Process for dyeing keratin hair fibres comprising application of (poly) carbodiimide compounds and colorants, application of steam and styling at specific temperatures

Abstract

The present invention relates to a process for dyeing keratin hair fibres, comprising: a) applying to the keratin hair fibres at least one composition C comprising:-at least one (poly) carbodiimide compound; and-at least one colorant selected from the group consisting of pigments, direct dyes and mixtures thereof; and then b) applying steam to the keratin hair fibres in an amount greater than or equal to 0.5 g / min by means of a device capable of generating steam, and c) shaping the keratin hair fibres at a temperature greater than or equal to 100 DEG C.

Description

Technical Field

[0001] The present invention relates to a method for dyeing keratinous hair fibers, which method comprises applying to the keratinous hair fibers a composition C comprising a (poly)carbodiimide compound and a colorant, followed by applying steam and shaping at a specific temperature. Background Art

[0002] In the field of dyeing keratinous hair fibers, it is known practice to dye keratinous hair fibers using direct dyes or pigments for non-permanent coloring or dye precursors for permanent coloring by various techniques.

[0003] Basically, there are three types of methods for dyeing keratinous hair fibers:

[0004] a) "Permanent" dyeing, which functions to provide a substantial change to the natural color and uses oxidative dyes that penetrate into the keratinous hair fibers and form a dyeing through an oxidative condensation process;

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

[0006] c) Temporary dyeing, which causes a change in the natural color of the keratinous hair fibers that remains from one shampoo wash to the next and is used to enhance or correct a tone that has already been obtained. It can also be compared to a "cosmetic" process.

[0007] Another dyeing method involves the use of pigments. Specifically, using pigments on the surface of keratin fibers generally enables a coloring to be obtained that is visible on dark keratinous hair fibers, since the surface pigments mask the natural color of the fibers. However, the coloring obtained by this dyeing method has the drawback of having poor resistance to shampoo washes and also to external agents such as sebum, sweat, brushing and / or friction.

[0008] Furthermore, temporary keratinous hair fiber dye compositions may result in cosmetically less than satisfactory properties, more particularly keratinous hair fiber conditioning properties, especially with regard to the smoothness feel of the keratinous hair fibers.

[0009] Accordingly, there is still a need for a method for dyeing keratinous hair fibers that has the following advantages: obtaining a uniform coloring coating on the keratinous hair fibers while forming a coating that is durable with respect to shampoo washes and the various stresses (such as brushing and / or friction) that the keratinous hair fibers may undergo, without damaging the keratinous hair fibers, and providing improved keratinous hair fiber conditioning properties, especially with regard to the smoothness feel of the keratinous hair fibers.

[0010] Accordingly, the object of the present invention is to develop a method for dyeing keratin hair fibers, which has the following advantages: obtaining a smooth and uniform coloring coating on the keratin hair fibers, while forming a coating that is durable against various stresses (such as brushing and / or friction) that the keratin hair fibers may undergo during shampooing and without damaging the keratin hair fibers, and providing improved conditioning properties for the keratin hair fibers, especially in terms of the smoothness of the keratin hair fibers. Summary of the Invention

[0011] Accordingly, a subject of the present invention is a method for dyeing keratin hair fibers, which comprises:

[0012] a) applying to the keratin hair fibers at least one composition C, which comprises:

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

[0014] - at least one colorant selected from pigments, direct dyes, and mixtures thereof; and then

[0015] b) applying steam to the keratin hair fibers in an amount greater than or equal to 0.5 g / min by means of a device capable of generating steam, and

[0016] c) shaping the keratin hair fibers at a temperature greater than or equal to 100 °C.

[0017] By means of the method for dyeing keratin hair fibers according to the present invention, coloring coatings are obtained on the keratin hair fibers, which enable obtaining a coloring that is visible on all types of keratin hair fibers and is durable against shampooing, while retaining the physical qualities of the keratin hair fibers. Such coatings can withstand external stresses that the keratin hair fibers may undergo, such as blow-drying and sweating. This coating particularly enables obtaining a uniform deposit.

[0018] For the purposes of the present invention, the term "coloring durable against shampooing" means that the coloring obtained after one shampooing, preferably after five shampooings, is durable.

[0019] The term "at least one" means one or more.

[0020] Unless otherwise indicated, the limits of a range of values are included within that range, especially in the expressions "between... and" and "ranging from... to...".

[0021] The present invention is not limited to the examples shown. The features of different examples can in particular be combined in variants not shown.

[0022] For the purposes of the present invention and unless otherwise indicated:

[0023] - "alkyl" denotes a straight-chain or branched-chain saturated group containing, for example, from 1 to 20 carbon atoms;

[0024] - "aminoalkyl" denotes an alkyl as previously defined, which alkyl contains an NH2 group;

[0025] - "hydroxyalkyl" denotes an alkyl as previously defined, which alkyl contains an OH group;

[0026] - "alkylene" denotes a straight-chain or branched-chain divalent saturated C2-C4 hydrocarbon-based group, such as methylene, ethylene or propylene;

[0027] - "cycloalkyl" or "alicyclic alkyl" denotes a saturated monocyclic or polycyclic, preferably monocyclic, hydrocarbon-based group containing from 1 to 3 rings, preferably 2 rings and containing from 3 to 24 carbon atoms, particularly from 3 to 20 carbon atoms, more particularly from 3 to 13 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, particularly cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl may be substituted by one or more (C1-C4) alkyls such as methyl; preferably, the cycloalkyl is isobornyl;

[0028] - "cycloalkylene" denotes a divalent cycloalkyl, where "cycloalkyl" is as previously defined, preferably C3-C 12 ;

[0029] - "aryl" is a monocyclic, bicyclic or tricyclic, fused or unfused, unsaturated and aromatic hydrocarbon-based cyclic group containing from 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms; preferably, the aryl contains 1 ring having 6 carbon atoms, such as phenyl, naphthyl, anthracenyl, phenanthryl and biphenyl, it being understood that the aryl may be substituted by one or more (C1-C4) alkyls such as methyl, preferably tolyl, xylyl or methylnaphthyl; preferably, the aryl represents phenyl;

[0030] - "arylene" is a divalent aryl, where "aryl" is as previously defined; preferably, the arylene represents phenylene;

[0031] - "heterocyclic" group denotes 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, including from 3 to 20 ring members, preferably between 5 and 10 ring members, such as imidazolyl, pyrrolyl and furyl;

[0032] - "Hetocycloalkyl" is a divalent heterocyclic group, where "heterocycle" is as defined previously;

[0033] - "Aryloxy" denotes aryl-oxy, where "aryl" is as defined previously;

[0034] - "Alkoxy" denotes alkyl-oxy, where "alkyl" is as defined previously;

[0035] - "Acetyloxy" denotes the ester group R-C(O)-O-, where R is an alkyl as defined previously;

[0036] - A "reactive" group is a group capable of forming a covalent bond with another identical or different group through a chemical reaction.

[0037] Unless otherwise indicated, when a compound is referred to in this patent application, it also includes its optical isomers, its geometric isomers, its tautomers or its salts, either alone or as a mixture.

[0038] The term "hair keratin fiber" means a keratin hair fiber or hair. In other words, the expressions "hair keratin fiber", "keratin hair fiber" and "hair" are equivalent in the following parts of the specification.

[0039] For the purposes of the present invention, the term "keratin hair fiber" means a keratin hair fiber of the head. This term does not correspond to body hair, eyebrows or eyelashes.

[0040] Polycarbodiimide compound

[0041] The composition C used in the context of the method according to the invention comprises at least one (poly)carbodiimide compound.

[0042] The composition may comprise at least two different (poly)carbodiimide compounds, present in the composition as a mixture.

[0043] The term "(poly)carbodiimide compound" means a compound containing 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.

[0044] The term "carbodiimide group" means a divalent straight-chain triatomic moiety of the general formula -(N=C=N)-.

[0045] The (poly)carbodiimide compound according to the present invention may optionally contain in its structure one or more reactive groups different from the carbodiimide group, and the reactive group is selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimide group alkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups.

[0046] The reactive group other than the carbodiimide group may be a side group or a terminal group. Preferably, the (poly)carbodiimide compound contains one or more terminal groups different from the carbodiimide group, preferably one or more terminal groups selected from: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimide group alkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups.

[0047] According to a specific embodiment, the (poly)carbodiimide compound is selected from the compounds of the following formula (I):

[0048]

[0049] Wherein:

[0050] -X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0051] -R1 and R2 independently represent: a group selected from hydrocarbon-based groups, preferably alkyl groups, optionally inserted with one or more heteroatoms; a group selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimide group alkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups; and hydrocarbon-based groups, preferably alkyl groups, optionally inserted with one or more heteroatoms and one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimide group alkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups;

[0052] -n indicates an integer ranging from 1 to 1000; and

[0053] -A is a monomer selected from the following compounds:

[0054]

[0055] According to another embodiment, the (poly)carbodiimide compound is selected from compounds of the following formula (I’):

[0056]

[0057] Wherein:

[0058] -X1 and X2 independently represent an oxygen atom O, a sulfur atom S, or an NH group;

[0059] -Y1 and Y2 independently represent a divalent organic group selected from saturated C1 to C 36 aliphatic groups or C6 to C 24 aromatic or alkylaromatic groups, and the aliphatic or aromatic group may optionally contain one or more non-side heteroatoms, such as nitrogen atoms, oxygen atoms, sulfur atoms, or combinations thereof;

[0060] - Z1 and Z2 independently represent a reactive end group or an inert end group;

[0061] - As an inert end group, Z1 and Z2 can independently represent a saturated straight-chain, branched-chain or cyclic C1 to C 50 aliphatic group, or a C6 to C 18 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 group may be partially or fully fluorinated; in this variant, Z1 and Z2 contain a bonding group CG that connects Z1 to Y1 and Z2 to Y2, and this 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 urethane group, a thiourethane group or a urea group;

[0062] - As a reactive end group, Z1 and Z2 can be selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidylalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide and aziridinyl groups;

[0063] - Q represents an organic polymer or an organic oligomer containing repeating units of a saturated straight-chain, branched-chain or alicyclic group, or an aromatic group or an alkyl aromatic group, and these repeating units are coupled via carbonate, ester, ether, amide, urethane or urea repeating bonds or combinations thereof;

[0064] - A represents a divalent aliphatic, aromatic, alkyl aromatic or straight-chain, saturated, branched-chain or cyclic group containing 2 to 30 carbon atoms, which may optionally contain one or more non-side heteroatoms such as nitrogen atoms, oxygen atoms, sulfur atoms, or combinations thereof in the aliphatic chain or aromatic chain;

[0065] - r indicates an integer equal to 0 or 1;

[0066] - m indicates an integer in the range from 0 to 1000, preferably equal to 0 or 1;

[0067] - m' indicates an integer in the range from 0 to 1000, preferably equal to 0 or 1;

[0068] -n denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1, where m+(m’*n)≥2.

[0069] Preferably, Z1 and Z2 independently represent reactive end groups; more preferably, Z1 and Z2 independently represent a group selected from the following: alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidylalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups.

[0070] Such (poly)carbodiimide compounds are, for example, sold by Stahl B.V under the name Permutex XR, or under the name RelcaLink10., or under the name Picassian XL, and Nisshinbo compounds are sold under the name Carbodilite with the series V-02, V-02-L2, SV-02, E-02, V-10, SW-12G, E-03A, E-04DG-T, E-05, V-04, V-02B, V-04PF, V-05.

[0071] Preferably, the (poly)carbodiimide compound is selected from compounds of the following formula (II):

[0072]

[0073] where:

[0074] -X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0075] -R1 and R2 independently represent a hydrocarbon-based group optionally inserted with one or more heteroatoms;

[0076] -n and z denote integers ranging from 1 to 20, where n+z≥2 and w denotes an integer ranging from 1 to 3;

[0077] -L1 independently represents a C1-C 18 divalent aliphatic hydrocarbon-based group, a C3-C 15 subcycloalkyl, a C3-C 12 subheterocycloalkyl or a C6-C 14 subaryl, and mixtures thereof;

[0078] -E independently represents a group selected from the following:

[0079] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0080] wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally inserted with one or more heteroatoms;

[0081] -R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally inserted with one or more heteroatoms;

[0082] -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally inserted with one or more heteroatoms.

[0083] The term "hydrocarbon-based group" means a saturated or unsaturated, straight-chain or branched-chain group containing 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 straight-chain group.

[0084] The hydrocarbon-based group may contain one or more cyclic groups.

[0085] The hydrocarbon-based group may be inserted with one or more heteroatoms particularly selected from O, S or N, and / or substituted with one or more cations, anions or zwitterions or cationic groups such as ammonium, anionic groups such as carboxylate, or zwitterionic groups, and / or contain metal ions that can be introduced in the form of salts.

[0086] The term "heteroatom" means an oxygen O, sulfur S or nitrogen N atom, and also halogen atoms such as Cl, F, Br and I. If the chain of the hydrocarbon-based group contains a heteroatom, the heteroatom is preferably selected from an oxygen O, sulfur S or nitrogen N atom.

[0087] Preferably, X1 and X2 independently represent an oxygen atom.

[0088] Preferably, R1 and R2 independently are selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols from which the hydroxy group has been removed, and mixtures thereof.

[0089] In a preferred embodiment, R1 and R2 independently are selected from the following groups (i) to (iv):

[0090] (i) A compound of the following formula (III):

[0091] R7-O-C(O)-C(R8)(H)-(III),

[0092] 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.

[0093] (ii) A compound of the following formula (IV):

[0094] R9-[O-CH2-C(H)(R 10 )] p -(IV),

[0095] wherein R9 represents a C1-C4 alkyl group, 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, ethyl or butyl group, R 10 is a hydrogen atom or a methyl group and p is equal to 1.

[0096] (iii) A compound of the following formula (V):

[0097] (R 11 )2N-CH2-C(H)(R 12 )-(V),

[0098] wherein 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 a methyl, ethyl or butyl group, and R 12 is a hydrogen atom or a methyl group.

[0099] (iv) A compound of the following formula (VI):

[0100] R 13 -[O-CH2-C(H)(R 14 )] q -(VI),

[0101] wherein 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 a methyl, ethyl or butyl group, and R 14 is a hydrogen atom or a methyl group.

[0102] 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.

