturated group containing from 6 to 16 carbon atoms), and

[0786] - at least one polydimethylsiloxane (PDMS) unit comprising at least one polymerizable group comprising at least one vinyl group.

[0787] More preferably, the dyeing composition comprises one or more silicone acrylic copolymers comprising:

[0788] - at least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (the alkyl group is a straight-chain or branched saturated group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms), and

[0789] - at least one polydimethylsiloxane (PDMS) unit comprising at least one polymerizable group comprising at least one vinyl group.

[0790] Even more preferably, the dyeing composition comprises one or more silicone acrylic copolymers comprising:

[0791] - at least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (the alkyl group is a straight-chain or branched saturated group containing from 6 to 16 carbon atoms), and

[0792] - at least one polydimethylsiloxane (PDMS) unit comprising at least one polymerizable group comprising at least one vinyl group.

[0793] Among the polysiloxane acrylic copolymers which can be used in the context of the present invention, mention may be made of the silicone acrylic copolymers sold by Wacker Chemie AG under the trade name The compound sold as P1101 has the INCI name Crotonic Acid / Vinyl C8-12 Isoalkyl Ester / VA / Bis-Vinyl Dimethicone Crosspolymer.

[0794] Preferably, the dyeing composition comprises an aqueous dispersion of at least one non-silicone acrylic polymer particles.

[0795] More preferably, the dyeing composition comprises an aqueous dispersion of at least one non-silicone acrylic polymer particles comprising one or more units derived from the following monomers:

[0796] a) (meth)acrylic acid; and

[0797] b) C1 to C 30 , more preferably C1 to C 20 , and better C1 to C 10 , and even more particularly C1 to C4 alkyl (meth)acrylates.

[0798] Preferably, the aqueous dispersion of non-silicone acrylic polymer particles has an acrylic polymer (or active material, or dry matter) content of from 20 to 60% by weight, more preferably from 22 to 55% by weight and better still from 25 to 50% by weight, based on the weight of the dispersion.

[0799] The total amount of compounds having at least one carboxylic acid group other than associative polymers preferably ranges from 0.1% to 35% by weight, more preferably from 0.5% to 30% by weight, better still from 1% to 25% by weight and even more preferably from 3% to 15% by weight relative to the total weight of the dyeing composition.

[0800] The total amount of aqueous dispersion of particles of polymers chosen from polyurethanes, non-silicone acrylic polymers, and mixtures thereof, other than the associative polymers as previously described, preferably ranges from 0.1% to 50% by weight, more preferably from 0.5% to 40% by weight, better still from 1% to 30% by weight and even more preferably from 3% to 20% by weight relative to the total weight of the dyeing composition.

[0801] According to a preferred embodiment, the total amount of aqueous dispersion of particles of non-silicone acrylic polymers other than associative polymers as previously described preferably ranges from 0.1% to 50% by weight, more preferably from 0.5% to 40% by weight, better still from 1% to 30% by weight and even more preferably from 3% to 20% by weight relative to the total weight of the dyeing composition.

[0802] Organic solvents

[0803] The dyeing composition used in the context of the method according to the invention may comprise one or more organic solvents.

[0804] Examples of organic solvents that may be mentioned include lower C1-C4-alkanols, such as ethanol and isopropanol, polyols and polyol ethers, for example 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether and diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and also aromatic alcohols, for example benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0805] Preferably, the dyeing composition comprises one or more organic solvents selected from C1-C4 lower alkanols, more preferably ethanol.

[0806] The organic solvent may be present in a total amount of approximately between 0.01% and 60% by weight, preferably between 0.05% and 50% by weight and more preferably between 0.1% and 40% by weight, relative to the total weight of the dyeing composition, and including the end values.

[0807] The dyeing composition used in the context of the method according to the invention is preferably aqueous. The water content may range from 20% to 99% by weight, preferably from 30% to 98% by weight and more preferably from 40% to 95% by weight relative to the total weight of the dyeing composition.

[0808] additive

[0809] The composition for dyeing keratin hair fibres used in the context of the process according to the invention may contain any auxiliary or additive commonly used.

[0810] Among the additives that may be included in the composition, there may be mentioned reducing agents, softeners, defoamers, humectants, UV screening agents, peptizers, solubilizers, fragrances, proteins, vitamins, polymers other than those previously described, anionic, cationic, nonionic or amphoteric surfactants, preservatives, oils, waxes and mixtures thereof.

[0811] The composition for dyeing keratin hair 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 multiple emulsion (W / O / W or polyol / O / W or O / W / O), in the form of a cream, a mousse, a stick, a vesicular dispersion, in particular a dispersion of ionic or nonionic lipids, or a two-phase or multiphase lotion.

[0812] A person skilled in the art can choose a suitable presentation form, and also a method for its preparation, based on his general knowledge, taking into account firstly the nature of the ingredients used, in particular their solubility in the carrier, and secondly the intended use of the composition.

[0813] Application of Composition D

[0814] The method according to the invention for removing color from keratin hair fibers, such as the hair, may also comprise a step of applying to the keratin hair fibers a composition D comprising at least one silicone compound comprising at least one carboxyl group, said application of composition D being carried out before the application of the color removing composition.

[0815] Preferably, the silicone compound containing at least one carboxyl group is a silicone compound other than the silicone acrylic copolymer containing at least one carboxyl group and the amino silicone as described above.

[0816] "Carboxyl" means COOH or COO - Functional group, COO - The counterion of the group may possibly be selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0817] The silicones that can be used may be soluble or insoluble in composition D; they may be in the form of oils, waxes, resins or gums; silicone oils and gums are preferred.

[0818] Silicones are described in particular detail in "Chemistry and Technology of Silicones" by Walter Noll (1968), Academic Press.

[0819] Preferably, the silicone compound comprising at least one carboxyl group is selected from the group consisting of organosiloxanes of the following formula (XXVII):

[0820]

[0821] in:

[0822] - R1 independently represents an alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms; a hydroxyl group; an alkoxy group having from 1 to 20 carbon atoms or an aryl group having from 6 to 12 carbon atoms;

[0823] -R2 independently represents a group R4-COOM, wherein R4 represents a linear or branched alkylene group having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, which is optionally interrupted by at least one heteroatom selected from a sulfur atom, a nitrogen atom, an oxygen atom and mixtures thereof, and M represents a hydrogen atom; an alkali metal or alkaline earth metal or a quaternary ammonium NR'3, wherein R' is the same or different and represents H or an alkyl group having from 1 to 4 carbon atoms; a pyrrolidone group containing a carboxyl group COOH or a group Ra-(ORb)x-COOM, wherein Ra represents a linear or branched alkylene group having from 1 to 4 carbon atoms, Rb represents an alkyl group having from 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200; and M represents a hydrogen atom, an alkali metal or alkaline earth metal or a quaternary ammonium NR'3, wherein R' is the same or different and represents H or an alkyl group having from 1 to 4 carbon atoms;

[0824] -R3 independently represents an alkyl group having from 1 to 20 carbon atoms; a hydroxyl group; a group R4-COOM, wherein R4 represents a linear or branched alkylene group having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, which is 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 a quaternary ammonium NR'3, wherein R' is the same or different and represents H or an alkyl group having from 1 to 4 carbon atoms; an alkoxy group having from 1 to 20 carbon atoms; an aryl group having from 6 to 12 carbon atoms or a group R a -(OR b ) x -COOM, where R a represents a straight or branched chain alkylene group having from 1 to 4 carbon atoms, R brepresents an alkyl group having from 1 to 4 carbon atoms, x is an integer ranging from 1 to 200; and M represents a hydrogen atom, an alkali metal or an alkaline earth metal or a quaternary ammonium NR'3, wherein R' is the same or different and represents H or an alkyl group having from 1 to 4 carbon atoms;

[0825] -n indicates an integer ranging from 1 to 1000;

[0826] -p indicates an integer ranging from 0 to 1000;

[0827] It is understood that at least one of the radicals R2 and / or R3 comprises a carboxyl group COOH or COOM, wherein M represents an alkali metal or alkaline earth metal or a quaternary ammonium NR'3, wherein R' is identical or different and represents H or an alkyl group having from 1 to 4 carbon atoms.