[0103] According to an alternative embodiment, R1 and R2 are different, and one of the groups R1 or R2 represents a compound of formula (IV) as described above, and the other of the groups R1 or R2 represents a compound of formula (VI) as described above.

[0104] Preferably, in formula (IV), R9 is methyl, ethyl or butyl, and R 10 is a hydrogen atom or methyl and p is equal to 1.

[0105] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl and q denotes an integer ranging from 4 to 30.

[0106] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), wherein R 13 represents C1-C4 alkyl or phenyl, preferably C1-C4 alkyl, more preferably methyl, R 14 represents a hydrogen atom or C1-C4 alkyl, preferably a hydrogen atom, and q denotes an integer ranging from 4 to 30.

[0107] Preferably, n denotes an integer ranging from 1 to 20, more preferably from 2 to 20.

[0108] Preferably, z denotes an integer ranging from 1 to 20, more preferably from 2 to 20.

[0109] Preferably, w is equal to 1.

[0110] Preferably, w is equal to 1 and n + z denotes an integer ranging from 4 to 10.

[0111] Preferably, L1 is selected from C1-C 18 divalent aliphatic hydrocarbon-based groups such as methylene, ethylene and propylene, C3-C 15 cycloalkylenes such as cyclopentylene, cycloheptylene and cyclohexylene, C3-C 12 heterocycloalkylenes such as imidazolylene, pyrrolylene and furanylene, or C6-C 14 arylenes such as phenylene, and mixtures thereof.

[0112] For example, L1 may be selected from groups derived from the following: 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.

[0113] Preferably, L1 is selected from C3-C 15 subcycloalkyl or C6-C 14 subaryl, and mixtures thereof, such as a compound of the following formula (VII):

[0114]

[0115] Preferably, L1 is 4,4-dicyclohexylenemethane corresponding to the following formula (VIII):

[0116]

[0117] According to another embodiment, when L1 is C6-C 14 subaryl, L1 is not m-tetramethylxylylene represented by the following formula (IX):

[0118]

[0119] As previously indicated, E independently represents a group selected from the following:

[0120] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0121] wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally inserted with one or more heteroatoms;

[0122] -R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally inserted with one or more heteroatoms; and

[0123] -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally inserted with one or more heteroatoms.

[0124] Preferably, R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 subaryl such as phenylene, C3-C 12Subcycloalkyl groups such as cyclopropylidene and cyclobutylidene, linear or branched C1-C 18 Alkylene groups such as methylene and ethylene, and mixtures thereof.

[0125] More preferably, R3 and R4 are independently selected from linear or branched C1-C alkylene groups optionally interrupted by one or more heteroatoms, 18 such as methylene, butylene, propylene or ethylene.

[0126] Preferably, when R5 is not a covalent bond, R5 is selected from C6-C arylene groups optionally interrupted by one or more heteroatoms, 14 such as phenylene, C3-C 12 Subcycloalkyl groups such as cyclopropylidene and cyclobutylidene, linear or branched C1-C 18 Alkylene groups such as methylene and ethylene, and mixtures thereof.

[0127] Preferably, R6 is selected from C6-C arylene groups optionally interrupted by one or more heteroatoms, 14 such as phenylene, C3-C 12 Subcycloalkyl groups such as cyclopropylidene and cyclobutylidene, linear or branched C1-C 18 Alkylene groups such as methylene and ethylene, and mixtures thereof.

[0128] Preferably, E represents the group -O-R3-O-, where R3 is selected from C6-C arylene groups, C3-C 14 subcycloalkyl groups, linear or branched C1-C 12 alkylene groups, and mixtures thereof. 18

[0129] More preferably, E represents the group -O-R3-O-, where R3 represents a linear or branched C1-C alkylene group optionally interrupted by one or more heteroatoms, 18 such as methylene, butylene, propylene or ethylene.

[0130] According to a specific embodiment, the (poly)carbodiimide compound is a copolymer derived from an α-methylstyryl isocyanate of the following formula (X):

[0131]

[0132] wherein R independently represents an alkyl group containing from 1 to 24 carbon atoms, a cycloalkyl group containing from 3 to 24 carbon atoms or an aryl group containing from 6 to 24 carbon atoms, and

[0133] n indicates an integer ranging from 2 to 100.

[0134] In this embodiment, the term "alkyl" is as previously defined.

[0135] In this embodiment, the term "cycloalkyl" is as defined previously.

[0136] In this embodiment, n may denote an integer ranging from 2 to 50, preferably from 3 to 30, and even more preferably from 5 to 10.

[0137] According to another specific embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI):

[0138]

[0139] wherein R independently represents an alkyl group containing from 1 to 24 carbon atoms, a cycloalkyl group containing from 3 to 24 carbon atoms, or an aryl group containing from 6 to 24 carbon atoms.

[0140] "Alkyl", "cycloalkyl" and "aryl" are as defined previously.

[0141] According to a preferred embodiment, the (poly)carbodiimide compound is selected from the compounds of formula (I) or formula (II), wherein:

[0142] - X1 and X2 independently represent an oxygen atom;

[0143] - R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols from which the hydroxy group has been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycols from which the hydroxy group has been removed, more preferably the compound of formula (VI) as described previously, 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 denotes an integer ranging from 4 to 30;

[0144] - n and z (when they are present) denote integers ranging from 1 to 20, where n + z ≥ 2 and w equals 1;

[0145] - L1 (when it is present) is selected from C1-C 18 divalent aliphatic hydrocarbon-based groups, C3-C 15 subcycloalkyls, C3-C 12 subheterocycloalkyls or C6-C 14 subaryls, and mixtures thereof, preferably C3-C 15 subcycloalkyls;

[0146] - A (when it is present) is selected from C1-C 18 divalent aliphatic hydrocarbon-based groups, C3-C 15 subcycloalkyls, C3-C 12Azaheterocycloalkyl or C6-C 14 Arylene, and mixtures thereof, preferably C3-C 15 Cycloalkylene;

[0147] -E (when present) independently represents a group selected from:

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

[0149] wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof;

[0150] -When R5 is not a covalent bond, R5 (when present) is selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof; and

[0151] -R6 (when present) is selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof.

[0152] Preferably, the (poly)carbodiimide compound is selected from the compounds of formula (II), wherein:

[0153] -X1 and X2 independently represent an oxygen atom;

[0154] -R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols from which the hydroxy group has been removed, and mixtures thereof;

[0155] -n and z indicate integers ranging from 1 to 20, where n + z ≥ 2 and w equals 1;

[0156] -L1 is selected from C1-C 18 Divalent aliphatic hydrocarbon-based groups, C3-C 15 Cycloalkylene, C3-C 12 Azaheterocycloalkyl or C6-C 14 Arylene, and mixtures thereof;

[0157] -E 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 arylene optionally inserted with one or more heteroatoms, C3-C cycloalkylene, linear or branched C1-C alkylene, and mixtures thereof; 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof;

[0160] - When R5 is not a covalent bond, R5 is selected from C6-C arylene optionally inserted with one or more heteroatoms, C3-C cycloalkylene, linear or branched C1-C alkylene, and mixtures thereof; and 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; and

[0161] - R6 is selected from C6-C arylene optionally inserted with one or more heteroatoms, C3-C cycloalkylene, linear or branched C1-C alkylene, and mixtures thereof. 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

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

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

[0164] - R1 and R2 are independently a monoalkyl ether of a (poly)alkylene glycol from which the hydroxyl groups have been removed;

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

[0166] - L1 is C3-C 15 cycloalkylene;

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

[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 arylene optionally inserted with one or more heteroatoms, C3-C cycloalkylene, linear or branched C1-C alkylene, and mixtures thereof; 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof;

[0170] - When R5 is not a covalent bond, R5 is selected from C6-C arylene optionally inserted with one or more heteroatoms, C3-C cycloalkylene, linear or branched C1-C alkylene, and mixtures thereof; 14Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof; and

[0171] -R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof.

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

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

[0174] -R1 and R2 independently represent the compound of the following formula (VI):

[0175] R 13 -[O-CH2-C(H)(R 14 )] q -(VI),

[0176] wherein R 13 represents C1-C4 alkyl or phenyl, preferably C1-C4 alkyl, more preferably methyl, R 14 represents a hydrogen atom or C1-C4 alkyl, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30;

[0177] -n and z indicate integers ranging from 1 to 20, wherein n + z ranges from 4 to 10 and w is equal to 1;

[0178] -L1 is C3-C 15 Cycloalkylene, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylmethane; and

[0179] -E represents the group -O-R3-O-, wherein R3 is selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof.

[0180] Even more preferably, the (poly)carbodiimide compound is selected from the compounds of formula (II), wherein:

[0181] -X1 and X2 independently represent an oxygen atom;

[0182] -R1 and R2 independently represent the compound of the following formula (VI):

[0183] R13 -[O-CH2-C(H)(R 14 )] q -(VI)

[0184] wherein R 13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, and 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;

[0185] -n and z indicate integers ranging from 1 to 20, where the range of n + z is from 4 to 10 and w equals 1;

[0186] -L1 is a C3-C 15 cycloalkanediyl group, such as cyclopentanediyl, cycloheptanediyl, cyclohexanediyl and 4,4-dicyclohexylmethanediyl, preferably 4,4-dicyclohexylmethanediyl; and

[0187] -E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C 18 alkanediyl group optionally inserted with one or more heteroatoms, such as methylene, propanediyl, butanediyl or ethanediyl.

[0188] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of the following formula (XII):

[0189]

[0190] where L1 is 4,4-dicyclohexylmethanediyl, n and z indicate integers ranging from 1 to 20, where the range of n + z is from 4 to 10, E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C 18 alkanediyl group optionally inserted with one or more heteroatoms, such as methylene, propanediyl, butanediyl or ethanediyl, and r and s indicate integers ranging from 4 to 30.

[0191] Advantageously, the total amount of the (poly)carbodiimide compound 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 and still better from 1% to 6% by weight, relative to the total weight of composition C.

[0192] Colorant

[0193] Composition C used in the context of the method according to the invention comprises one or more colorants selected from pigments, direct dyes and mixtures thereof.

[0194] Preferably, the composition C used in the context of the method according to the invention comprises one or more pigments.

[0195] The term "pigment" refers to any pigment that imparts color to the keratin material. They have a solubility in water at 25 °C and atmospheric pressure (760 mmHg) of less than 0.05% by weight, and preferably less than 0.01%.

[0196] Pigments that can be used are especially selected from organic and / or mineral pigments known in the art, especially those described in Kirk - Othmer’s Encyclopedia of Chemical Technology and Ullmann’s Encyclopedia of Industrial Chemistry.

[0197] They can be natural, of natural origin or non - natural.

[0198] These pigments can be in the form of pigment powder or paste. They can be coated or uncoated.

[0199] Pigments can be selected, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacre or glitter flakes, and mixtures thereof.

[0200] The pigment can be a mineral pigment. The term "mineral pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann’s encyclopedia. Among the mineral pigments available in the present invention, iron oxides, chromium oxides, manganese violet, ultramarine, chromium hydrates, iron blue and titanium oxides can be mentioned.

[0201] The pigment can be an organic pigment. The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann’s Encyclopedia.

[0202] Organic pigments can especially be selected from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complexes, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

[0203] 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.

[0204] 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:

[0205] - Cosmenyl Yellow 10G: Yellow 3 pigment (CI 11710);

[0206] - Cosmenyl Yellow G: Yellow 1 pigment (CI 11680);

[0207] - Cosmenyl Orange GR: Orange 43 pigment (CI 71105);

[0208] - Cosmenyl Red R: Red 4 pigment (CI 12085);

[0209] - Cosmenyl Carmine FB: Red 5 pigment (CI 12490);

[0210] - Cosmenyl Violet RL: Violet 23 pigment (CI 51319);

[0211] - Cosmenyl Blue A2R: blue 15.1 pigment (CI 74160);

[0212] - Cosmenyl Green GG: Pigment Green 7 (CI 74260);

[0213] - Cosmenyl Black R: Pigment Black 7 (CI 77266).

[0214] The pigments according to the invention can also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments can in particular consist of particles which comprise an inorganic core, at least one binder for attaching the organic pigment to the core and at least one organic pigment covering at least partly the core.

[0215] The organic pigment can also be a lake. The term "lake" means a dye adsorbed on an insoluble particle, the assembly thus obtained remaining insoluble during use.

[0216] The inorganic substrate on which the dye is adsorbed is for example alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.

[0217] Among these dyes, carminic acid can be mentioned. Dyes known under the following names can also be mentioned: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI15 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).

[0218] Examples of lakes which can be mentioned are products known under the following names: D&C Red 7 (CI 15 850:1).

[0219] The pigment can also be a pigment with special effects. The term "pigment with special effects" means a pigment which generally produces a non-uniform coloured appearance (characterized by a certain chromaticity, a certain vivacity and a certain brightness level) which varies with the observation conditions (light, temperature, angle of observation, etc.). Thus, they are different from coloured pigments which provide standard uniform opaque, translucent or transparent tones.

[0220] There are several types of special effects pigments: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacre, interference pigments or glitter flakes.

[0221] Examples of pigments with special effects that may be mentioned include pearlescent pigments such as mica coated with titanium or bismuth oxychloride; colored pearlescent pigments such as mica coated with titanium and iron oxides, mica coated with iron oxides, mica coated with titanium and especially with iron blue or chromium oxides, mica coated with titanium and an organic pigment as previously defined, and also pearlescent pigments based on bismuth oxychloride. Pearlescent pigments that may be mentioned include nacre 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.

[0222] Mention may also be made of nacreous pigments 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); nacreous pigments with a bronze color 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); nacreous pigments with an orange color 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 Matte Orange (17449) (Microna); nacreous pigments with a brown color sold, in particular, by BASF under the names Nu-antique Copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); nacreous pigments with a copper-colored shade sold, in particular, by BASF under the name Copper 340A (Timica); nacreous pigments with a red-colored shade sold, in particular, by Merck under the name Sienna Fine (17386) (Colorona); nacreous pigments with a yellow-colored shade sold, in particular, by BASF under the name Yellow (4502) (Chromalite); nacreous pigments with a red color and a golden-colored shade sold, in particular, by BASF under the name Sunstone G012 (Gemtone); nacreous pigments with a pink color sold, in particular, by BASF under the name Tan Opale G005 (Gemtone); nacreous pigments with a black color and a golden-colored shade sold, in particular, by BASF under the name Nu-antique Bronze 240AB (Timica); nacreous pigments with a blue color sold, in particular, by Merck under the name Matte Blue (17433) (Microna); nacreous pigments with a white color and a silver-colored shade sold, in particular, by Merck under the name Xirona Silver; and nacreous pigments with a golden-green, pink, orange color sold, in particular, by Merck under the name Indian Summer (Xirona); and mixtures thereof.

[0223] Still as examples of nacreous pigments, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

[0224] Particles comprising a glass substrate coated with titanium oxide are in particular sold by Toyal under the name Metashine MC1080RY.

[0225] Finally, examples of nacre that can also be mentioned include polyethylene terephthalate glitter flakes, in particular those sold by Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver glitter flakes). Multilayer pigments based on synthetic substrates can also be envisaged, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.

[0226] Pigments with special effects can also be selected from reflective particles, i.e. in particular from particles whose size, structure, in particular the thickness of the layer they form, and their physical and chemical properties as well as surface state allow them to reflect incident light. If appropriate, when applied to the carrier to be made up, this reflection can have an intensity sufficient to produce high - light points visible to the naked eye on the surface of the composition or mixture, i.e. points that make them appear to sparkle and are brighter in contrast to their surroundings.

[0227] Reflective particles can be chosen so as not to significantly alter the coloring effect produced by the colorants combined with them, and more particularly so as to optimize this effect in terms of color reproduction. They can more particularly have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or hue.

[0228] These particles can have different forms and can in particular be in the form of flakes or spheres, especially in the spherical form.

[0229] Regardless of their form, reflective particles can have or can not have a multilayer structure, and in the case of a multilayer structure, can have for example at least one layer of uniform thickness, in particular a layer of reflective material.

[0230] When the reflective particles do not have a multilayer structure, they can be composed of, for example, metal oxides, in particular titanium or iron oxides obtained synthetically.

[0231] 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 mineral materials.

[0232] More particularly, it can be selected from glass, ceramics, graphite, metal oxides, alumina, silica, silicates (in particular aluminosilicates and borosilicates), and synthetic mica, and mixtures thereof, the list not being limiting.

[0233] The reflective material may include a metal layer or a layer of a metallic material.

[0234] Reflective particles are described in particular in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0235] In addition, as an example 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.

[0236] Particles having a silver-coated glass substrate in the form of flakes are sold by Toyo Corporation under the name Microglass Metashine REFSX 2025PS. Particles having a glass substrate coated with a nickel / chromium / molybdenum alloy are sold by the same company under the names Crystal Star GF 550 and GF 2525.

[0237] Particles comprising a metallic substrate such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium may also be used, said substrate being coated with at least one layer of at least one metal oxide such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxide, and mixtures thereof.

[0238] Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiO2, which are sold by Eckart under the name Visionaire.

[0239] Interference pigments not attached to a substrate may also be mentioned, 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, for example sold by Quantum Dots Corporation.

[0240] The various pigments that can be used in the compositions according to the invention make it possible to obtain a wide range of colours, as well as specific optical effects such as metallic effects or interference effects.

[0241] The size of the pigments used in the compositions 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.

[0242] The pigment may be dispersed in the composition by a dispersant.

[0243] Dispersants are used to protect the dispersed particles from agglomeration or flocculation. The dispersants can be surfactants, oligomers, polymers or mixtures of several thereof carrying one or more functional groups with 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.

[0244] 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.

[0245] The pigments used in the composition may be surface treated with an organic agent.

[0246] Thus, pigments that have been pre-surface treated and are available in the context of the present invention are pigments that have been subjected, in whole or in part, to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic reagent and are then dispersed in the composition according to the present invention, such organic reagents being, in particular, those described in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53 - 64. These organic reagents may be selected, for example, 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 their 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 polymers such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds such as silicones, in particular polydimethylsiloxane; organic fluorine compounds such as perfluoroalkyl ethers; fluorosilicone compounds.

[0247] The surface-treated pigments that can be used in the composition may also have been treated with a mixture of these compounds and / or may have undergone several surface treatments.

[0248] The surface-treated pigments that can be used 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 commercially available as such.

[0249] Preferably, the surface-treated pigments are coated with an organic layer.

[0250] The organic reagent for treating the pigment can be attached to the pigment by evaporation of the solvent, chemical reaction between the molecules of the surfactant or formation of a covalent bond between the surfactant and the pigment.

[0251] The surface treatment can thus be carried out, for example, by a chemical reaction of the surfactant with the pigment surface and formation of a covalent bond between the surfactant and the pigment or filler. This method is described in particular in patent US 4 578 266.

[0252] Organic reagents that are covalently bonded to the pigment are preferably used.

[0253] The reagent for surface treatment can be present in an amount, by weight, from 0.1% to 50%, preferably from 0.5% to 30% and even more preferably from 1% to 20% relative to the total weight of the surface-treated pigment.

[0254] Preferably, the surface treatment agent for the pigment is selected from the following treatment agents:

[0255] - PEG-silicone treatment agents, such as the AQ surface treatment agent sold by LCW;

[0256] - Polymethylsiloxane treatment agents, such as the SI surface treatment agent sold by LCW;

[0257] - Polydimethylsiloxane treatment agents, such as the Covasil 3.05 surface treatment agent sold by LCW;

[0258] - Polydimethylsiloxane / trimethylsilyl silicate treatment agents, such as the Covasil 4.05 surface treatment agent sold by LCW;

[0259] - Magnesium myristate treatment agents, such as the MM surface treatment agent sold by LCW;

[0260] - Aluminum dimyristate treatment agents, such as the MI surface treatment agent sold by Miyoshi;

[0261] - Perfluoropoly(methyl isopropyl ether) treatment agents, such as the FHC surface treatment agent sold by LCW;

[0262] - Isostearyl sebacate treatment agents, such as the HS surface treatment agent sold by Miyoshi;

[0263] - Perfluoroalkyl phosphate treatment agents, such as the PF surface treatment agent sold by Daito;

[0264] - Acrylate / polydimethylsiloxane copolymer and perfluoroalkyl phosphate treatment agents, such as the FSA surface treatment agent sold by Daito;

[0265] - Polymethylhydrosiloxane / perfluoroalkyl phosphate treatment agents, such as the FS01 surface treatment agent sold by Daito;

[0266] - Acrylate copolymer / polydimethylsiloxane treatment agents, such as the ASC surface treatment agent sold by Daito;

[0267] - Isopropyl triisostearoyl titanate treatment agents, such as the ITT surface treatment agent sold by Daito;

[0268] - Acrylate copolymer treatment agents, such as the APD surface treatment agent sold by Daito;

[0269] - Perfluoroalkyl phosphate / isopropyl triisostearoyl titanate treatment agents, such as the PF+ITT surface treatment agent sold by Daito.

[0270] According to specific embodiments of the present invention, the dispersant is present together with organic or mineral pigments in the form of submicron-sized particles.

[0271] The term "sub-micron sized" or "sub-micron" means that the pigment has a particle size that has been micronized by a micronization method and has an average particle size of less than one micron (μm), particularly between 0.1 and 0.9 μm and preferably between 0.2 and 0.6 μm.

[0272] According to one embodiment, the dispersant and the pigment are present in an amount (dispersant:pigment) according to a weight ratio between 1:4 and 4:1, particularly between 1.5:3.5 and 3.5:1 or even better between 1.75:3 and 3:1.

[0273] Thus, the dispersant can have a silicone backbone, such as dispersants of the silicone polyether and aminosilicone types. Among suitable dispersants, mention may be made of:

[0274] - aminosilicones, i.e., silicones containing one or more amine groups, such as those sold under the following names and index numbers: BYK LPX 21879 from BYK Chemie GmbH, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967, and GP-988-1 sold by Genesee Polymers,

[0275] - silicone acrylates, such as those sold by Evonik RC 902, RC 922, RC 1041 and RC 1043,

[0276] - carboxyl-carrying polydimethylsiloxane (PDMS) silicones such as X-22162 and X-22370 from Shin-Etsu Chemical Co., Ltd., epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695 from Genesee Polymers, or RC 1401, RC 1403, RC 1412 from Evonik.

[0277] According to a specific embodiment, the dispersant is of the aminosilicone type and is cationic.

[0278] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments, or organic pigments.

[0279] In a variant of the present invention, the pigment is an organic pigment, preferably an organic pigment surface-treated with an organic reagent selected from silicone compounds. In another variant of the present invention, the pigment is a mineral pigment.

[0280] Preferably, the pigment is selected from iron oxides, in particular red, brown or black iron oxides. As an example of an iron oxide, mention may be made of the iron oxide sold by Sun Chemical under the name Red Iron Oxide.

[0281] Direct dyes

[0282] The composition C used in the context of the process according to the invention may comprise one or more direct dyes.

[0283] The term "direct dye" means natural and / or synthetic dyes, other than oxidation dyes. These are dyes that spread superficially on the fiber.

[0284] They can be ionic or non-ionic, preferably cationic or non-ionic.

[0285] Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryl dyes; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, either alone or in the form of a mixture.

[0286] The direct dye is preferably a cationic direct dye. Mention may be made of the hydrazinium cation dyes of the following formulas (XIII) and (XIV) and the azo cation dyes of the formulas (XV) and (XVI):

[0287] Het + -N(Ra)-N=C(Rb-Ar,Q- (XIII),

[0288] Het + -C(Ra)=N-N(Rb)-Ar,Q (XIV),

[0289] Het + -N=N-Ar,Q- (XV),

[0290] Ar + -N=N-Ar”,Q- (XVI),

[0291] In the formulas (XIII) to (XVI):

[0292] -Het + represents a cationic heteroaryl such as imidazolium, indolium or pyridinium which preferably carries a cationic charge within the ring and which is optionally preferably substituted by at least one (C1-C8) alkyl group such as methyl;

[0293] -Ar +An aryl carrying a cationic charge outside the ring, preferably ammonium, especially tri(C1-C8)alkylammonium such as trimethylammonium, such as phenyl or naphthyl;

[0294] -Ar represents an aryl, especially phenyl, which is optionally preferably substituted by one or more electron-donating groups, such as i) an optionally substituted (C1-C8)alkyl, ii) an optionally substituted (C1-C8)alkoxy, iii) a (di)(C1-C8)(alkyl)amino optionally substituted by a hydroxyl group on the alkyl, iv) an aryl(C1-C8)alkylamino, v) an optionally substituted N-(C1-C8)alkyl-N-aryl(C1-C8)alkylamino, or alternatively, Ar represents a julolidine group;

[0295] -Ar” represents an optionally substituted (hetero)aryl, such as phenyl or pyrazolyl, which is optionally preferably substituted by one or more (C1-C8)alkyls, hydroxyl groups, (di)(C1-C8)(alkyl)aminos, (C1-C8)alkoxys or phenyls;

[0296] -Ra and Rb may be the same or different and represent a hydrogen atom or an optionally preferably hydroxyl-substituted (C1-C8)alkyl;

[0297] Alternatively, the substituent Ra together with the substituent of Het+ and / or the substituent Rb together with the substituent of Ar form a (hetero)cycloalkyl with the atoms carrying them; in particular, Ra and Rb represent a hydrogen atom or an optionally hydroxyl-substituted (C1-C4)alkyl;

[0298] -Q- represents an organic or inorganic anion counterion, such as a halide ion or an alkyl sulfate.

[0299] In particular, azo and hydrazo direct dyes carrying a cationic charge inside the ring as defined previously, more particularly cationic direct dyes carrying a cationic charge inside the ring described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954 can be mentioned, preferably the following direct dyes:

[0300]

[0301] In formulas (XVII) and (XVIII):

[0302] -R 1 represents a (C1-C4)alkyl such as methyl;

[0303] -R 2 and R 3 may be the same or different and represent a hydrogen atom or a (C1-C4)alkyl, such as methyl; and

[0304] -R 4 represents a hydrogen atom or an electron-donating group, such as an optionally substituted (C1-C8) alkyl group, an optionally substituted (C1-C8) alkoxy group, or a bis(C1-C8)(alkyl)amino group optionally substituted by a hydroxyl group on the alkyl group; in particular, R 4 is a hydrogen atom;

[0305] -Z represents a CH group or a nitrogen atom, preferably CH;

[0306] -Q- is an anionic counterion as previously defined, especially a halide ion such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0307] In particular, the dyes of formulas (XV) and (XVI) are selected from Basic Red 51, Basic Yellow 87, and Basic Orange 31 or derivatives thereof, where Q’ is an anionic counterion as previously defined, especially a halide ion such as chloride, or an alkyl sulfate such as methyl sulfate or mesyl.

[0308] The direct dyes can be selected from anionic direct dyes. The anionic direct dyes of the present invention are dyes that are generally referred to as "acid" direct dyes due to their affinity for basic substances. The term "anionic direct dye" means any direct dye that includes at least one CO2R or SO3R substituent in its structure, where R indicates a hydrogen atom or a cation derived from a metal or an amine, or an ammonium ion. The anionic dyes can be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigo dyes, and natural acid dyes.