[0828] In particular, the silicone compound comprising at least one carboxyl group may be selected from the organosiloxanes of the following formula (XXVIII):

[0829]

[0830] in:

[0831] - R1 independently represents a linear or branched alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and better still from 1 to 6 carbon atoms, preferably a methyl group;

[0832] - R4 independently represents a straight or branched alkylene group having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, which is 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 -, where R a represents a straight or branched chain alkylene group having from 1 to 4 carbon atoms, R b represents an alkylene group having from 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200;

[0833] -M independently represents a hydrogen atom, an alkali metal or alkaline earth metal or a quaternary ammonium NR'3, wherein R' is the same or different and represents H or an alkyl group having from 1 to 4 carbon atoms;

[0834] -n indicates an integer ranging from 1 to 1000;

[0835] - an organosiloxane of the following formula (XXIX):

[0836]

[0837] in:

[0838] - R1 independently represents an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably a methyl group;

[0839] - R4 represents a linear or branched saturated or unsaturated alkylene group having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, which may be 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 -, where R a represents a straight or branched chain alkylene group having from 1 to 4 carbon atoms, R b represents an alkylene group having from 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200;

[0840] -M represents a hydrogen atom, an alkali metal or alkaline earth metal or a quaternary ammonium NR'3, wherein R' is identical or different and represents H or an alkyl group having from 1 to 4 carbon atoms;

[0841] -p indicates an integer ranging from 1 to 1000;

[0842] -n indicates an integer ranging from 1 to 1000;

[0843] - an organosiloxane of the following formula (XXX):

[0844]

[0845] in:

[0846] - R1 independently represents an alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and better still from 1 to 6 carbon atoms, preferably a methyl group;

[0847] - R4 represents a straight or branched alkylene group having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, which may be 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 -, where R a represents a straight or branched chain alkylene group having from 1 to 4 carbon atoms, R b represents an alkylene group having from 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200;

[0848] - R3 represents an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms or an aryl group having from 6 to 12 carbon atoms;

[0849] -M independently represents a hydrogen atom, an alkali metal or alkaline earth metal or a quaternary ammonium NR'3, wherein R' is the same or different and represents H or an alkyl group having from 1 to 4 carbon atoms;

[0850] -n indicates an integer ranging from 1 to 1000;

[0851] - an organosiloxane of the following formula (XXXI):

[0852]

[0853] in:

[0854] - R8 represents an alkyl group having from 1 to 6 carbon atoms, preferably a methyl group;

[0855] -m indicates an integer ranging from 1 to 1000;

[0856] -n indicates an integer ranging from 1 to 1000;

[0857] - and mixtures thereof.

[0858] Among the organosiloxanes of formula (XXVIII), mention may be made of polydimethylsiloxanes (PDMS) carrying carboxyl terminal functional groups, such as the compound sold under the trade name Silform INX by the company Momentive (INCI name: Dicarboxydecyl Polydimethicone).

[0859] Among the organosiloxanes of formula (XXIX), mention may be made of polydimethylsiloxanes (PDMS) carrying pendant carboxyl functional groups, such as the compound sold under the trade name X-22-3701 E by the company Shin-Etsu.

[0860] Among the organosiloxanes of formula (XXX), mention may be made of polydimethylsiloxanes (PDMS) carrying a carboxyl terminal functional group, such as the compound sold under the trade name X-22-3710 by the company Shin-Etsu.

[0861] Among the organosiloxanes of formula (XXXI), mention may be made of the compound sold under the trade name Grandsil SiW-PCA-10 by Grant Industries (INCI name: Dimethicone (and) PCA Dimethicone (and) Butylene Glycol (and) Decyl Glucoside).

[0862] The silicone compound comprising carboxyl groups may correspond, for example, to the compounds described in patent application EP 186 507 in the name of Chisso Corporation, which is incorporated herein by reference.

[0863] Preferably, the silicone compound comprising at least one carboxyl group is selected from the group consisting of organopolysiloxanes of formula (XXVIII), polyorganosiloxanes of formula (XXIX), and mixtures thereof.

[0864] More preferably, the silicone compound comprising at least one carboxyl group is selected from the group consisting of organopolysiloxanes of the following formula (XXVIII):

[0865]

[0866] in:

[0867] - R1 independently represents a linear or branched alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and better still from 1 to 6 carbon atoms, preferably a methyl group;

[0868] - R4 independently represents a straight or branched alkylene group having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, which is 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 -, where R a represents a straight or branched chain alkylene group having from 1 to 4 carbon atoms, R b represents an alkylene group having from 1 to 4 carbon atoms, and x is an integer ranging from 1 to 200;

[0869] -M independently represents a hydrogen atom, an alkali metal or alkaline earth metal or a quaternary ammonium NR'3, wherein R' is the same or different and represents H or an alkyl group having from 1 to 4 carbon atoms;

[0870] -n indicates an integer ranging from 1 to 1000.

[0871] Advantageously, the total amount of silicone compounds comprising at least one carboxyl group ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferably from 0.5% to 10% by weight and better still from 1% to 5% by weight relative to the total weight of composition D.

[0872] Oil

[0873] Composition D may comprise one or more oils in addition to the previously described silicone compounds comprising carboxyl groups.

[0874] Preferably, composition D comprises one or more oils. More preferably, composition D comprises one or more oils chosen from alkanes.

[0875] “Oil” means oil at room temperature (25°C) and atmospheric pressure (760 mmHg or 1.013×10 5Pa) is a fatty substance that is liquid below 4000 Pa.

[0876] Oils can be volatile or non-volatile.

[0877] "Volatile oil" means an oil that evaporates in less than one hour when in contact with the skin at room temperature and atmospheric pressure. Volatile oils are cosmetic volatile oils that are liquid at room temperature. More specifically, volatile oils have an evaporation rate between 0.01 and 200 mg / cm 2 / min, including the limit values ​​(see the protocol for measuring the evaporation rate indicated below).

[0878] "Non-volatile oil" means an oil that remains on the skin or keratin hair fibers at room temperature and atmospheric pressure. More specifically, the evaporation rate of a non-volatile oil is strictly less than 0.01 mg / cm2 / min (see the protocol for measuring the evaporation rate indicated below).

[0879] Preferably, the composition comprises one or more selected from C6-C 16 Oils of alkanes and / or mixtures thereof.

[0880] As for C6-C 16 Alkanes, which may be straight-chain or branched, and optionally cyclic.

[0881] Particular mention may be made of branched C8-C 16 Alkanes, such as C8-C 16 Isoalkanes (also called isoparaffins), isododecane, isodecane or isohexadecane, and oils sold for example under the trade names Isopar or Permethyl, and mixtures thereof.

[0882] Mention may also be made of linear alkanes, preferably of plant origin, comprising from 7 to 15 carbon atoms, in particular from 9 to 14 carbon atoms and more particularly from 11 to 13 carbon atoms.

[0883] As examples of linear alkanes suitable for the present invention, mention may be made of n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14) and n-pentadecane (C15), and mixtures thereof (and in particular the mixture of n-undecane (C11) and n-tridecane (C13) described by the company Cognis in example 1 of patent application WO 2008 / 155 059).

[0884] Mention may also be made of n-dodecane (C12) and n-tetradecane (C14), sold respectively by Sasol under the references Parafol 12-97 and Parafol 14-97, and also mixtures thereof.

[0885] As examples of alkanes suitable for the invention, mention may be made of the alkanes described in patent applications WO 2007 / 068 371 and WO 2008 / 155 059. These alkanes are obtained from fatty alcohols which themselves are obtained from coconut kernel oil or palm oil.

[0886] According to a particular embodiment, the composition comprises isododecane. Such a compound is for example the isododecane sold by Ineos under the reference Isododecane.