[0309] As acid dyes that can be used in the present invention, mention may be made of the dyes of the following formulas (XIX), (XIX’), (XX), (XX’), (XXI), (XXI’), (XXII), (XXII’), (XXIII), (XXIV), (XXV), and (XXVI):

[0310] a) Diaryl anionic azo dyes of formula (XIX) or (XIX’):

[0311]

[0312] In formulas (XIX) and (XIX’):

[0313] -R7, R8, R9, R 10 , R’7, R’8, R’9 and R’ 10 may be the same or different and represent a hydrogen atom or a group selected from:

[0314] -alkyl;

[0315] -Alkoxy, alkylthio;

[0316] -Hydroxy, mercapto;

[0317] -Nitro, nitroso;

[0318] -R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”, where R° represents a hydrogen atom or an alkyl or aryl group; X, X’ and X” may be the same or different and represent an oxygen or sulfur atom, or NR, where R represents a hydrogen atom or an alkyl group;

[0319] -(O)2S(O - )-, M + where M + represents a hydrogen atom or a cationic counterion;

[0320] -(O)CO - -, M + where M + is as previously defined;

[0321] -R”-S(O)2-, where R” represents a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferably phenylamino or phenyl;

[0322] -R”’-S(O)2-X’-, where R”’ represents an optionally substituted alkyl or aryl group and X’ is as previously defined;

[0323] -(Di)(alkyl)amino;

[0324] -Aryl(alkyl)amino, optionally substituted by one or more groups selected from: i) nitro; ii) nitroso; iii) (O)2S(O - )-, M + and iv) alkoxy, where M + is as previously defined;

[0325] -Optionally substituted heteroaryl; preferably benzothiazolyl;

[0326] -Cycloalkyl, especially cyclohexyl;

[0327] -Ar-N=N-, where Ar represents an optionally substituted aryl group; preferably phenyl optionally substituted by one or more alkyl groups, (O)2S(O - )-, M + or phenylamino;

[0328] -Alternatively, two adjacent groups R7 and R8 or R8 and R9 or R9 and R 10together 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 form a fused benzo group B'; wherein A' and B' are optionally substituted by one or more groups selected from: i) nitro; ii) nitroso; iii) (O)2S(O - )-, M + ; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; wherein M + 、R°, X, X', X'' and Ar are as previously defined;

[0329] -W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent group i) -NR-, where R is as previously defined, or ii) methylene-C(Ra)(Rb)-, where Ra and Rb may be the same or different and represent a hydrogen atom or an aryl group, or alternatively, Ra and Rb together with the carbon atom carrying them form a spiroalkyl group; preferably, W represents a sulfur atom or Ra and Rb together form a cyclohexyl group;

[0330] It should be understood that formula (XIX) and (XIX') contain at least one sulfonate group (O)2S(O - )-, M + or a carboxylate group (O)CO - -, M + ; preferably sodium sulfonate.

[0331] As examples of the 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 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or Sunset Yellow;

[0332] And, as examples of the dyes of formula (XIX'), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38;

[0333] b) Pyrazolone anion azo dyes of formula (XX) and (XX’):

[0334]

[0335] In formula (XX) and (XX’):

[0336] -R 11 、R 12 and R 13 may be the same or different and represent a hydrogen or halogen atom, an alkyl group or -(O)2S(O - ),M + , where M + is as previously defined;

[0337] -R 14 represents a hydrogen atom, an alkyl group or the group -C(O)O - ,M + , where M + is as previously defined;

[0338] -R 15 represents a hydrogen atom;

[0339] -R 16 represents an oxo group, in which case R' 16 is absent, or alternatively, R 15 and R 16 together form a double bond;

[0340] -R 17 and R 18 may be the same or different and represent a hydrogen atom or a group selected from:

[0341] -(O)2S(O - ),M + , where M + is as previously defined;

[0342] -Ar-O-S(O)2-, where Ar represents an optionally substituted aryl group; preferably a phenyl group optionally substituted by one or more alkyl groups;

[0343] -R 19 and R 20 together form a double bond, or an optionally substituted benzoyl group D’;

[0344] -R’ 16 、R’ 19 and R’ 20 may be the same or different and represent a hydrogen atom, an alkyl group or a hydroxyl group;

[0345] -R 21represents a hydrogen atom, an alkyl group or an alkoxy group;

[0346] - Ra and Rb may be the same or different, as previously defined; preferably, Ra represents a hydrogen atom and Rb represents an aryl group;

[0347] - Y represents a hydroxyl group or an oxo group;

[0348] - represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;

[0349] It should be understood that formula (XX) and (XX’) contain at least one sulfonate group (O)2S(O - )-,M + or a carboxylate group -C(O)O - ,M + ; preferably sodium sulfonate.

[0350] As examples of the 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 the dyes of formula (XX’), mention may be made of: Acid Yellow 17;

[0351] c) Anthraquinone dyes of formula (XXI) and (XXI’):

[0352]

[0353] In formula (XXI) and (XXI’):

[0354] - R 22 、R 23 、R 24 、R 25 、R 26 and R 27 may be the same or different and represent a hydrogen or halogen atom, or a group selected from:

[0355] - alkyl;

[0356] - hydroxyl, mercapto;

[0357] - alkoxy, alkylthio;

[0358] - optionally substituted aryloxy or arylthio, which is preferably substituted by one or more groups selected from alkyl and (O)2S(O - )-,M + where M + is as previously defined;

[0359] - aryl(alkyl)amino, which is optionally substituted by one or more groups selected from alkyl and (O)2S(O - )-,M+ is substituted by a group, where M + is as defined previously;

[0360] -(di)(alkyl)amino;

[0361] -(di)(hydroxyalkyl)amino;

[0362] -(O)2S(O - ),M + where M + is as defined previously;

[0363] -Z’ represents a hydrogen atom or a group NR 28 R 29 where R 28 and R 29 can be the same or different and represent a hydrogen atom or a group selected from the following:

[0364] -alkyl;

[0365] -polyhydroxyalkyl, such as hydroxyethyl;

[0366] -aryl optionally substituted by one or more groups especially the following: i) alkyl, such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O - ),M + where M + is as defined previously; iii) R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”, where R°, X, X’ and X” are as defined previously, preferably R° represents alkyl;

[0367] -cycloalkyl, especially cyclohexyl;

[0368] -Z represents a group selected from hydroxy and NR’ 28 R’ 29 where R’ 28 and R’ 29 can be the same or different and represent an atom or a group the same as R 28 and R 29 as defined previously;

[0369] It should be understood that formula (XXI) and (XXI’) contain at least one sulfonate group (O)2S(O - ),M + or a carboxylate group C(O)O - ,M + ; preferably sodium sulfonate.

[0370] As examples of the dyes of formula (XXI), mention may be made of: 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 the dyes of formula (XXI’), mention may be made of: Acid Black 48;

[0371] d) Nitro dyes of formula (XXII) and (XXII’):

[0372]

[0373]

[0374] In formulae (XXII) and (XXII'):

[0375] -R 30 、R 31 and R 32 may be the same or different and represent a hydrogen atom or a halogen atom or a group selected from:

[0376] -alkyl;

[0377] -alkoxy optionally substituted by one or more hydroxyl groups, alkylthio optionally substituted by one or more hydroxyl groups;

[0378] -hydroxyl, mercapto;

[0379] -nitro, nitroso;

[0380] -polyhaloalkyl;

[0381] -R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”, where R°, X, X’ and X” are as defined previously;

[0382] -(O)2S(O - )-,M + where M + is as defined previously;

[0383] -(O)CO - -,M + where M + is as defined previously;

[0384] -(di)(alkyl)amino;

[0385] -(di)(hydroxyalkyl)amino;

[0386] -heteroalkyl, such as piperidino, piperazino or morpholino; In particular, R30 , R 31 and R 32 represent a hydrogen atom;

[0387] -Rc and Rd may be the same or different and represent a hydrogen atom or an alkyl group;

[0388] -W is as defined previously; W particularly represents an -NH- group;

[0389] -ALK represents a straight-chain or branched divalent C1-C6 alkylene group; particularly, ALK represents a -CH2-CH2- group;

[0390] -n is 1 or 2;

[0391] -p represents an integer between 1 and 5 inclusive;

[0392] -q represents an integer between 1 and 4 inclusive;

[0393] -u is 0 or 1;

[0394] -When n is 1, J represents a nitro or nitroso group; particularly, nitro;

[0395] -When n is 2, J represents an oxygen or sulfur atom, or a divalent group -S(O)m-, where m represents the integer 1 or 2; preferably, J represents a -SO2- group;

[0396] -M’ represents a hydrogen atom or a cationic counterion;

[0397] - may be present or absent and represents an optionally substituted benzogroup by one or more groups R as defined previously 30 substituted;

[0398] It should be understood that formula (XXII) and (XXII’) contain at least one sulfonate group (O)2S(O - ), M + or a carboxylate group C(O)O - , M + ; preferably sodium sulfonate.

[0399] As examples of the dyes of formula (XXII), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of the dyes of formula (XXII’), mention may be made of: Acid Yellow 1, 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidyl-5-nitrobenzenesulfonic acid, 2-(4’-N,N-(2”-hydroxyethyl)amino-2’-nitro)aniline ethane sulfonic acid, the sodium salt of 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; External D&C Yellow 7 (EXT D&C Yellow 7);

[0400] e) Triarylmethane dyes of formula (XXIII):

[0401]

[0402] In formula (XXIII):

[0403] - R 33 、R 34 、R 35 and R 36 may be the same or different and represent a hydrogen atom or a group selected from: alkyl, optionally substituted aryl and optionally substituted aralkyl; in particular alkyl and optionally substituted by the group (O) m S(O - )-, M + substituted benzyl, where M + and m are as defined previously;

[0404] - R 37 、R 38 、R 39 、R 40 、R 41 、R 42 、R 43 and R 44 may be the same or different and represent a hydrogen atom or a group selected from:

[0405] - alkyl;

[0406] - alkoxy, alkylthio;

[0407] - (di)(alkyl)amino;

[0408] - hydroxy, mercapto;

[0409] - nitro, nitroso;

[0410] - R°- C(X)- X’-, R°- X’- C(X)-, R°- X’- C(X)- X”, where R° represents a hydrogen atom or alkyl or aryl; X, X’ and X” may be the same or different and represent an oxygen or sulfur atom, or NR, where R represents a hydrogen atom or alkyl;

[0411] - (O)2S(O - )-, M + , where M + represents a hydrogen atom or a cationic counterion;

[0412] - (O)CO - -, M + , where M + is as defined previously;

[0413] - Or alternatively, two adjacent groups R41 with R 42 or R 42 with R 43 or R 43 with R 44 together form a fused benzo group: I'; where I' is optionally substituted with one or more groups selected from: i) nitro; ii) nitroso; iii) (O)2S(O - )-, M + ; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)- and ix) R°-X'-C(X)-X''-; where M + , R°, X, X' and X'' are as previously defined;

[0414] In particular, R 37 to R 40 represent hydrogen atoms, and R 41 to R 44 can be the same or different and represent hydroxy or (O)2S(O - )-, M + ; and when R 43 and R 44 together form a benzo group, it is preferably substituted with an (O)2S(O - )- group;

[0415] It should be understood that at least one of the rings G, H, I or I' contains at least one sulfonic acid group (O)2S(O - )- or a carboxylic acid group -C(O)O - ; preferably sulfonate.

[0416] As examples of the 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.

[0417] f) Xanthene-based dyes of formula (XXIV):

[0418]

[0419] In formula (XXIV):

[0420] -R 45 , R 46 , R 47 and R 48 can be the same or different and represent hydrogen or halogen atoms;

[0421] -R 49 , R 50 , R 51and R 52 may be the same or different and represent a hydrogen or halogen atom or a group selected from the following:

[0422] -alkyl;

[0423] -alkoxy, alkylthio;

[0424] -hydroxy, mercapto;

[0425] -nitro, nitroso;

[0426] -(O)2S(O - )-, M + , where M + represents a hydrogen atom or a cationic counterion;

[0427] -(O)CO - -, M + , where M + is as previously defined;

[0428] In particular, R 49 , R 50 , R 51 and R 52 represent a hydrogen or halogen atom;

[0429] -G represents an oxygen or sulfur atom or the group NRe, where Re is as previously defined; in particular, G represents an oxygen atom;

[0430] -L represents an alkoxide O - , M + ; a thiolate S - , M + or the group NRf, where Rf represents a hydrogen atom or an alkyl group, and M + is as defined above; M + is particularly sodium or potassium;

[0431] -L’ represents an oxygen or sulfur atom or an ammonium group: N + RfRg, where Rf and Rg may be the same or different and represent a hydrogen atom or an optionally substituted alkyl or aryl group; L’ particularly represents an oxygen atom or a phenylamino group optionally substituted by one or more alkyl or (O) m S(O - )-, M + groups, where m and M + are as previously defined;

[0432] -Q and Q’ may be the same or different and represent an oxygen or sulfur atom; in particular, Q and Q’ represent an oxygen atom;

[0433] -M + is as previously defined.

[0434] As examples of the 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;

[0435] g) indole-based dyes of formula (XXV):

[0436]

[0437] In formula (XXV):

[0438] -R 53 、R 54 、R 55 、R 56 、R 57 、R 58 、R 59 and R 60 may be the same or different and represent a hydrogen atom or a group selected from:

[0439] -alkyl;

[0440] -alkoxy, alkylthio;

[0441] -hydroxy, mercapto;

[0442] -nitro, nitroso;

[0443] -R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”, where R° represents a hydrogen atom or an alkyl or aryl group; X, X’ and X” may be the same or different and represent an oxygen or sulfur atom, or NR, where R represents a hydrogen atom or an alkyl group;

[0444] -(O)2S(O - )-,M + where M + represents a hydrogen atom or a cationic counterion;

[0445] -(O)CO - -,M + where M + is as previously defined;

[0446] -G represents an oxygen or sulfur atom or the group NRe, where Re is as previously defined; in particular, G represents an oxygen atom;

[0447] -Ri and Rh may be the same or different and represent a hydrogen atom or an alkyl group;

[0448] It is to be understood that formula (XXIII) contains at least one sulfonate group (O)2S(O - )-,M +or a carboxylate group -C(O)O - , M + ; preferably sodium sulfonate.

[0449] As examples of the dyes of formula (XXV), mention may be made of: Acid Blue 74;

[0450] h) quinoline-based dyes of formula (XXVI):

[0451]

[0452] In formula (XXVI):

[0453] -R 61 represents a hydrogen or halogen atom or an alkyl group;

[0454] -R 62 , R 63 and R 64 may be the same or different and represent a hydrogen atom or the group (O)2S(O - ), -M + , where M + represents a hydrogen atom or a cationic counterion;

[0455] Or alternatively, R 61 together with R 62 , or R 61 together with R 64 forms a benz group, which benz group is optionally substituted by one or more groups (O)2S(O - ), -M + , where M + represents a hydrogen atom or a cationic counterion;

[0456] It should be understood that formula (XXVI) contains at least one sulfonate group (O)2S(O - ), -M + , preferably sodium sulfonate.

[0457] As examples of the dyes of formula (XXVI), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0458] Among the natural direct dyes that can be used according to the present invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, gallic acid, protocatechaldehyde, indigo, indigo carmine, curcumin, penicillic acid, apigenidin and orcein. Extracts or decoctions containing these natural dyes can also be used and in particular poultices or extracts based on henna.