[0887] Preferably, composition D comprises one or more oils selected from C8-C 16 The alkane is more preferably selected from isododecane, isohexadecane, tetradecane and / or mixtures thereof.

[0888] More preferably, composition D comprises isododecane.

[0889] Composition D may comprise one or more oils other than silicone compounds containing carboxyl groups, these oils being present in a total amount of between 30% and 99% by weight, preferably between 50% and 99% by weight and better still between 70% and 99% by weight relative to the total weight of composition D.

[0890] Composition D may comprise at least one colorant chosen from the pigments, direct dyes and mixtures thereof as previously described.

[0891] Color removal composition

[0892] As previously indicated, the method for removing color from keratin hair fibers, in particular hair, comprises applying to keratin hair fibers that have previously been dyed using at least one composition for dyeing keratin hair fibers as defined above, at least one color removing composition comprising at least one alkyl carbonate or alkylene carbonate.

[0893] This depigmenting composition is intended to produce a chemical action aimed at modifying the integrity of the coloring coat formed around the keratinous hair fibers, thus allowing the removal of this coloring coat from said keratinous hair fibers.

[0894] Alkyl carbonate or alkylene carbonate

[0895] "Alkyl carbonate" means an alkyl carbonate or a dialkyl carbonate.

[0896] Preferably, the alkyl carbonate or alkylene carbonate is a C1-C 30 , preferably C1-C6 alkyl ester, or C1-C6 carbonate 30 , preferably C1-C6 alkylene esters.

[0897] More preferably, the alkyl carbonate or alkylene carbonate is chosen from alkylene carbonates, better still from propylene carbonate, butylene carbonate, pentylene carbonate and mixtures thereof.

[0898] Particularly preferably, the alkyl carbonate or alkylene carbonate is selected from propylene carbonate.

[0899] Advantageously, the total content of alkyl carbonate or alkylene carbonate ranges from 10% to 60% by weight, preferably from 15% to 50% by weight relative to the total weight of the decolorizing composition.

[0900] Glycol Ethers

[0901] The color-removing composition used in the context of the method according to the invention may also comprise at least one glycol ether.

[0902] "Glycol ether" means one or more glycol ethers containing or not containing hydroxyl groups.

[0903] Preferably, the glycol ether is selected from the formula R 11 (-O-CH(CH3)-CH2) n Those of OH, where R 11 Instructions C1-C 30 , preferably C1-C6 and more preferably C1-C4 alkyl, and wherein n is from 1 to 50, preferably from 2 to 50, still more preferably from 2 to 10, preferably 2 to 5.

[0904] Advantageously, the glycol ether has the formula CH3(-O-CH(CH3)-CH2) n OH, wherein n is from 2 to 50, preferably from 2 to 10, more preferably from 2 to 5.

[0905] 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.

[0906] The total content of glycol ethers may range from 0.1 to 40% by weight, preferably from 1 to 30% by weight and more preferably from 5 to 20% by weight relative to the total weight of the color removing composition.

[0907] Polyols

[0908] The color-removing composition used in the context of the method according to the invention may also comprise at least one polyol other than the glycol ethers previously described.

[0909] For the purposes of the present invention, "polyol" means an organic compound consisting of a hydrocarbon-based chain optionally interrupted by one or more oxygen atoms and carrying 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.

[0910] More particularly, the polyol comprises from 2 to 30 hydroxyl groups, more preferably from 2 to 10 hydroxyl groups, even more preferably still from 2 to 3 hydroxyl groups.

[0911] The color removing composition may comprise one or more polyols selected from the group consisting of diglycerol, glycerol, propylene glycol, propane-1,3-diol, 1,3-butanediol, pentane-1,2-diol, octan-1,2-diol, dipropylene glycol, hexylene glycol, ethylene glycol, polyethylene glycol, sorbitol, sugars such as glucose, and mixtures thereof.

[0912] Particularly preferably, the polyol is propylene glycol.

[0913] Advantageously, when the polyol is present, its content ranges from 1% to 70% by weight, preferably from 5% to 60% by weight, more preferably from 10% to 50% by weight relative to the total weight of the depigmenting composition.

[0914] The color-removing composition used in the context of the method according to the invention may comprise water.

[0915] According to another embodiment, the color removing composition does not contain any water.

[0916] Furthermore, additives as mentioned above may be comprised in the color removal composition used in the context of the method according to the invention.

[0917] The decolorizing composition used in the context of the method according to the invention may contain one or more non-carboxylic acid anionic thickeners as described above, the total content of which preferably ranges from 0.01% to 10% by weight, preferably from 0.1% to 5% by weight, and better still from 0.2% to 2% by weight relative to the total weight of the composition.

[0918] Clamps for keratin hair fibers

[0919] As previously indicated, the method for removing color from keratin hair fibers, in particular hair, consists in applying a clamp comprising two arms A and B to said keratin hair fibers that have previously been dyed using a dyeing composition as previously described and from which the color has been removed by a color removing composition, said keratin hair fibers passing between said arms.

[0920] The clamp for keratin hair fibers, in particular hair, as described above can have an articulation axis (Z) about which the arms A and B are articulated.

[0921] According to a preferred embodiment, arms A and B are articulated about an articulation axis (Z) and can be moved angularly towards each other.

[0922] Each arm A and B comprises a supporting portion and a movable portion.

[0923] The supporting portion corresponds to the portion where the user grips the clamp. The active portion corresponds to the portion that comes into contact with the keratin hair fibers.

[0924] The arms A and B are movable between a spaced apart position in which the movable parts are at a distance from each other and a closed position in which these movable parts are directed towards each other.

[0925] According to a preferred embodiment, the movable parts of arms A and B are arranged facing each other.

[0926] According to a preferred embodiment, arms A and B are articulated about an articulation axis (Z) and can be moved angularly towards each other so that the movable parts of arms A and B are in contact with each other.

[0927] When the active parts of arms A and B come into contact, the keratin hair fiber is clamped between the active parts of arms A and B.

[0928] The movable portions of arms A and B may comprise an active face and an opposite face, the active face having bristles.

[0929] The bristles may be arranged in tufts of bristles.

[0930] There is free space between each tuft of bristles.

[0931] Preferably, the active surfaces of arms A and B have bristle tufts and free space.

[0932] The bristle tufts are typically made from natural materials such as natural silk or animal hair such as squirrel, boar or goat hair.

[0933] The use of natural materials for the production of such clamps significantly increases their manufacturing costs, and therefore clamps have been developed in which the bristle tufts are made of synthetic hair which substantially reproduce the mechanical properties of clamps in which the bristle tufts are made of natural hair.

[0934] Each movable portion of arms A and B may include several rows of bristle tufts.

[0935] There is free space between each row of bristle tufts.

[0936] Preferably, the active surfaces of arms A and B have rows of tufts of bristles separated by free spaces.

[0937] According to a preferred embodiment, the rows of bristle tufts of the active parts are arranged parallel to each other.

[0938] In this embodiment, each row of bristle tufts is separated by free spaces.

[0939] Keratin hair fibers may be placed between the bristle clusters to form the waves.

[0940] In the closed position of the movable part, the bristles of arms A and B are interlaced so as to clamp the keratin hair fibers without blocking them.

[0941] Preferably, in the closed position of the active parts of arms A and B, the rows of tufts of arm A are interdigitated with the rows of tufts of bristles of arm B so as to clamp the keratinous hair fibres without blocking them.

[0942] In the closed position of the arms A and B, the clamp according to the invention can be moved along the keratin hair fibers, ie from the root to the tip of the keratin hair fibers, without blocking them.

[0943] By moving the clamp according to the invention along the keratin hair fibers while maintaining the closed position of arms A and B, the bristle tufts of arms A and B exert friction forces on the keratin hair fibers that have been dyed and from which the color has then been removed, so as to remove the remainder of the coloring coating present on the keratin hair fibers.

[0944] The friction force applied to the keratin hair fiber is between 5N and 20N.