[0459] Preferably, the direct dye is selected from anionic direct dyes.

[0460] The colorant may be present in a total amount ranging from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, relative to the total weight of composition C; preferably, the colorant is selected from pigments.

[0461] The pigment may be present in a total amount ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight, and still more preferably from 0.5% to 10% by weight, relative to the total weight of composition C.

[0462] The direct dye may be present in a total amount ranging from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight, relative to the total weight of composition C.

[0463] Compound containing at least one carboxyl functional group

[0464] Composition C used in the context of the method according to the invention may further comprise at least one compound containing at least one carboxyl functional group.

[0465] Preferably, composition C used in the context of the method according to the invention comprises at least one compound containing at least one carboxyl functional group.

[0466] Preferably, the compound containing at least one carboxyl functional group is selected from silicone compounds containing at least one carboxyl, polyurethanes, acrylic polymers, and mixtures thereof.

[0467] Polyurethane and acrylic polymer

[0468] According to a preferred embodiment, composition C comprises at least one compound containing at least one carboxyl functional group, which is selected from polyurethanes, acrylic polymers, and mixtures thereof.

[0469] Preferably, the compound containing at least one carboxyl functional group is in the form of an aqueous dispersion of polymer particles selected from polyurethanes, acrylic polymers, and mixtures thereof.

[0470] Preferably, composition C comprises at least one compound containing at least one carboxyl functional group, which is in the form of an aqueous dispersion of particles of polyurethanes, acrylic polymers, and mixtures thereof.

[0471] The dispersion may be a simple dispersion in the aqueous medium of the cosmetic composition. As a particular case of the dispersion, mention may be made of latex.

[0472] The aqueous dispersion of polymer particles may be selected from the aqueous dispersion of polyurethane particles.

[0473] More particularly, the polyurethanes present in the aqueous dispersions used in the present invention are produced by the reaction of:

[0474] - a prepolymer of the following formula (A):

[0475]

[0476] wherein:

[0477] - R1 represents a divalent group of a dihydroxylated compound;

[0478] - R2 represents a group of an aliphatic or cycloaliphatic polyisocyanate;

[0479] - R3 represents a group of a low molecular weight diol, optionally substituted by one or more ionic groups;

[0480] - n represents an integer ranging from 1 to 5, and

[0481] - m is greater than 1;

[0482] - at least one chain extender according to the following formula (B):

[0483] H2N-R4-NH2 (B),

[0484] where R4 represents an alkylene or alkyleneoxy group not substituted by one or more ionic or potentially ionic groups; and

[0485] - at least one chain extender according to the following formula (C):

[0486] H2N-R5-NH2 (C),

[0487] where R5 represents an alkylene group substituted by one or more ionic or potentially ionic groups.

[0488] Among the dihydroxylated compounds that can be used according to the present invention, mention may be made in particular of compounds containing two hydroxyl groups and having a number average molecular weight of from about 700 to about 16,000, and preferably from about 750 to about 5000. By way of example 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 polybutadienes, polyhydroxylated polysulfides, and mixtures thereof. Preferably, the hydroxylated compounds are selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0489] The polyisocyanates that can be used according to the present invention are in particular selected from organic diisocyanates having a molecular weight of from about 112 to 1000, and preferably from about 140 to 400.

[0490] Preferably, the polyisocyanate is selected from diisocyanates and more particularly from those represented by the general formula R2(NCO)2, where R2 represents a divalent aliphatic hydrocarbon-based group having 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon-based group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon-based group having 7 to 15 carbon atoms or a divalent aromatic hydrocarbon-based group having 6 to 15 carbon atoms.

[0491] Preferably, R2 represents an organic diisocyanate. As examples of organic diisocyanates, the following may be mentioned in particular: tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanato-3-methylcyclohexyl)methane, isomers of toluene diisocyanate (TDI) such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, diphenylmethane 4,4'-diisocyanate and mixtures with its isomers diphenylmethane 2,4-diisocyanate and optionally diphenylmethane 2,2'-diisocyanate, naphthalene 1,5-diisocyanate, and mixtures thereof.

[0492] Preferably, the diisocyanate is an aliphatic and cycloaliphatic diisocyanate, and more preferably is selected from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate, and mixtures thereof.

[0493] According to the invention, the term "low molecular weight diol" means a diol having a molecular weight of from about 62 to 700, and preferably from 62 to 200. These diols may contain aliphatic, cycloaliphatic or aromatic groups. Preferably, they contain only aliphatic groups.

[0494] Preferably, R3 represents a low molecular weight diol having more than 20 carbon atoms, and is more preferably selected from ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, butylethylpropanediol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), and mixtures thereof.

[0495] The low molecular weight diol 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 dimethylolbutyric acid, dimethylolpropionic acid, carboxyl-containing polycaprolactone diols, and mixtures thereof.

[0496] If a low molecular weight diol containing ionic or potentially ionic groups is used, it is preferably used in an amount such that less than 0.30 meq of COOH / g of polyurethane is present in the polyurethane dispersion.

[0497] The prepolymer is chain-extended by two families of chain extenders. The first type of chain extender corresponds to compounds of formula (B).

[0498] The chain extenders of formula (B) are preferably selected from alkylenediamines such as hydrazine, ethylenediamine, propylenediamine, 1,4-butanediamine, piperazine; alkylenediamine oxides 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 A from DuPont), hexamethylenediamine, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), etheramines of the DPA series available from Tomah 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 cyclohexane-1,4-dimethanol; and mixtures thereof.

[0499] The second type of chain extender corresponds to compounds of formula (C). Such compounds preferably have ionic or potentially ionic groups and two groups capable of reacting with isocyanate groups. Such compounds may optionally contain two groups capable of reacting with isocyanate groups and one group that is an ionic group or capable of forming an ionic group.

[0500] The ionic or potentially ionic groups may preferably be selected from tertiary 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 tertiary ammonium or quaternary ammonium group salts may be carried out before or during mixing with water.

[0501] The chain extender of formula (C) is preferably selected from diamino sulfonates, 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.

[0502] The polyurethanes that can be used according to the present invention may optionally further comprise compounds (chain terminators) located at the chain ends and terminating the chains. Such compounds are described in particular in patents US 7 445 770 and / or US 7 452 770.

[0503] 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 less than 1000. Even more preferably, the aqueous polyurethane dispersion has a glass transition temperature of less than 0 °C.

[0504] Also preferably, based on the weight of the dispersion, the aqueous polyurethane dispersion has a polyurethane (or active material, or solid) content by weight of from 20% to 60%, more preferably from 25% to 55% by weight and even better from 30% to 50% by weight. This is intended to mean 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 from 30% to 50% by weight relative to the total weight of the dispersion.

[0505] Also preferably, the aqueous dispersion of polyurethane particles has a glass transition temperature (Tg) of less than or equal to -25 °C, preferably less than -35 °C and more preferably less than -40 °C.

[0506] The polyurethane particles can have an average diameter ranging up to about 1000 nm, for example from about 50 nm to about 800 nm, even better from about 100 nm to about 500 nm. These particle sizes can be measured using a laser particle size analyzer (such as Brookhaven BI90).

[0507] As non-limiting examples of aqueous polyurethane dispersions, mention may be made of those sold by Bayer under the name such as 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).

[0508] The following aqueous polyurethane dispersions may also be mentioned: isophthalic acid / adipic acid copolymer / hexanediol / neopentyl glycol / dimethylolpropionic acid / isophorone diisocyanate (INCI name: polyurethane-1, such as PUR, BASF), polyurethane of polycarbonate, polyurethane of aliphatic polyester and aliphatic polyurethane (such as or DSM series, such as R989 and R-2202).

[0509] According to a preferred embodiment, the aqueous dispersion of polyurethane particles may be selected from the aqueous dispersion of particles of a compound having the INCI name polyurethane-35 or a compound having the INCI name polyurethane-34.

[0510] Preferably, the compound containing at least one carboxyl functional group is in the form of an aqueous dispersion of particles of an acrylic polymer, and more preferably in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0511] For the purposes of the present invention, the term "polymer" means a compound corresponding to the repetition of one or more units (these units being derived from compounds called monomers). The unit or units are repeated at least twice and preferably at least three times.

[0512] The term "film-forming polymer" means a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous film, and preferably an adhesive film, on a support, in particular on keratin hair fibers.

[0513] For the purposes of the present invention, the term "acrylic polymer" means a polymer synthesized from at least one monomer selected from (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylamide.

[0514] The unit of the (meth)acrylic monomer derived from the polymer may optionally be in the form of a salt, in particular an alkali metal salt, an alkaline earth metal salt or an ammonium salt, or an organic base salt.

[0515] (Meth)acrylic acid ester (also called (meth)acrylate) is preferably selected from (meth)acrylic acid alkyl esters, especially (meth)acrylic acid C1 to C 30 alkyl esters, preferably (meth)acrylic acid C1 to C 20 alkyl esters and even better (meth)acrylic acid C1 to C 10 alkyl esters; (meth)acrylic acid aryl esters, especially (meth)acrylic acid C6 to C 10Aryl esters; and hydroxyalkyl (meth)acrylates, especially C2-C6 hydroxyalkyl (meth)acrylates.

[0516] 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.

[0517] Among the hydroxyalkyl (meth)acrylates, mention may be made of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0518] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0519] Particularly preferred (meth)acrylates are alkyl, preferably C1-C 30 、more preferably C1-C 20 、even better C1-C 10 、and even more particularly C1-C4 alkyl (meth)acrylates.

[0520] According to the invention, the alkyl of the ester may be fluorinated or even perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl are replaced by fluorine atoms.

[0521] As (meth)acrylamides, examples that may be mentioned include (meth)acrylamide and also N-alkyl (meth)acrylamides, especially N-(C2-C 12 alkyl)(meth)acrylamides. Among the N-alkyl (meth)acrylamides that may be mentioned are N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide and N-undecylacrylamide.

[0522] The acrylic polymers according to the invention may be homopolymers or copolymers, advantageously copolymers, even better copolymers of (meth)acrylic acid and (meth)acrylates.

[0523] Preferably, the acrylic polymers according to the invention comprise one or more units derived from the following monomers:

[0524] a) (meth)acrylic acid; and

[0525] b) C1-C 30 、more preferably C1-C 20 、even better C1-C 10 、and even more particularly C1-C4 alkyl (meth)acrylates.

[0526] Preferably, the aqueous dispersion of acrylic polymer particles does not contain any surfactant.

[0527] The term "surfactant" refers to any reagent capable of changing the surface tension between two surfaces.

[0528] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and (meth)acrylic acid methyl ester or (meth)acrylic acid ethyl ester, in particular copolymers of methacrylic acid and acrylic acid ethyl ester, such as the compound sold by BASF under the trade name Luvimer MAE, or the compound polyacrylate-2 crosslinked polymer sold by Lubrizol under the trade name Fixate Superhold Polymer, or the compound acrylate copolymer sold by Daito Kasei Kogyo under the trade name Daitosol 3000VP3, or the compound acrylate polymer sold by Daito Kasei Kogyo under the trade name Daitosol 3000SLPN-PE1.

[0529] The acrylic polymer may optionally contain one or more additional monomers other than (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylamide monomers.

[0530] As additional monomers, mention will be made, for example, of styrene monomers, in particular styrene and α-methylstyrene, and preferably styrene.

[0531] In particular, the acrylic polymer may be a styrene / (meth)acrylate copolymer, and in particular is selected from the group consisting of at least one styrene monomer and at least one (meth)acrylic acid C1 to C 20 alkyl ester, preferably (meth)acrylic acid C1 to C 10 a polymer of a copolymer produced by polymerization of alkyl ester monomers.

[0532] (meth)acrylic acid C1 to C 10 alkyl ester monomers may be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate.

[0533] As acrylic polymers, mention may be made of styrene / (meth)acrylate copolymers sold by BASF under the name Joncryl 77, by Akzo Nobel under the name Yodosol GH41F and by Interpolymer under the name Syntran 5760CG.

[0534] Preferably, composition C comprises an aqueous dispersion of at least one acrylic polymer particle.

[0535] More preferably, composition C comprises an aqueous dispersion of at least one acrylic polymer particle, which comprises one or more units derived from the following monomers:

[0536] a) (meth)acrylic acid; and

[0537] b) C1 to C 30 and more preferably C1 to C 20 even better C1 to C 10 and even more particularly C1 to C4 alkyl (meth)acrylates.

[0538] Preferably, based on the weight of the dispersion, the aqueous dispersion of acrylic polymer particles has an acrylic polymer (or active material, or solid) content of from 20% to 60% by weight, more preferably from 22% to 55% by weight and even better from 25% to 50% by weight.

[0539] Silicone acrylate copolymer

[0540] According to a specific embodiment, the silicone compound containing at least one carboxyl group is selected from silicone acrylic copolymers.

[0541] Thus, according to a specific embodiment, the compound containing at least one carboxyl functional group is selected from silicone acrylic copolymers.

[0542] Preferably, the silicone acrylic copolymer comprises:

[0543] - at least one acrylic acid or methacrylic acid or crotonic acid unit; and

[0544] - at least one polydimethylsiloxane (PDMS) unit.

[0545] For the purposes of the present invention, according to what is commonly accepted, the term "polydimethylsiloxane" (also abbreviated as PDMS) denotes any organosilicon polymer or oligomer having a linear structure with variable molecular weight, which is obtained by polymerizing and / or polycondensing appropriately functionalized silanes and is essentially composed of repeating main units in which silicon atoms are linked together via oxygen atoms (siloxane bond Si-O-Si-), containing methyl groups directly linked to said silicon atoms via carbon atoms.

[0546] The PDMS chains that can be used to obtain the copolymer used according to the present invention contain at least one polymerizable group, which is preferably located at at least one end of the chain. That is, the PDMS can, for example, contain polymerizable groups at each of the two ends of the chain or contain a polymerizable group at one end of the chain and a trimethylsilyl end group at the other end of the chain.

[0547] The term "polymerizable group" means a group capable of polymerizing with other polymerizable groups or monomers. Preferably, the polydimethylsiloxane unit contains at least one polymerizable group.

[0548] Preferably, the polymerizable group contains at least one vinyl group.

[0549] Preferably, the polydimethylsiloxane (PDMS) unit contains at least one polymerizable group containing at least one vinyl group, preferably at least two polymerizable groups containing at least one vinyl group, which are preferably located at at least one chain end.

[0550] As previously indicated, the silicone acrylic copolymer preferably contains at least one acrylic acid or methacrylic acid or crotonic acid unit, that is, at least one unit containing a carboxyl group.

[0551] The term "carboxyl group" means COOH or COO - functional group, COO - The counterion of the group is likely to be selected from alkali metals, alkaline earth metals, and quaternary ammonium.

[0552] Preferably, the silicone acrylic copolymer contains:

[0553] - at least one acrylic acid or methacrylic acid or crotonic acid unit, and at least one acrylate or methacrylate or vinyl ester unit; and

[0554] - at least one polydimethylsiloxane (PDMS) unit.

[0555] More preferably, the composition contains one or more silicone acrylic copolymers, which contain:

[0556] - at least one crotonic acid unit and at least one unit selected from the following: crotonic acid alkyl ester units, where the alkyl is a straight-chain or branched-chain saturated group containing from 1 to 20 carbon atoms; vinyl acetate units; vinyl alkyl ester units, where the alkyl is a straight-chain or branched-chain saturated group containing from 2 to 20 carbon atoms; and mixtures thereof; and

[0557] - at least one polydimethylsiloxane (PDMS) unit.

[0558] The term "crotonic acid unit" means a unit derived from a crotonic acid monomer or its salt.

[0559] The term "alkyl crotonate unit" means a unit derived from an alkyl crotonate monomer, which contains a saturated straight-chain or branched alkyl group having from 1 to 20 carbon atoms.

[0560] The term "vinyl alkyl ester unit" means a unit derived from a vinyl ester monomer, which contains a saturated straight-chain or branched alkyl group having from 2 to 20 carbon atoms.

[0561] The term "vinyl acetate unit" means a unit derived from a vinyl acetate monomer.

[0562] According to a preferred embodiment, the silicone acrylate copolymer comprises:

[0563] - 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 saturated straight-chain or branched group having from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms), and

[0564] - at least one polydimethylsiloxane (PDMS) unit, which preferably contains at least one polymerizable group containing at least one vinyl group.

[0565] According to a particularly preferred embodiment, the silicone acrylate copolymer comprises:

[0566] - 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 having from 6 to 16 carbon atoms), and

[0567] - at least one polydimethylsiloxane (PDMS) unit, which contains at least one polymerizable group containing at least one vinyl group.

[0568] More preferably, the composition comprises one or more silicone acrylate copolymers, which comprise:

[0569] - 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 saturated straight-chain or branched group having from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms); and

[0570] - at least one polydimethylsiloxane (PDMS) unit, which contains at least one polymerizable group containing at least one vinyl group.

[0571] Even more preferably, the composition comprises one or more silicone acrylate copolymers, which comprise:

[0572] - At least one crotonic acid unit, at least one vinyl acetate unit, and at least one vinyl alkyl ester unit (wherein the alkyl is a saturated straight-chain or branched-chain group containing from 6 to 16 carbon atoms); and

[0573] - At least one polydimethylsiloxane (PDMS) unit, which contains at least one polymerizable group containing at least one vinyl group.

[0574] Among the silicone acrylate copolymers that can be used in the context of the present invention, mention may be made of the compound sold by Wacker Chemie AG under the trade name P1101, having the INCI name Crotonic Acid / Vinyl C8 - 12 Isoalkyl Ester / VA / Bis-Vinyl Polydimethylsiloxane Crosspolymer.

[0575] The total amount of the compound containing at least one carboxyl functional group preferably ranges from 0.1% to 30% by weight, more preferably from 0.5% to 20% by weight, still better from 1% to 15% by weight, and even more preferably from 2% to 10% by weight relative to the total weight of Composition C.

[0576] The total amount of the aqueous dispersion of particles of a polymer selected from polyurethanes, acrylic polymers, and mixtures thereof preferably ranges from 0.1% to 40% by weight, more preferably from 0.5% to 30% by weight, still better from 1% to 25% by weight, and even more preferably from 2% to 20% by weight relative to the total weight of Composition C.

[0577] According to a specific embodiment, the total amount of the aqueous dispersion of acrylic polymer particles preferably ranges from 0.1% to 40% by weight, more preferably from 0.5% to 30% by weight, still better from 1% to 25% by weight, and even more preferably from 2% to 20% by weight relative to the total weight of Composition C.

[0578] Advantageously, the total amount of the silicone acrylate copolymer ranges from 0.1% to 30% by weight, more preferably from 0.5% to 20% by weight, still better from 1% to 15% by weight, and even more preferably from 2% to 10% by weight relative to the total weight of Composition C.

[0579] Non-carboxylic acid anionic thickener

[0580] Composition C used in the context of the method according to the present invention may further contain at least one non-carboxylic acid anionic thickener.

[0581] For the purposes of the present invention, the term "non-carboxylic acid reagent" means a reagent that does not contain any carboxylic acid functional group (-COOH) or carboxylate functional group (-COO- ) reagent.

[0582] For the purposes of the present invention, the term "thickener" means a compound which, at room temperature (25 °C), at atmospheric pressure and at a shear rate of 1 s -1 increases the viscosity of a composition into which the compound is introduced to a concentration of 0.05% by weight relative to the total weight of the composition by at least 20 cps, preferably at least 50 cps (the viscosity can be measured using a cone / plate viscometer, a Haake R600 rheometer, etc.).

[0583] Preferably, the non-carboxylic acid anionic thickener is selected from non-carboxylic acid anionic polymers, and more preferably from anionic polymers carrying sulfonic groups.

[0584] For the purposes of the present invention, the term "anionic polymer" means a polymer containing one or more anionic or anionizable groups and not containing any cationic or cationizable groups.

[0585] Advantageously, the non-carboxylic acid anionic thickener is selected from anionic polymers containing at least one ethylenically unsaturated monomer carrying a sulfonic group, the monomer being in free form or in partially or fully neutralized form.

[0586] These polymers can be crosslinked or non-crosslinked. They are preferably crosslinked.

[0587] These polymers can be associative or non-associative, preferably non-associative.

[0588] It should be understood that an "associative polymer" is a polymer capable of associating reversibly with each other or with other molecules in an aqueous medium.

[0589] Their chemical structure more particularly contains at least one hydrophilic region and at least one hydrophobic region.

[0590] The term "hydrophobic group" means a saturated or unsaturated, straight-chain or branched hydrocarbon-based chain containing at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, particularly from 12 to 30 carbon atoms, and more preferably from 18 to 30 carbon atoms, or a polymer.

[0591] Preferably, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group can be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It can also denote a hydrocarbon-based polymer, such as polybutadiene.

[0592] The ethylenically unsaturated monomers carrying sulfonic groups are particularly selected from vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylamido(C1-C 22 )alkyl sulfonic acid, N-(C1-C 22)alkyl(meth)acrylamido (C1-C 22 )alkylsulfonic acids such as undecylacrylamidomethanesulfonic acid and also their partially or fully neutralized forms.

[0593] More preferably, (meth)acrylamido (C1-C 22 )alkylsulfonic acids will be used, such as acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and also their partially or fully neutralized forms.

[0594] Particularly preferably, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and also its partially or fully neutralized forms are used.

[0595] Among the 2-acrylamido-2-methylpropanesulfonic acid copolymers, mention may be made of the partially or fully neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide; particular mention may be made of the product described in Example 1 of EP 503 853, and reference may be made to said document regarding these polymers.

[0596] Also mention may be made of the copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts and hydroxyethyl acrylate, such as the compound sold by SEPPIC under the name Sepinov EMT 10 (INCI name: hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer).

[0597] The associative AMPS polymers may in particular be selected from the statistically associative AMPS polymers modified by reaction with C6-C 22 n-monoalkylamines or di-n-alkylamines, and those as described in patent application WO 00 / 31154 (which forms 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 obtained with monohydric alcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, or mixtures of these compounds.

[0598] The preferred polymers of this family are selected from the associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0599] These same copolymers may also contain one or more ethylenically unsaturated monomers that do not contain a fatty chain, such as (meth)acrylic acid derivatives, especially the esters obtained therefrom with monohydric alcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, or mixtures of these compounds.

[0600] These copolymers are described in particular in patent application EP-A 750 899, patent US 5 089 578 and the following publications by Yotaro Morishima:

[0601] -Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40, (2000), 323-336;

[0602] -Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering, Macromolecules, Vol. 33, No. 10, (2000), 3694-3704;

[0603] -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;

[0604] - Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers - Polym. Preprint, Div. Polym. Chem. 40(2), (1999), 220 - 221.

[0605] Among these polymers, mention may be made of:

[0606] - Crosslinked or non-crosslinked, neutralized or non-neutralized copolymers comprising 15% to 60% by weight of AMPS units and 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 - A750 899;

[0607] - Terpolymers comprising 10 mol% to 90 mol% of acrylamide units, 0.1 mol% to 10 mol% of AMPS units and 5 mol% to 80 mol% of n-(C6 - C 18 ) alkylacrylamide units, such as those described in patent US - 5 089 578.

[0608] Also mention may be made of copolymers of fully neutralized AMPS and dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and n-dodecylmethacrylamide, such as those described in the above-mentioned Morishima article.

[0609] Preferably, the non-carboxylic acid anionic thickener is selected from the sodium 2-(acrylamido)-2-methylpropanesulfonate / hydroxyethyl acrylate copolymer (INCI name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer) sold by Ciba.

[0610] Advantageously, the total amount of the non-carboxylic acid anionic thickener ranges from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, more preferably from 0.1% to 5% by weight and even more preferably from 0.1% to 3% by weight relative to the total weight of composition C.

[0611] Associative polymer

[0612] The composition C according to the invention may also comprise at least one associative polymer different from the compounds containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickeners as previously defined.

[0613] It is to be understood that "associative polymers" are polymers capable of associating reversibly with one another or with other molecules in an aqueous medium.

[0614] Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.

[0615] The term "hydrophobic group" means a saturated or unsaturated, straight-chain or branched hydrocarbon-based chain containing at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, particularly from 12 to 30 carbon atoms, and more preferably from 18 to 30 carbon atoms, or a polymer.

[0616] Preferably, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecanol or decanol. It may also denote a hydrocarbon-based polymer, such as polybutadiene.

[0617] The associative polymers may have nonionic, anionic, cationic or amphoteric properties.

[0618] Preferably, the associative polymers are selected from anionic associative polymers.

[0619] Among the associative polymers of the anionic type, mention may be made of:

[0620] -(a) those comprising at least one hydrophilic unit and at least one fatty chain allyl ether unit, more particularly those whose hydrophilic unit is constituted by an ethylenically unsaturated anionic monomer, even more particularly by a vinyl carboxylic acid and most particularly by acrylic acid or methacrylic acid or a mixture thereof.

[0621] Among these anionic associative polymers, those which are particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and / or methacrylic acid, 5% to 60% by weight of lower alkyl (meth)acrylates, 2% to 50% by weight of fatty chain allyl ethers and 0% to 1% by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenically unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.

[0622] Among the latter polymers, the most particularly preferred ones are crosslinked terpolymers of methacrylic acid, ethyl acrylate and polyethylene glycol (10 EO) stearyl ether (steareth-10), in particular those sold by Ciba under the name Salcare SC and Salcare SC which are 30% aqueous emulsions of crosslinked terpolymers of methacrylic acid, ethyl acrylate and allyl ether of steareth-10 (40 / 50 / 10);

[0623] -(b) those comprising i) at least one hydrophilic unit of the unsaturated olefinic carboxylic acid type and ii) at least one hydrophobic unit of the type such as (C10-C30) alkyl esters of unsaturated carboxylic acids.

[0624] The (C 10 -C 30 ) alkyl esters of unsaturated carboxylic acids which can be used in the present invention 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.

[0625] For example, this type of anionic polymer is described and prepared according to patents US 3 915 921 and US 4 509 949.

[0626] Among this type of anionic associative polymers, those which will be used more particularly are those consisting of 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit) and 0% to 6% by weight of crosslinkable polymerizable monomer, or alternatively those consisting of 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinkable polymerizable monomer, as previously described.

[0627] Among the polymers described above, those which are most particularly preferred according to the present invention are those sold by Goodrich under the trade name Pemulen Pemulen Carbopol and even more preferably Pemulen and those sold by Ciba under the name Coatex Products for sale.

[0628] Also mentionable is the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer sold by ISP under the name Acrylidone LM.

[0629] -(c) Maleic anhydride / C 30 -C 38 α-olefin / maleic acid alkyl ester terpolymers, such as those sold by Newphase Technologies under the name Performa V Products for sale (maleic anhydride / C 30 -C 38 α-olefin / isopropyl maleate copolymer).

[0630] -(d) Acrylic acid terpolymers, comprising:

[0631] i) Approximately 20% to 70% by weight of an α,β-monoethylenically unsaturated carboxylic acid [A],

[0632] ii) Approximately 20% to 80% by weight of an α,β-monoethylenically unsaturated non-surfactant monomer other than [A],

[0633] iii) Approximately 0.5% to 60% by weight of a nonionic mono-carbamate, which is the reaction product of a mono-surfactant and a monoethylenically unsaturated monoisocyanate,

[0634] Such as those described in patent application EP-A-0 173 109, and more particularly the terpolymer described in Example 3, namely the methacrylic acid / methyl acrylate / behenyl dimethyl-m-isopropenylbenzyl isocyanate ethoxylated (40EO) terpolymer, as a 25% aqueous dispersion.

[0635] -(e) Copolymers, which contain among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid with an oxyalkylated fatty alcohol.

[0636] Preferably, these compounds also contain, as monomers, esters of α,β-monoethylenically unsaturated carboxylic acids and C1-C4 alcohols.

[0637] Examples of compounds of this type that can be mentioned are Aculyn & Haas) sold by Rohm and Haas which is a methacrylic acid / ethyl acrylate / oxyalkylated stearyl methacrylate terpolymer; and also Aculyn 88, which is also sold by Rohm and Haas.

[0638] Advantageously, the associative polymers that are different from compounds containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickeners described previously are selected from acrylic associative polymers, more preferably carboxylic acid acrylic associative polymers.

[0639] Particularly preferably, the associative polymers that are different from compounds containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickeners described previously are selected from copolymers that include among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkyleneated fatty alcohol.