[0945] The present invention may be better understood by reading the following detailed description and by referring to the accompanying drawings, in which:

[0946] - Figure 1 shows a schematic front view of an example of a clamp for keratin hair fibers produced according to the invention;

[0947] - Figure 2 Separately shown are placed side by side Figure 1 The active surface of the active part of arms A and B.

[0948] Figure 1A clamp 1 for keratin hair fibers, in particular hair, is shown, as described above. The clamp 1 comprises two arms A and B between which the keratin hair fibers pass.

[0949] The arms A and B are articulated about an articulation axis (Z) and can be moved angularly towards each other, in particular via one or more springs (not shown).

[0950] The arms A and B are capable of closing the keratin hair fiber under the drive of an external force so as to move along the keratin hair fiber.

[0951] Each arm A and B comprises a supporting part 2 and a movable part 3 .

[0952] The movable parts 3 of the arms A and B may be arranged facing each other.

[0953] The two arms A and B are articulated about an articulation axis (Z) and are angularly movable towards each other so that said movable parts 3 of arms A and B are in contact with each other.

[0954] Said active portion 3 of arms A and B comprises an active face 4 and an opposite face 5 .

[0955] The active faces 4 of the arms A and B have bristles 6. Preferably, the opposite faces of the arms A and B do not have bristles.

[0956] The bristles can be grouped together into tufts of bristles 6 .

[0957] Figure 2 The active surfaces 4 of the active parts 3 of arms A and B are shown side by side.

[0958] The active surfaces of arms A and B have bristles 6 which are arranged in the form of tufts of bristles 6 .

[0959] There may be free spaces 8 between each tuft of bristles 6 .

[0960] The active surfaces of arms A and B may comprise several rows 7 of tufts of bristles 6 .

[0961] Between each row 7 of tufts of bristles 6 there may be a free space 8 .

[0962] The rows 7 of tufts of bristles 6 may be parallel to each other.

[0963] Thus, keratin hair fibers can be placed between the bristle clusters so as to form waves.

[0964] The rows 7 of tufts of bristles 6 of the active face 4 of arm A are complementary to the rows 7 of tufts of bristles 6 of the active face 4 of arm B.

[0965] To use the clamp, the user places a lock of keratin hair fibers at the active portion between arms A and B when the clamp is in the spaced apart position (ie the active portions 3 are at a distance from each other).

[0966] The user then applies a compressive force to the clamp in order to bring the clamp into a closed position (ie, to bring the movable parts toward each other).

[0967] In the closed position of the movable part, the bristles of arms A and B are interlaced so as to clamp the keratin hair fibers without blocking them.

[0968] The user can slide the clamp along the lock (ie from the root to the tip of the lock) while maintaining a certain pressing force.

[0969] The clamp can be moved repeatedly along the strands of keratin hair fibers.

[0970] plan

[0971] The composition for dyeing keratin hair fibres described above and the optional composition D can be used on dry or wet keratin hair fibres and also on any type of light or dark, natural or pigmented, permanently wavy, bleached or relaxed keratin hair fibres.

[0972] According to a preferred embodiment, the dyeing composition and the composition D are applied simultaneously to the keratin hair fibres.

[0973] According to another preferred embodiment, the composition D is applied to the keratin hair fibers after the dyeing composition has been applied to the keratin hair fibers.

[0974] According to another preferred embodiment, composition D is applied to the keratin hair fibres before applying the composition for dyeing keratin hair fibres.

[0975] According to a particular embodiment of the invention, the keratinous hair fibres, such as the hair, are washed before applying the composition for dyeing keratinous hair fibres and optionally the composition D.

[0976] Preferably, a washing, rinsing, draining or drying step is carried out after applying the dyeing composition to the keratin hair fibres and optionally before applying the composition D to the keratin hair fibres.

[0977] The application of the composition for dyeing keratin hair fibres and of the optional composition D to the keratin hair fibres is generally carried out at room temperature (between 15° C. and 25° C.).

[0978] According to a preferred embodiment, applying the composition for dyeing keratin hair fibres and optionally the composition D to the keratin hair fibres is carried out at a temperature between 15 and 50°C, more preferably between 20 and 40°C.

[0979] After applying the dyeing composition to the keratin hair fibers, it is possible to wait between 1 minute and 6 hours, in particular between 1 minute and 2 hours, more particularly between 1 minute and 1 hour, more preferably between 1 minute and 30 minutes, for example before applying composition D to the keratin hair fibers or before a washing, rinsing, draining or drying step.

[0980] Preferably, there is no leave-on time after application of the dyeing composition to the keratin hair fibres and before application of the composition D to the keratin hair fibres.

[0981] After application of the dyeing composition and of the optional composition D, the fibres may be left to dry or may be dried, for example, at a temperature greater than or equal to 30°C.

[0982] Thus, the method according to the invention may comprise the step of applying heat to the keratin hair fibers using a heating tool.

[0983] The heat application step of the method of the present invention can be performed using a hood, a hair dryer, a straightening iron or curling iron, a Climazone...

[0984] Preferably, the heat application step of the method of the present invention is performed using a hair dryer.

[0985] When the method of the invention involves a step of applying heat to the keratin hair fibres, this step of applying heat to the keratin hair fibres is carried out after applying the composition for dyeing keratin hair fibres and the optional composition D to the keratin hair fibres.

[0986] During the step of applying heat to the keratin hair fibers, a mechanical action may be applied to the locks, such as combing, brushing or running the fingers through.

[0987] When the step of applying heat to the keratin hair fibres is carried out using a hood or a hairdryer, the temperature is preferably between 30 and 110°C, preferably between 50 and 90°C.

[0988] When the step of applying heat to the keratin hair fibres is performed using a straightener, the temperature is preferably between 110°C and 220°C, preferably between 140°C and 200°C.

[0989] In a particular variant, the method of the invention involves a step (b1) of applying heat using a hood, a hair dryer or a Climazon, preferably a hair dryer, and a step (b2) of applying heat using a straightener or a curling iron, preferably a straightener.

[0990] Step (b1) may be performed before step (b2).

[0991] During step (b1 ), also called drying step, the keratin hair fibers may be dried, for example, at a temperature greater than or equal to 30° C. According to a particular embodiment, this temperature is greater than 40° C. According to a particular embodiment, this temperature is greater than 45° C. and less than 110° C.

[0992] Preferably, if keratin hair fibers are dried, they are dried with a stream of air in addition to the supply of heat. This stream of air during drying enables improved strand separation of the coating.

[0993] During drying, the locks may be subjected to mechanical action, such as combing, brushing or running the fingers through.

[0994] During step (b2), the passage of a straightener or curling iron, preferably a straightener, may be carried out at a temperature ranging from 110 to 220°C, preferably between 140 and 200°C.

[0995] After the heating step, a shaping step may be carried out, for example with a straightener; the temperature for the shaping step is between 110°C and 220°C, preferably between 140°C and 200°C.

[0996] Preferably, the step of applying the dyeing composition to the keratin hair fibers is repeated several times.

[0997] According to a preferred embodiment, the method of the invention is a method for removing color from keratin hair fibers that have previously been dyed, which method notably comprises a step of mixing at least two compositions A and B extemporaneously at the time of use to obtain a composition for dyeing keratin hair fibers as defined above and a step of applying the dyeing composition to the keratin hair fibers, wherein:

[0998] - Composition A comprises at least one (poly)carbodiimide compound as described above; and

[0999] - Composition B comprises at least one colorant chosen from pigments, direct dyes, and mixtures thereof.

[1000] According to a preferred embodiment, the method of the invention is a method for removing color from keratin hair fibers that have previously been dyed, which method notably comprises a step of mixing at least two compositions A and B extemporaneously at the time of use to obtain a composition for dyeing keratin hair fibers as defined above and a step of applying the dyeing composition to the keratin hair fibers, wherein:

[1001] - Composition A comprises at least one (poly)carbodiimide compound as described above;

[1002] - composition B comprises at least one compound having at least one carboxylic acid group, other than an associative polymer as described above;

[1003] Composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof.