[0640] Advantageously, the total amount of the associative polymers that are different from compounds containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickeners described previously ranges from 0.05% to 15% by weight, preferably from 0.05% to 10% by weight, more preferably from 0.1% to 5% by weight, and even more preferably from 0.1% to 1% by weight relative to the total weight of composition C.

[0641] organic solvent

[0642] Composition C according to the invention may comprise one or more organic solvents.

[0643] Examples of organic solvents that may be mentioned include C1-C4 lower alkanols such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether, and also aromatic alcohols (especially aromatic monohydric alcohols such as benzyl alcohol or phenoxyethanol), and mixtures thereof.

[0644] The organic solvent may be present in a total amount between 0.01% and 60% by weight, preferably between 0.05% and 50% by weight, and more preferably between 0.1% and 45% by weight and including the end values relative to the total weight of composition C.

[0645] Composition C used in the context of the method according to the invention may be aqueous. The water content may range from 1% to 90% by weight, preferably from 10% to 80% by weight, and more preferably from 20% to 75% by weight relative to the total weight of composition C.

[0646] additive

[0647] Composition C used in the context of the method according to the invention may contain any auxiliaries or additives customarily used.

[0648] Among the additives that can be included in the composition, reducing agents, softening agents, defoaming agents, humectants, UV screening agents, peptizing agents, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers previously described, preservatives, silicones different from the compounds previously described, oils, waxes and mixtures thereof may be mentioned.

[0649] The composition C used in the context of the method according to the invention may in particular be in the form of a suspension, a dispersion, a gel, an 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 vesicle dispersion, in particular a vesicle dispersion of ionic or nonionic lipids, or a two-phase or multi-phase lotion.

[0650] A person skilled in the art can, based on their general knowledge, first consider the nature of the ingredients used, in particular their solubility in the carrier, and secondly the intended application of the composition, to select the appropriate form of presentation, as well as its preparation method.

[0651] Applying steam to and shaping keratinous hair fibers

[0652] According to steps b) and c) of the method according to the invention, steam is applied to the keratinous hair fibers in an amount greater than or equal to 0.5 g / min by means of a device capable of generating steam, and the keratinous hair fibers are shaped at a temperature greater than or equal to 100 °C.

[0653] According to a specific embodiment, the step b) of applying steam is separated from the step c) of shaping the keratinous hair fibers; preferably, the step b) of applying steam is followed by the step c) of shaping.

[0654] According to another specific embodiment, the step b) of applying steam and the step c) of shaping the keratinous hair fibers are carried out simultaneously.

[0655] The application of steam can be carried out using any device known per se capable of generating steam in an amount greater than or equal to 0.5 g / min. The device includes at least one tank for containing water that can be heated.

[0656] According to a specific embodiment, the device is portable, i.e. the tank can be in contact with the part of the device including the steam distribution orifice.

[0657] Preferably, the device used in the method according to the invention is a handpiece. It may include at least one arm and at least one tank for containing water that can be heated.

[0658] Preferably, the device comprises two arms which are movable relative to one another between a configuration in which they are close to one another for treating keratin hair fibres in their entirety and a separated configuration in which the keratin hair fibres to be treated are engaged.

[0659] These arms are articulated relative to one another by means of a hinge pin.

[0660] An elastic return member may be provided to return the arms to the separated configuration.

[0661] These arms delimit therebetween a keratin hair fibre treatment zone intended to receive a lock of keratin hair fibres to be treated, the handpiece moving along this keratin hair fibre treatment zone during treatment. The device may move, for example, in the direction from the root to the end of the lock of keratin hair fibres. Such a device allows steam to be easily applied to the keratin hair fibres.

[0662] Keratin hair fibre shaping may be carried out using any type of device known in the art allowing heating to a temperature greater than or equal to 100 °C. A keratin hair fibre shaping device is, for example, a device having a heating surface capable of coming into contact with the keratin hair fibres and exerting (although slightly) a tension on the keratin hair fibres, in particular allowing the keratin hair fibres to be straightened, shaped or untangled.

[0663] Shaping of the keratin hair fibres may be carried out using conventional shaping devices such as straighteners or curlers, or by blow-drying using a hair dryer and a brush; such shaping is generally carried out at a temperature between 100 °C and 250 °C, preferably between 150 °C and 230 °C. According to a preferred embodiment, shaping is carried out using a straightener.

[0664] The application of steam and shaping may be carried out in the same device which first of all comprises a tank containing a liquid (preferably water), means for heating the tank to form steam, and a system for delivering the steam to the keratin hair fibres which may be located in the straightener. Such a device is called a Steampod.

[0665] Thus, in addition to the system for emitting steam described previously, each arm may also comprise means for heating the keratin hair fibres, which means are in particular in the form of a plate made of a thermally conductive material or a light radiation system of the IR or LED type, defining a contact surface with the keratin hair fibres, bringing the temperature on the keratin hair fibres to be, for example, greater than or equal to 100 °C and making it possible to carry out shaping.

[0666] Advantageously, the amount of steam ranges from 0.5 to 60 g / min, preferably from 0.5 to 20 g / min, more preferably from 0.5 to 10 g / min, even more preferably from 0.5 to 5 g / min, still better from 0.5 to 1 g / min.

[0667] Advantageously, the shaping temperature during step c) ranges from 100 °C to 250 °C, preferably from 150 °C to 250 °C, more preferably from 150 °C to 230 °C, and even more preferably from 180 °C to 220 °C.

[0668] Application of composition G

[0669] The dyeing method according to the invention may comprise applying to the keratinous hair fibers at least one composition G after the steam application step b) and the shaping step c) have been carried out, the composition G comprising:

[0670] - at least one (poly)carbodiimide compound;

[0671] - optionally at least one compound comprising at least one carboxyl functional group.

[0672] The (poly)carbodiimide compound is as previously defined and has the same preferences as those indicated for composition C.

[0673] The (poly)carbodiimide compound used in composition G is the same as or different from that used in composition C, preferably the same.

[0674] Advantageously, the total amount of the (poly)carbodiimide compound in composition G 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 and still better from 1% to 6% by weight, relative to the total weight of composition G.

[0675] The compound comprising at least one carboxyl functional group is as previously defined and has the same preferences as those indicated for composition C.

[0676] The compound comprising at least one carboxyl functional group used in the context of composition G is the same as or different from that used in composition C, preferably the same.

[0677] Advantageously, the total amount of the compound comprising at least one carboxyl functional group ranges from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 1% to 15% by weight and still better from 2% to 10% by weight, relative to the total weight of composition G.

[0678] Composition G may also comprise a colorant selected from the pigments, direct dyes and mixtures thereof as described above.

[0679] Preferably, composition G does not contain any colorant selected from pigments, direct dyes, and mixtures thereof.

[0680] Composition G may also contain a non-carboxylic acid anionic thickener and / or an associative polymer as defined above.

[0681] According to a particularly preferred embodiment, composition G contains the same (poly)carbodiimide compound as composition C and the same compound containing at least one carboxyl functional group as composition C, and preferably composition G does not contain any colorant.

[0682] After applying this composition G, it may also be a step of applying heat, such as a step of drying at a temperature between 50 °C and 110 °C, a step of straightening keratin hair fibers with a straightener, or a step of applying steam in an amount greater than or equal to 0.5 g / min with a device capable of generating steam, and a step of shaping at a temperature greater than or equal to 100 °C, which steps are the same as steps b) and c) described previously.

[0683] According to a specific embodiment, the method according to the invention includes, after step c), additional steps:

[0684] d) applying to the keratin hair fibers at least one composition G comprising at least one (poly)carbodiimide compound as described previously; and then

[0685] e) optionally, a step of drying the keratin hair fibers; and then

[0686] f) applying steam to the keratin hair fibers in an amount greater than or equal to 0.5 g / min with a device capable of generating steam, and

[0687] g) shaping the keratin hair fibers at a temperature greater than or equal to 100 °C, preferably between 150 °C and 230 °C.

[0688] According to a specific embodiment, the step f) of applying steam is separated from the step g) of shaping the keratin hair fibers; preferably, the step f) of applying steam is followed by the step g) of shaping.

[0689] According to another specific embodiment, the step f) of applying steam and the step g) of shaping the keratin hair fibers are carried out simultaneously.

[0690] According to another specific embodiment, the method according to the invention includes, after step c), additional steps:

[0691] d) applying to the keratin hair fibers at least one composition G comprising at least one (poly)carbodiimide compound as described previously; and then

[0692] e) a step of drying the keratin hair fibers; and then

[0693] f) Optionally, steam is applied to the keratinous hair fibers in an amount greater than or equal to 0.5 g / min by means of a device capable of generating steam, and

[0694] g) Optionally, the keratinous hair fibers are shaped at a temperature greater than or equal to 100 °C, preferably between 150 °C and 230 °C.

[0695] Scheme

[0696] The composition C described above can be used on wet or dry keratinous hair fibers, and also on any type of keratinous hair fibers that are blond or brown, natural or dyed, permanently waved, bleached or relaxed.

[0697] According to a specific embodiment of the invention, the keratinous hair fibers are washed before applying the composition C.

[0698] Preferably, a washing, rinsing, draining or drying step is carried out after applying the composition C to the keratinous hair fibers.

[0699] More preferably, a drying step is carried out after applying the composition C to the keratinous hair fibers. Thus, preferably, the method according to the invention comprises a drying step between step a) and step b).

[0700] The application of the composition C to the keratinous hair fibers can be carried out by any conventional means, in particular using a comb, a fine brush, a coarse brush, a sponge or with the fingers.

[0701] The application of the composition C to the keratinous hair fibers is generally carried out at room temperature (between 15 °C and 25 °C).

[0702] After applying the composition C to the keratinous hair fibers, it is possible to wait between 1 minute and 6 hours, particularly between 1 minute and 2 hours, more particularly between 1 minute and 1 hour, and more preferably between 1 minute and 30 minutes, before, for example, a washing, rinsing, draining and / or drying step.

[0703] After applying the composition C, the keratinous hair fibers are left to dry or dried, for example, with a hair dryer at a temperature greater than or equal to 30 °C.

[0704] During the step of drying the keratinous hair fibers, a mechanical action can be exerted on the tresses, such as combing, brushing or passing the fingers through.

[0705] When the step of drying the keratinous hair fibers is carried out using a hood or a hair dryer, the temperature is preferably between 30 °C and 110 °C, preferably between 50 °C and 90 °C.

[0706] Preferably, if keratin hair fibers are dried, they are dried with an air stream in addition to the supply of heat. During drying, this air stream enables improved strand separation of the coating.

[0707] After the drying step, when the drying step is carried out, step b) of the method according to the invention is carried out.

[0708] Preferably, the present invention is a method for dyeing keratin hair fibers, the method comprising the following steps:

[0709] i) applying to the keratin hair fibers at least one composition C, the composition comprising:

[0710] - at least one (poly)carbodiimide compound as previously described; and

[0711] - at least one colorant selected from pigments, direct dyes and mixtures thereof as previously described; and then

[0712] ii) optionally allowing the composition C to have a residence time of from 1 minute to 30 minutes, preferably from 1 to 20 minutes, on these keratin hair fibers; and then

[0713] iii) optionally drying the keratin hair fibers; and then

[0714] iv) applying steam to the keratin hair fibers in an amount greater than or equal to 0.5 g / min by means of a device capable of generating steam, and

[0715] v) shaping the keratin hair fibers at a temperature greater than or equal to 100 °C.

[0716] The method according to the invention may comprise additional steps, in particular the step of applying a composition G comprising at least one (poly)carbodiimide compound as previously described.

[0717] Advantageously, the (poly)carbodiimide compound used in the context of the composition G is the same as or different from, preferably the same as, the one used in the context of the composition C. It may also contain a compound comprising at least one carboxyl functional group as defined previously.

[0718] The compound comprising at least one carboxyl functional group used in the context of the composition G is the same as or different from, preferably the same as, the one used in the context of the composition C.

[0719] The composition G may also comprise a colorant selected from pigments, direct dyes and mixtures thereof.

[0720] Preferably, the composition G does not contain any colorant selected from pigments, direct dyes, and mixtures thereof.

[0721] Composition G may also contain a non-carboxylic acid anionic thickener and / or an associative polymer as defined above.

[0722] According to one embodiment, after the application of composition G, there is a step e) of drying the keratin hair fibers and / or a step f) of applying steam to the keratin hair fibers in an amount greater than or equal to 0.5 g / min by means of a device capable of generating steam, and a step g) of shaping the keratin hair fibers at a temperature greater than or equal to 100 °C, as previously described.

[0723] According to a specific embodiment, step f) is separated from step g); preferably, step f) is followed by step g).

[0724] According to another specific embodiment, steps f) and g) are carried out simultaneously.

[0725] According to a preferred embodiment, composition G does not contain any colorant as previously described.

[0726] Preferably, composition C further comprises at least one compound containing at least one carboxyl functional group as previously described, preferably an acrylic polymer.

[0727] Preferably, composition C further comprises at least one non-carboxylic acid anionic thickener as previously described, preferably an associative copolymer selected from AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0728] Preferably, composition C further comprises at least one associative polymer different from the compound containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickener as previously defined, preferably an acrylic associative polymer, more preferably a carboxylic acid acrylic associative polymer.

[0729] Advantageously, the step of applying composition C to the keratin hair fibers is repeated several times.

[0730] According to a preferred embodiment, step a) comprises instantaneously mixing at least two compositions A and B at the time of use to obtain composition C and comprises applying composition C to the keratin hair fibers, wherein:

[0731] - Composition A contains at least one (poly)carbodiimide compound as previously defined;

[0732] - Composition B contains at least one compound containing at least one carboxyl functional group as previously defined;

[0733] Composition A and / or composition B contains at least one colorant selected from pigments, direct dyes and mixtures thereof as previously defined.

[0734] According to a preferred embodiment, the dyeing method according to the invention is a method for dyeing keratin hair fibers, which method comprises:

[0735] a) Immediately mixing at least two compositions A and B during use to obtain composition C and including applying composition C to the keratin hair fibers, wherein:

[0736] - Composition A contains at least one (poly)carbodiimide compound as previously defined;

[0737] - Composition B contains a compound containing at least one carboxyl functional group as previously defined;

[0738] Composition A and / or composition B contains at least one colorant selected from pigments, direct dyes and mixtures thereof as previously defined; and then

[0739] Drying the keratin hair fibers by applying heat and / or an air stream; and then

[0740] b) Applying steam to the keratin hair fibers in an amount greater than or equal to 0.5 g / min by means of a device capable of generating steam, and

[0741] c) Shaping the keratin hair fibers at a temperature greater than or equal to 100 °C.