[1004] According to another preferred embodiment, the method of the invention is a method for removing color from keratin hair fibers that have previously been dyed, which method comprises in particular a step of mixing extemporaneously at the time of use at least two compositions A and B to obtain a composition for dyeing keratin hair fibers as defined above and a step of applying the dyeing composition to the keratin hair fibers, wherein:

[1005] - Composition A comprises at least one (poly)carbodiimide compound as described above;

[1006] - composition B comprises at least one compound having at least one carboxylic acid group, other than an associative polymer as described above;

[1007] Composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof; and

[1008] Before and / or after, preferably after, the application of the mixture of compositions A and B to the keratinous hair fibres, a composition D as previously described is applied to the keratinous hair fibres.

[1009] Preferably, compositions A and B are mixed preferably less than 15 minutes before application to the keratin hair fibers, more preferably less than 10 minutes before application, better still less than 5 minutes before application.

[1010] The weight ratio between composition A and composition B preferably ranges from 0.1 to 10, preferably from 0.2 to 5 and better still from 0.5 to 2, or even from 0.6 to 1.5.

[1011] In a specific embodiment, the weight ratio between composition A and composition B is equal to 1.

[1012] Preferably, composition A comprises at least one aminosilicone as described above.

[1013] Preferably, composition A comprises at least one non-carboxylic acid anionic thickener as described above.

[1014] Preferably, composition B comprises at least one aminosilicone as described above.

[1015] Preferably, composition B comprises at least one associative polymer as previously described other than a non-carboxylic acid anionic thickener.

[1016] Preferably, composition B comprises, other than an associative polymer, at least one compound having at least one carboxylic acid group as previously described.

[1017] The total amount of (poly)carbodiimide compounds preferably ranges from 0.01% to 40% by weight, more preferably from 0.1% to 30% by weight, better still from 0.5% to 20% by weight and even more preferably from 1% to 12% by weight relative to the total weight of composition A.

[1018] The total amount of compounds having at least one carboxyl group preferably ranges from 2 to 60% by weight relative to the total weight of composition B, more preferably from 5 to 40% by weight and better still from 5 to 20% by weight.

[1019] The aminosilicone may be present in a total amount ranging from 0.01% to 20% by weight relative to the total weight of composition A and / or composition B, preferably from 0.05% to 15%, more preferably from 0.1% to 10% and even more preferably still from 0.5% to 5%.

[1020] The non-carboxylic acid anionic thickeners may be present in a total amount ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, better still from 0.1% to 5% by weight and even better still from 0.1% to 3% by weight relative to the total weight of composition A.

[1021] Next, as previously indicated, the process according to the invention for removing color from keratin hair fibers that have previously been dyed comprises applying at least one color-removing composition as defined above to keratin hair fibers that have previously been dyed using at least one composition for dyeing keratin hair fibers as defined above.

[1022] Preferably, the decolorizing composition is left on for 30 seconds to 60 minutes, preferably from 1 to 40 minutes, more preferably from 1 to 30 minutes and better still from 2 to 20 minutes.

[1023] According to a particular embodiment, the method according to the invention also comprises a step of massaging the keratin hair fibers after applying the depigmenting composition.

[1024] During this massage step, specific tools such as an exfoliating glove can be used.

[1025] Preferably, during the massaging step, the fingers are moved five times along the lock of hair. The total duration of the five movements may range, for example, from 30 seconds to 2 minutes per 1 g of lock of hair.

[1026] The step of massaging the keratin hair fibers may be repeated several times, for example twice, optionally with intermediate rest times.

[1027] The step of applying the color removing composition may be repeated several times, optionally with intermediate rinsing.

[1028] The time between the step of applying the composition for dyeing keratin hair fibers and the step of applying the color removing composition can range from a few minutes to several days, for example tens of days. Preferably, the time between the step of applying the composition for dyeing keratin hair fibers and the step of applying the color removing composition ranges from 1 hour to 30 days, more preferably from 1 day to 15 days.

[1029] The optional massage step may be followed by a step of washing the keratin hair fibers (e.g. with a shampoo). The keratin hair fibers may then be massaged, rinsed and dried.

[1030] Preferably, there is no step of washing, rinsing, draining or drying the keratinous hair fibers between the application of the color removing composition and the use of the clamp as previously described.

[1031] After applying the depigmenting composition as described above, the method according to the invention consists in applying to the keratin hair fibers a clamp as previously described.

[1032] The time between the step of applying the color removing composition and the step of applying the fixture can range from a few seconds to a few minutes, preferably from 30 seconds to 60 minutes, preferably from 1 to 40 minutes, more preferably from 1 to 30 minutes, and even better from 2 to 20 minutes.

[1033] Preferably, the clamp as described above is applied from the root to the tip of the keratin hair fiber.

[1034] Preferably, the clamp as described above is applied along the keratinous hair fibers for 10 to 150 passes; more preferably, the clamp as described above is applied along the keratinous hair fibers for 10 to 100 passes.

[1035] The clamp as previously described can be applied to wet or dry keratin hair fibers.

[1036] Preferably, a clamp as previously described is applied to wet keratinous hair fibers.

[1037] The step of applying the clamp as described above may be followed by a step of washing the keratin hair fibers (for example using a shampoo). The keratin hair fibers may then be massaged, rinsed and dried.

[1038] Preferably, the method according to the invention comprises the step of washing the keratin hair fibres, for example by shampooing, after applying the clamp to the keratin hair fibres.

[1039] Preferably, the present invention is a method for removing color from keratin hair fibers that have previously been dyed, the method comprising in particular:

[1040] i) applying to keratinous hair fibers a composition for dyeing keratinous hair fibers as described above, and then

[1041] ii) optionally leaving the dyeing composition on the fibers for a leave-on time of from 1 minute to 30 minutes, preferably from 1 to 20 minutes, and then

[1042] iii) optionally washing, rinsing, draining or drying the fibers, and then

[1043] iv) optionally applying to the keratin hair fibers a composition D comprising at least one silicone compound comprising at least one carboxyl group as previously described; then

[1044] v) optionally leaving said composition D on the keratin hair fibers for a leave-on time of from 1 minute to 30 minutes, preferably from 1 to 20 minutes, and then

[1045] vi) optionally carrying out a step of washing, rinsing, draining or drying the keratinous hair fibers,

[1046] vii) applying to previously dyed keratin hair fibers a color removing composition as described above,

[1047] viii) optionally carrying out a step of massaging the keratinous hair fibers, preferably at the roots of the keratinous hair fibers,

[1048] ix) optionally leaving the dyeing composition on the fibers for a leave-on time of from 1 minute to 30 minutes, preferably from 1 to 20 minutes, and then

[1049] x) applying one or more passes of the clamp as described above to the keratinous hair fibers, and then

[1050] xi) optionally carrying out a step of washing, rinsing, draining or drying the keratin hair fibres.

[1051] According to a preferred embodiment, the method for removing color from previously dyed keratin hair fibers is a method for removing color from keratin hair fibers, the method comprising in particular:

[1052] i) a step of mixing extemporaneously at the time of use at least two compositions A and B in order to obtain a composition for dyeing keratin hair fibres as defined above, wherein:

[1053] - Composition A comprises at least one (poly)carbodiimide compound as described above;

[1054] - Composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof; then

[1055] ii) applying the dyeing composition to keratinous hair fibers, then

[1056] iii) optionally applying to the keratin hair fibers a composition D comprising at least one silicone compound comprising at least one carboxyl group as previously described; then

[1057] iv) applying at least one color removing composition as previously described to keratinous hair fibers previously colored by said coloring composition; then

[1058] v) optionally carrying out a step of massaging the keratinous hair fibers, preferably at the roots of the keratinous hair fibers,

[1059] vi) applying a clamp as described above to the keratinous hair fibers, and then

[1060] vii) optionally carrying out a step of washing the keratinous hair fibres (for example using a shampoo).

[1061] According to a preferred embodiment, the method for removing color from previously dyed keratin hair fibers is a method for removing color from keratin hair fibers, the method comprising in particular:

[1062] i) a step of mixing extemporaneously at the time of use at least two compositions A and B in order to obtain a composition for dyeing keratin hair fibres as defined above, wherein:

[1063] - Composition A comprises at least one (poly)carbodiimide compound as described above;

[1064] - composition B comprises at least one compound having at least one carboxylic acid group, other than an associative polymer as described above;

[1065] Composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof; then

[1066] ii) applying the dyeing composition to keratinous hair fibers, then

[1067] iii) optionally applying to the keratin hair fibers a composition D comprising at least one silicone compound comprising at least one carboxyl group as previously described; then

[1068] iv) applying at least one color removing composition as previously described to keratinous hair fibers previously colored by said coloring composition; then

[1069] v) optionally carrying out a step of massaging the keratinous hair fibers, preferably at the roots of the keratinous hair fibers,

[1070] vi) applying a clamp as described above to the keratinous hair fibers, and then

[1071] vii) optionally carrying out a step of washing the keratinous hair fibres (for example using a shampoo).

[1072] Multi-compartment device (test kit)

[1073] The invention also relates to a device for coloring and decoloring keratinous hair fibers, such as hair, comprising a plurality of compartments, the compartments comprising:

[1074] - a dyeing composition in the first compartment, comprising:

[1075] - at least one (poly)carbodiimide compound as described above;

[1076] - at least one colorant selected from pigments, direct dyes and mixtures thereof,

[1077] - a composition in the second compartment for removing color from keratin hair fibers previously dyed by said dyeing composition, comprising at least one alkyl carbonate or alkylene carbonate as previously defined, and

[1078] - A clamp as previously described.

[1079] According to a preferred embodiment, the device for dyeing and removing color from keratinous hair fibers, such as hair, comprises a plurality of compartments, comprising:

[1080] - a composition A in the first compartment, comprising at least one (poly)carbodiimide compound as described above;

[1081] - a composition B in the second compartment comprising at least one colorant chosen from pigments, direct dyes and mixtures thereof,

[1082] - a composition for removing color from keratin hair fibers previously dyed by said dyeing composition, comprising at least one alkyl carbonate or alkylene carbonate as previously defined, and

[1083] - A clamp as previously described.

[1084] According to a preferred embodiment, the device for dyeing and removing color from keratinous hair fibers, such as hair, comprises a plurality of compartments, which include:

[1085] - a composition A in the first compartment, comprising at least one (poly)carbodiimide compound as described above;

[1086] - a composition B in the second compartment comprising at least one colorant chosen from pigments, direct dyes and mixtures thereof,

[1087] - a composition for removing color from keratin hair fibers previously dyed by said dyeing composition, comprising at least one alkyl carbonate or alkylene carbonate as previously defined, in the third compartment,

[1088] - the clamp as previously described, and

[1089] - optionally in a fourth compartment a composition D comprising at least one silicone compound comprising at least one carboxyl group as previously described.

[1090] According to a preferred embodiment, the device for dyeing and removing color from keratinous hair fibers, such as hair, comprises a plurality of compartments, comprising:

[1091] - a composition A in the first compartment, comprising at least one (poly)carbodiimide compound as described above;

[1092] a composition B in the second compartment comprising, other than an associative polymer, at least one compound having at least one carboxylic acid group as previously described,

[1093] Composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof,

[1094] - a composition for removing color from keratin hair fibers previously dyed by said dyeing composition, comprising at least one alkyl carbonate or alkylene carbonate as previously defined, in the third compartment,

[1095] - the clamp as previously described, and

[1096] - optionally in a fourth compartment a composition D comprising at least one silicone compound comprising at least one carboxyl group as previously described.

[1097] The present invention will now be described more specifically by way of examples, which do not limit the scope of the present invention in any way. However, these examples enable specific features, variants and preferred embodiments of the present invention to be supported.

[1098] Examples

[1099] The (poly)carbodiimides of the invention are obtainable via synthesis methods known to the person skilled in the art from commercial products or reagents which can be synthesized according to chemical reactions also known to the person skilled in the art. For example, the book Sciences of Synthesis-Houben-Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D-70469 Stuttgart, or U.S. Pat. No. 4,284,730 or Canadian Patent Application No. CA2,509,861 may be mentioned.

[1100] More specifically, the process for preparing the (poly)carbodiimide of the present invention involves in a first step a diisocyanate reagent (1):

[1101] O=C=N-L1-N=C=O (1),

[1102] In formula (1), L1 is as defined previously, which is reacted in the presence of a carboimidation catalyst (2) (such as those described in US Pat. No. 4,284,730, in particular a phosphorus-based catalyst, in particular selected from phospholene oxides and phospholene sulfoxides, diaza- and oxaza-phosphacyclopentanes), preferably under an inert atmosphere (nitrogen or argon), and in particular in a polar solvent (preferably an aprotic 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 at about 140° C.; to obtain the carbodiimide diisocyanate compound (3):

[1103] O=C=N-L1-(N=C=N-L1) n -N=C=O (3),

[1104] In formula (3), L1 and n are as defined previously. A benzoyl halide such as benzoyl chloride may be added to deactivate the catalyst.

[1105] In order to obtain "symmetrical" (poly)carbodiimides, during the second step of the preparation process, compound (3) is reacted with 1 molar equivalent (1 eq.) of a nucleophile R1-X1-H and then with 0.5 eq. of the reagent HEH, wherein R1, X1 and E are as previously defined, to obtain "symmetrical" compounds (4) according to the invention:

[1106] [R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)]2-E (4),

[1107] In formula (4), R1, X1, L1, n and E are as defined previously. According to one variant of obtaining compound (4) from (3), 0.5 equivalents of the reagent HEH can be added first, and then 1 equivalent of the reagent R1-X1-H.

[1108] In order to obtain "asymmetric" (poly)carbodiimides, during the second step of the preparation process, compound (3) is reacted with 1 molar equivalent (1 eq.) of a nucleophilic reagent R1-X1-H and then with 1 eq. of the reagent HEH, wherein R1, X1 and E are as defined above, to obtain compound (5):

[1109] R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EH (5),

[1110] In formula (5), R1, X1, L1, n and E are as defined previously.

[1111] According to one variant of obtaining compound (5) from (3), it is possible to first add 1 equivalent of the reagent R1-X1-H and then 0.5 equivalent of the reagent HEH.

[1112] During the third step, compound (5) is reacted with 1 equivalent of compound (6)

[1113] R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O (6); the compound (6) is prepared in advance from the compound (3')

[1114] O=C=N-L1-(N=C=N-L1) z -N=C=O(3'),

[1115] In formula (3'), L1 and z are as previously defined, which reacts with 1 equivalent of a nucleophile R2-X2-H, wherein L1, R2, X2 and z are as previously defined, to give an asymmetric compound (7):

[1116] 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),

[1117] In formula (7), R1, X1, L1, R2, X2, n, z and E are as previously defined.

[1118] One molar equivalent of the compound O=C=N-L1-(N=C=N-L1) can be made z -N=C=O (3') is reacted with 1 / w molar equivalent of HEH and then with 1 equivalent of nucleophile R2-X2-H to obtain compound (8):

[1119] H-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NH-C(O)-X2-R2 (8),

[1120] In formula (8), L1, R2, X2, z and E are as defined previously, and w is an integer between 1 and 3; more preferably, w=1.

[1121] This final compound (8) can then be reacted with 1 equivalent of compound (4'):

[1122] 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 equivalents of a nucleophilic reagent R1-X1-H with 1 equivalent of a compound (3)) to obtain the (poly)carbodiimide (9) of the present invention:

[1123] R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NHC(O)-X2-R2 (9),

[1124] In formula (9), L1, R1, X1, R2, X2, n, z, w and E are as previously defined.

[1125] The (poly)carbodiimide compounds and similarly all reaction intermediates and reagents 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.

[1126] Example 1: Method for synthesizing (poly)carbodiimide compounds

[1127] 50 g of 4,4′-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphole 1-oxide were placed in a 500 ml three-necked round-bottom flask equipped with a thermometer, a stirrer and a reflux tube under stirring.

[1128] The reaction medium was heated at 140° C. for 4 hours under nitrogen and the results were determined by infrared spectroscopy at 2200 and 2300 cm -1 The reaction was monitored by the absorption of isocyanate functional groups between the reaction mixtures and then cooled to 120°C.

[1129] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol was introduced into the reaction medium under stirring. The temperature was maintained at 120°C until the isocyanate functional groups had completely disappeared. The infrared spectrum showed that the isocyanate functional groups at 2200-2300 cm -1 Monitor and then cool to room temperature.

[1130] After cooling to room temperature, the reaction medium was poured dropwise into a 500 ml glass beaker filled with 85 g of distilled water under vigorous stirring to obtain the desired product in the form of a translucent yellow liquid.

[1131] Example 2:

[1132] The compositions described below were prepared: Unless otherwise mentioned, the amounts are expressed as g of as-obtained starting material / 100 g.

[1133] Dye composition:

[1134] [Table 1]

[1135]

[1136] (1) synthesized according to the synthesis method described in Example 1 (containing 40% active material in water),

[1137] (2) sold by Sepinov under the name Sepinov EMT10 (containing 90% active material),

[1138] (3) Sold by Wacker under the name Belsil ADM LOG 1 (15% active material).

[1139] [Table 2]

[1140]

[1141]

[1142] (4) Sold by Daito Chemical Industry Co., Ltd. under the trade name Daitosol 3000SLPN-PE1 (aqueous dispersion containing 30% active material)

[1143] (5) Sold by Rohm and Haas under the trade name Aculyn (Oxyalkylened methacrylic acid / ethyl acrylate / stearyl methacrylate terpolymer containing 30% active material)

[1144] Composition A was mixed with composition B in a mass ratio of 50 / 50 to obtain dyeing composition C.

[1145] Next, a composition D was prepared as follows: the respective amounts are expressed in g / 100 g of the starting material obtained.

[1146] [Table 3]

[1147] Composition D <![CDATA[Bis-carboxy decyl polydimethylsiloxane (6) > 2 Isododecane Appropriate amount up to 100

[1148] (6) Sold by Momentive Performance Materials under the trade name SilformINX

[1149] Color removal composition:

[1150] In the meantime, a decolorizing composition according to the invention was prepared and is described in the following table: the respective amounts are expressed in g / 100 g of the starting material obtained.

[1151] [Table 4]

[1152] Composition E Propylene carbonate 39.5 PPG-3 Methyl Ether 10 <![CDATA[Polyacryloyldimethyltaurine ammonium (7) > 0.5 Propylene glycol Appropriate amount up to 100

[1153] (7) Marketed by Clariant under the trade name Hostacerin AMPS

[1154] Staining protocol:

[1155] Coloring composition C is applied to a dry natural hair tress containing 90% white hair in an amount of 0.8 g of composition per gram of tress using a small brush. The tress is then detangled and dried with a hairdryer at medium heat.

[1156] Next, composition D is applied to the hair lock previously treated with composition C in an amount of 0.5 g of composition per gram of lock.

[1157] The tresses were then detangled and dried with a hair dryer on medium heat.

[1158] The tresses were then subjected to an accelerated ageing process by placing them in an oven at a temperature of 60°C for 48 hours before applying the colour removing composition.

[1159] This accelerated ageing step makes it possible to simulate the natural ageing of the coloured coating on the hair in vivo; this ageing corresponds to 2 weeks at room temperature under natural conditions.

[1160] Solutions for removing color:

[1161] Three different methods for removing color from the locks colored with composition C+D were carried out:

[1162] - Comparative method 1, in which only the color-removing composition E is applied to the dyed hair locks;

[1163] - Comparative method 2, in which only the clamp as described above was applied to the dyed hair locks (Brosse Pince Ceramik Defrisage from the company Anself);

[1164] - Method 3 according to the invention, in which the depigmenting composition E is applied to the dyed hair lock and then a clamp as described above is applied to the hair lock (Brosse Pince Ceramik Defrisage from the company Anself).

[1165] In comparative method 1, the depigmenting composition E is applied to the dyed hair tresses using the fingers in an amount of 2 g of composition per g of tress.

[1166] The lock is then combed 6 times using a comb in order to properly distribute composition E on the lock.

[1167] The tresses were allowed to sit at room temperature for 4 minutes before being subjected to the shampooing regimen described below.

[1168] In comparative method 2, water was applied to the dyed hair tresses using the fingers in an amount of 2 g of water per g of tresses.

[1169] The tress is then combed 6 times using a comb in order to distribute the water properly on the tress.

[1170] The lock of hair is then clamped between arms A and B of a clamp according to the invention, and 100 passes of the clamp along the lock of hair from root to tip are then made.

[1171] The shampoo washing regimen described below was then followed.

[1172] In method 3 according to the invention, the depigmenting composition E is applied to the dyed hair locks using the fingers in an amount of 2 g of composition per g of lock.

[1173] The lock is then combed 6 times using a comb in order to properly distribute composition E on the lock.

[1174] The lock of hair is then clamped between arms A and B of a clamp according to the invention, and 100 passes of the clamp along the lock of hair from root to tip are then made.

[1175] The shampoo washing regimen described below was then followed.

[1176] Shampoo washing program:

[1177] The tresses were combed, moistened with water at 35°C and then passed between the fingers five times for 5 seconds. The tresses were then squeezed dry between two fingers.

[1178] Standard shampoo (Garnier Ultra Doux) was evenly applied to the dyed tresses at a rate of 0.4 g standard shampoo per gram of tress, and the tresses were gently massaged for 15 seconds along their length from root to tip (6 passes).

[1179] The tresses were then placed on a watch glass and allowed to sit for 1 minute.

[1180] Next, rinse the tress with water while passing it between your fingers (15 passes). Then squeeze the tress dry between two fingers before moving on to the next shampoo wash.

[1181] Comb the locks of hair and dry them with a hairdryer.

[1182] result

[1183] The permanence of the color of the hair locks was evaluated in the CIE L*a*b* system using a Minolta spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, including specular reflection component).

[1184] In the L*a*b* system, L* represents the intensity of the color, a* represents the green / red axis and b* represents the blue / yellow axis.

[1185] The permanence of the coloring is evaluated by the color difference ΔE between the dyed locks before the step of removing the color and then after undergoing the above-described protocol for removing color from previously dyed hair locks. The lower the value of ΔE, the more permanent the color is, considering the above-described protocol for removing color from previously dyed hair locks.

[1186] Calculate the ΔE value according to the following equation:

[1187]

[1188] In this equation, L*a*b* represents the values ​​measured after the hair is colored and after the color removal step, and L0*a0*b0* represents the values ​​measured after the hair is colored but before the color removal step.

[1189] [Table 5]

[1190] plan L* a* b* ΔE Stained control tress 43.4 20.3 28.7 - Color removal method 1 (comparative) 49.9 19.7 27.8 6.6 Color removal method 2 (comparative) 50.4 19.4 27.4 7.2 Color removal method 3 (the present invention) 65.8 1.8 15.1 32.1

[1191] It was observed that the method for removing color from dyed keratin hair fibers according to the invention has a superior ability to remove color from keratin hair fibers compared to the comparative method.

[1192] The process for removing color from keratin hair fibers according to the invention thus makes it possible to obtain an effective removal of the color of hair locks that have previously been dyed using a composition for dyeing keratin hair fibers comprising a (poly)carbodiimide compound and a colorant chosen from pigments, direct dyes, and mixtures thereof.

Claims

1. A method for removing color from keratinous hair fibers previously dyed by at least one composition for dyeing keratinous hair fibers, said composition comprising: - at least one (poly)carbodiimide compound; and - at least one colorant selected from pigments, direct dyes and mixtures thereof; The method comprises the following steps: i) applying to said keratin hair fibers previously dyed by said dyeing composition at least one color removing composition comprising: - at least one alkyl carbonate or alkylene carbonate; and ii) applying a clamp (1) comprising two arms A and B to the keratin hair fiber, the keratin hair fiber passing between the arms, Each arm A and B comprises a supporting part (2) and a movable part (3), The arms A and B are movable between a spaced apart position in which the movable parts (3) are spaced apart from each other by a certain distance and a closed position in which the movable parts (3) are facing each other. The movable part (3) comprises an movable surface (4) and an opposite surface (5), wherein the movable surface (4) has bristles (6). Therein, in the closed position of the movable part (3), the bristles (6) of the arms A and B are interlaced with each other so as to clamp the keratin hair fibers without blocking them.

2. The method according to claim 1, characterized in that The (poly)carbodiimide compound is selected from the following compounds of formula (I): in: -X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; - R1 and R2 independently represent: a group selected from a hydrocarbon-based group, preferably an alkyl group, optionally interrupted by one or more heteroatoms; selected from an alkoxysilyl group, a hydroxysilyl group, an acetoxysilyl group, a vinylsilyl group, an acryloylalkylsilyl group, a methacryloylalkylsilyl group, a crotonylalkylsilyl group, a carboxyanhydridealkylsilyl group, a carboxyalkylsilyl group, a hydroxyalkylsilyl group, an aldehydealkylsilyl group, a mercaptoalkylsilyl group, a norbornenylsilyl group, an acylpentadienylalkylsilyl group, a maleimidoalkylsilyl group, a sulfonylalkylsilyl group, a (meth)acryloylalkyl group, a crotonylalkyl group, an alkylepoxide such as a propylepoxide or a butylepoxide and an aziridine group and hydrocarbon-based groups, preferably alkyl groups, which are optionally interrupted by one or more heteroatoms and one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacryloylalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonylalkyl, alkylepoxides such as propylepoxide or butylepoxide and aziridine groups; -n indicates an integer ranging from 1 to 1000; and -A is a monomer selected from the following compounds:

3. The method according to claim 1, characterized in that The (poly)carbodiimide compound is selected from the following compounds of formula (II): in -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 indicate integers ranging from 1 to 20, wherein n+z≥2 and w indicates an integer ranging from 1 to 3; -L1 independently represents C1-C 18 Divalent aliphatic hydrocarbon-based groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocycloalkylene or C6-C 14 Arylene, and mixtures thereof; -E independently represents a group selected from the following: -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 saturated divalent 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.

4. The method according to claim 3, characterized in that The (poly)carbodiimide compound is selected from the compounds of 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; - n and z indicate integers ranging from 1 to 20, where n+z≥2 and w is equal to 1; -L1 is selected from C1-C 18 Divalent aliphatic hydrocarbon-based groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocycloalkylene or C6-C 14 Arylene, and mixtures thereof; -E independently represents a group selected from the following: --O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene and mixtures thereof; - When R5 is not a covalent bond, R5 is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof; and -R6 is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof.

5. The method according to claim 3 or 4, characterized in that: The (poly)carbodiimide compound is selected from the compounds of formula (II), wherein: -X1 and X2 independently represent an oxygen atom; - R1 and R2 are independently monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed; - n and z indicate integers ranging from 1 to 20, where n+z≥2 and w is equal to 1; -L1 is C3-C 15 Cycloalkylene; -E independently represents a group selected from the following: -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene and mixtures thereof; - When R5 is not a covalent bond, R5 is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof; and -R6 is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof.

6. The method according to any one of claims 3 to 5, characterized in that The (poly)carbodiimide compound is selected from the compounds of formula (II), wherein: -X1 and X2 independently represent an oxygen atom; - R1 and R2 independently represent a compound of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q -(WE), Where R 13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30; - n and z indicate integers ranging from 2 to 20, wherein n+z ranges from 4 to 10 and w is equal to 1; -L1 is C3-C 15 Cycloalkylene, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, and -E represents a group -O-R3-O-, wherein R3 is selected from C6-C 14 Arylene, C3-C 12 Cycloalkylene, straight or branched C1-C 18 Alkylene, and mixtures thereof.

7. The method according to any one of claims 3 to 6, characterized in that The (poly)carbodiimide compound is selected from the compounds of formula (II), wherein: -X1 and X2 independently represent an oxygen atom; - R1 and R2 independently represent the compound of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q -(WE), Where R 13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30; - n and z indicate integers ranging from 2 to 20, wherein n+z ranges from 4 to 10 and w is equal to 1; -L1 is C3-C 15 Cycloalkylene, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and -E represents a group -O-R3-O-, wherein R3 represents a straight or branched C1-C 18 Alkylene groups, such as methylene, propylene, butylene, and ethylene.

8. The method according to any one of claims 3 to 7, characterized in that The (poly)carbodiimide compound is selected from the following compounds of formula (XII): wherein L1 is 4,4-dicyclohexylene methane, n and z indicate integers ranging from 2 to 20, wherein n+z ranges from 4 to 10, and E represents a group -O-R3-O-, wherein R3 represents a straight or branched C1-C ... 18 Alkylene groups such as methylene, propylene, butylene, ethylene, and r and s indicate integers ranging from 4 to 30.

9. The method according to any one of the preceding claims, characterized in that The total amount of the (poly)carbodiimide compounds ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferably from 0.2% to 10% by weight, even more preferably from 0.5% to 8% by weight, better still from 1% to 6% by weight, relative to the total weight of the dyeing composition.

10. The method according to any one of the preceding claims, characterized in that The total amount of coloring agent ranges from 0.001% to 20% by weight and preferably from 0.005% to 15% by weight relative to the total weight of the dyeing composition; preferably, the coloring agent is chosen from pigments.

11. The method according to any one of the preceding claims, characterized in that The alkyl carbonate or alkylene carbonate is a C1-C 30 , preferably C1-C6 alkyl ester or C1-C6 carbonate 30 , preferably C1-C6 alkylene ester; more preferably, the alkyl carbonate or alkylene carbonate is selected from alkylene carbonate, and better still is selected from propylene carbonate, butylene carbonate, pentylene carbonate and mixtures thereof.

12. The method according to any one of the preceding claims, characterized in that The total content of the alkyl carbonate or alkylene carbonate ranges from 10 to 60% by weight, preferably from 15 to 50% by weight, relative to the total weight of the color removing composition.

13. The method according to any one of the preceding claims, characterized in that The two arms A and B are articulated about an articulation axis (Z) and are angularly movable towards each other so that the movable parts (3) of arms A and B are in contact with each other.

14. The method according to any one of the preceding claims, characterized in that The bristles (6) are arranged in the form of bristle tufts, and the bristles are preferably made of natural materials such as natural silk or animal hair such as squirrel, wild boar or goat hair.

15. The method according to claim 14, characterized in that The active surfaces of arms A and B have a plurality of rows (7) of tufts of bristles (6) separated by free spaces (8), the rows (7) of tufts of bristles (6) of the active part (3) being arranged parallel to each other.

16. The method according to any one of the preceding claims, characterized in that The method comprises the step of washing the keratin hair fibers, for example by shampooing, after applying the clamp to the keratin hair fibers.

17. A device for coloring and removing color from keratinous hair fibers, such as hair, said device comprising a plurality of compartments, said compartments comprising: - a composition A in the first compartment, comprising at least one (poly)carbodiimide compound as defined in any one of claims 2 to 8, and - a composition B in the second compartment comprising at least one colorant chosen from pigments, direct dyes and mixtures thereof, - a composition in the third compartment for removing color from keratin hair fibers previously dyed by said dyeing composition, comprising at least one alkyl carbonate or alkylene carbonate as defined in any one of claims 11 and 12, and - A clamp (1) as defined in any one of claims 1 and 13 to 15.

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