[0742] According to a specific embodiment, step b) is separated from step c); preferably, step c) follows step b).

[0743] According to another specific embodiment, step b) and step c) are carried out simultaneously.

[0744] Composition A and / or composition B may optionally contain at least one non-carboxylic acid anionic thickener as previously described and / or at least one associative polymer different from the compound containing at least one carboxyl functional group as described above and different from the non-carboxylic acid anionic thickener as previously defined.

[0745] Advantageously, composition A contains at least one non-carboxylic acid anionic thickener as previously described.

[0746] Advantageously, composition B contains at least one associative polymer different from the compound containing at least one carboxyl functional group as described above and different from the non-carboxylic acid anionic thickener as previously defined.

[0747] Preferably, composition B contains at least one colorant selected from pigments, direct dyes and mixtures thereof as previously described.

[0748] Preferably, composition A does not contain any colorant selected from pigments, direct dyes and mixtures thereof as previously described.

[0749] According to this embodiment, compositions A and B are preferably mixed less than 15 minutes, more preferably less than 10 minutes, still better less than 5 minutes before being applied to the keratinous hair fibers.

[0750] The weight ratio between composition A and composition B preferably ranges from 0.1 to 10, preferably from 0.2 to 5, still better from 0.5 to 2, or even from 0.6 to 1.5. In a specific embodiment, the weight ratio between composition A and composition B is equal to 1.

[0751] The total amount of the (poly)carbodiimide compound preferably ranges from 0.01% to 40% by weight, more preferably from 0.1% to 30% by weight, still better 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.

[0752] The total amount of the compound containing at least one carboxyl functional group preferably ranges from 0.2% to 60% by weight, more preferably from 1% to 40% by weight, still better from 1% to 30% by weight, and even more preferably from 2% to 20% by weight relative to the total weight of composition B.

[0753] According to a specific embodiment, the method according to the invention includes, after step c), additional steps:

[0754] d) applying composition G to the keratinous hair fibers as previously described; and then

[0755] e) optionally, drying the keratinous hair fibers as previously described; and then

[0756] f) applying steam as previously described, and

[0757] g) shaping the keratinous hair fibers as previously described.

[0758] According to a specific embodiment, step f) and step g) are separate; preferably, step g) follows step f).

[0759] According to another specific embodiment, step f) and step g) are carried out simultaneously.

[0760] According to another specific embodiment, the method according to the invention includes, after step c), additional steps:

[0761] d) applying composition G to the keratinous hair fibers as previously described; and then

[0762] e) drying the keratinous hair fibers as previously described; and then

[0763] f) Optionally, steam is applied to the keratinous hair fibers in an amount greater than or equal to 0.5 g / min by means of a device capable of generating steam, and

[0764] g) Optionally, the keratinous hair fibers are shaped at a temperature greater than or equal to 100°C, preferably between 150°C and 230°C.

[0765] According to a specific embodiment, the method according to the invention further comprises, in the following order:

[0766] d) Applying composition G as previously defined; and then

[0767] e) Drying by means of an air stream, in particular using a hair dryer; and then

[0768] f) Applying steam, and g) shaping the keratinous hair fibers as described for steps b) and c).

[0769] The total amount of the aqueous dispersion of the particles of the polymer selected from polyurethanes, acrylic polymers, and mixtures thereof preferably ranges from 0.2% to 60% by weight, more preferably from 1% to 50% by weight, still better from 1% to 40% by weight, and even more preferably from 2% to 30% by weight relative to the total weight of composition B.

[0770] According to a specific embodiment, the total amount of the aqueous dispersion of the acrylic polymer particles preferably ranges from 0.2% to 60% by weight, more preferably from 1% to 50% by weight, still better from 1% to 40% by weight, and even more preferably from 2% to 30% by weight relative to the total weight of composition B. Detailed Description

[0771] The present invention will now be described more specifically by way of examples, which in no way limit the scope of the invention. However, these examples enable the support of the specific features, variants, and preferred embodiments of the invention.

[0772] Examples

[0773] The (poly)carbodiimides of the present invention are obtainable from commercial products or reagents which can be synthesized according to chemical reactions known to those skilled in the art by synthesis methods known to those skilled in the art. For example, reference can be made to the book Sciences of Synthesis - Houben - Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D - 70469 Stuttgart, or US Patent US 4 284 730 or Canadian Patent Application CA2 509 861.

[0774] More specifically, the method for preparing the (poly)carbodiimides of the present invention involves in a first step a diisocyanate reagent (1):

[0775] O=C=N - L1 - N=C=O (1),

[0776] In formula (1), L1 is as previously defined, and in the presence of a carboimidation catalyst (2) (such as those described in US 4 284 730, especially phosphorus - based catalysts particularly selected from cyclophosphene oxides and cyclophosphene sulfoxides, diaza - and oxa - phospholanes), preferably under an inert atmosphere (nitrogen or argon), and especially in a polar solvent (preferably an aprotic solvent such as THF, diglyme, triglyme, 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 a carbodiimide diisocyanate compound (3):

[0777] O=C=N - L1 - (N=C=N - L1) n - N=C=O (3),

[0778] In formula (3), L1 and n are as previously defined. A benzoyl halide such as benzoyl chloride can be added to deactivate the catalyst.

[0779] To obtain a "symmetric" (poly)carbodiimide, during the second step of the preparation method, compound (3) is reacted with 1 molar equivalent (1 equivalent) of a nucleophilic reagent R1 - X1 - H, and then with 0.5 equivalent of the reagent H - E - H, where R1, X1 and E are as previously defined, to obtain the "symmetric" compound (4) according to the present invention:

[0780] [R1 - X1 - C(O) - NH - L1 - (N=C=N - L1) n - NH - C(O)]2 - E (4),

[0781] 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 H-E-H can be added first, and then 1 equivalent of the reagent R1-X1-H can be added.

[0782] To obtain an “asymmetric” (poly)carbodiimide, during the second step of the preparation method, compound (3) is reacted with 1 molar equivalent (1 equivalent) of the nucleophilic reagent R1-X1-H, and then with 1 equivalent of the reagent H-E-H, where R1, X1, and E are as defined previously, to obtain compound (5):

[0783] R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-E-H (5),

[0784] In formula (5), R1, X1, L1, n, and E are as defined previously.

[0785] According to one variant of obtaining compound (5) from (3), 1 equivalent of the reagent R1-X1-H can be added first, and then 0.5 equivalent of the reagent H-E-H can be added.

[0786] During the third step, compound (5) is reacted with 1 equivalent of compound (6)

[0787] R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O(6), and the compound (6) is prepared in advance from compound (3’):

[0788] O=C=N-L1-(N=C=N-L1) z -N=C=O(3’),

[0789] In formula (3’), L1 and z are as defined previously, and it is reacted with 1 equivalent of the nucleophilic reagent R2-X2-H, where L1, R2, X2, and z are as defined previously, to obtain the asymmetric compound (7):

[0790] R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-E-C(O)-NH-L1-(N=C=N-L1) z -NH-C(O)-X2-R2 (7),

[0791] In formula (7), R1, X1, L1, R2, X2, n, z, and E are as defined previously.

[0792] 1 molar equivalent of the compound O═C═N-L1-(N═C═N-L1) z -N═C═O (3’) can be reacted with 1 / w molar equivalents of H-E-H and then with 1 equivalent of the nucleophile R2-X2-H to obtain the compound (8):

[0793] H-[E-C(O)-NH-L1-(N═C═N-L1) z w -NH-C(O)-X2-R2 (8),

[0794] 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.

[0795] This last compound (8) can then be reacted with 1 equivalent of the compound (4’):

[0796] 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 equivalent of the nucleophile R1-X1-H with 1 equivalent of the compound (3)), to obtain the (poly)carbodiimide (9) of the present invention:

[0797] R1-X1-C(O)-NH-L1-(N═C═N-L1) n -NH-C(O)-[E-C(O)-NH-L1-(N═C═N-L1) z w -NH-C(O)-X2-R2 (9),

[0798] In formula (9), L1, R1, X1, R2, X2, n, z, w and E are as defined previously.

[0799] (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.

[0800] Example 1: Method for synthesizing (poly)carbodiimide compounds

[0801] 50 g of 4,4’-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phospholene 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.

[0802] ​​The reaction medium was heated under nitrogen at 140 °C for 4 hours, and the reaction was monitored by infrared spectroscopy by means of the absorption of isocyanate functional groups between 2200 and 2300 cm -1 and then cooled to 120 °C.

[0803] 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 with stirring. The temperature of 120 °C was maintained until the isocyanate functional groups had completely disappeared, monitored by infrared spectroscopy at 2200 - 2300 cm -1 and then cooled to room temperature.

[0804] After cooling to room temperature, the reaction medium was poured dropwise into a 500 mL glass beaker containing 85 g of distilled water with vigorous stirring to obtain the desired product in the form of a translucent yellow liquid.

[0805] Example 2

[0806] Compositions A and B as described in Tables 1 and 2 below were prepared: Unless otherwise mentioned, the amounts are expressed as g of starting material as obtained / 100 g.

[0807] [Table 1]

[0808]

[0809] (1) Synthesized according to the synthesis method described in Example 1 (40% active material in water),

[0810] (2) Sold by SEPPIC under the name Sepinov EMT10 (90% active material),

[0811] (3) Sold by WACKER under the name Belsil ADM LOG 1 (15% active material).

[0812] [Table 2]

[0813]

[0814]

[0815] (4) Sold by Daito Kasei Kogyo Co., Ltd. under the trade name Daitosol 3000SLPN-PE1 (aqueous dispersion containing 30% active material)

[0816] (5) Sold by Rohm and Haas under the trade name Aculyn (oxyalkylated methacrylic acid / ethyl acrylate / stearyl methacrylate terpolymer containing 30% active material)

[0817] Then, Composition A and Composition B are mixed at a mass ratio of 50 / 50 to obtain Composition C according to the present invention.

[0818] Scheme

[0819] Two application methods were used.

[0820] According to the first method (referred to as Method P1), Composition C was manually applied to a tress of dry natural keratin hair fibers containing 90% white keratin hair fiber strands at a rate of 0.8 g of composition per gram of tress using a brush. Then, the tress of keratin hair fibers was detangled and dried with a hair dryer, and then combed.

[0821] Therefore, this is a comparative method.

[0822] According to the second method (referred to as Method P2), Composition C was manually applied to a tress of dry natural keratin hair fibers containing 90% white keratin hair fiber strands at a rate of 0.8 g of composition per gram of tress using a brush. Then, the tress of keratin hair fibers was detangled and dried with a hair dryer, and then combed.

[0823] Then, steam was applied to the tress of keratin hair fibers at a rate of 0.8 g / min, and the tress of keratin hair fibers was shaped or straightened at a temperature of 210 °C.

[0824] The application of steam and shaping were carried out separately using a steam straightener (sold under the name Steampod 3). Two passes were made using this device.

[0825] Therefore, this is a method according to the present invention.

[0826] The applied methods are summarized in Table 3 below:

[0827] [Table 3]

[0828] Method P1 (comparison) P2 (the present invention) Application of composition C Yes Yes Apply steam and shape - Yes

[0829] Then, the tresses of keratin hair fibers treated by Methods P1 and P2 were subjected to a test including several repeated shampoo washes in order to evaluate the tolerance (persistence) of the obtained coloring with respect to shampoo washing according to the shampoo washing protocol described below.

[0830] Shampoo washing scheme:

[0831] The tresses of dyed keratin hair fibers were combed, wetted with water at 35 °C and then passed between the fingers five times for 5 seconds. Then, the tresses of keratin hair fibers were squeezed dry between two fingers.

[0832] The standard shampoo (Garnier Ultra Doux) was uniformly applied to the dyed tresses at a ratio of 0.4 g of standard shampoo per gram of tress, and the tresses of keratin hair fibers were gently massaged for 15 seconds along the length from the roots to the tips (6 passes).

[0833] Then the tresses of keratin hair fibers were placed on a petri dish and left to stand for 1 minute.

[0834] Next, the tresses were rinsed with water while passing them between the fingers (15 passes). Then the tresses of keratin hair fibers were squeezed dry between two fingers and then subjected to the next shampoo wash.

[0835] After several shampoo wash tests, the tresses of keratin hair fibers were combed and dried with a hair dryer.

[0836] Result

[0837] The color fastness of the tresses was evaluated using a Minolta CM3610A spectrophotometer (light source D65, angle 10°, including specular reflection component) in the CIE L*a*b* system.

[0838] In this L*a*b* system, L* represents the intensity of the color, a* represents the green / red axis, and b* represents the blue / yellow axis.

[0839] The color fastness of the coloring was evaluated by the color difference ΔE between the measurements made on the dyed tresses before the shampoo wash and then after undergoing five shampoo washes according to the protocol described above.

[0840] The ΔE value was calculated according to the following equation:

[0841]

[0842] In this equation, L*, a*, and b* represent the values measured after dyeing the keratin hair fibers and after the shampoo wash, and L0*, a0*, and b0* represent the values measured after dyeing the keratin hair fibers but before the shampoo wash.

[0843] [Table 6]

[0844]

[0845]

[0846] Tresses of keratin hair fibers treated by method P2 according to the present invention and washed with five shampoos had a significantly lower color difference than tresses of keratin hair fibers treated by the comparative method P1.

[0847] Thus, the colored coating obtained by means of the method according to the invention shows an improved tolerance to shampooing.

[0848] Example 3

[0849] In this example, tresses of keratin hair fibers are treated via the method according to the invention (hereinafter referred to as method P2’).

[0850] At the end of protocol P2 as previously described (after application of steam and shaping), under the same conditions as described in Example 2, a mixture obtained from composition A as described in Example 2 and composition B’ corresponding to composition B as described in Example 2 but without the pigment (red iron oxide) is applied to the keratin hair fibers.

[0851] After drying and combing, the tresses are treated with steam and shaped according to the protocol of Example 2.

[0852] Then the tresses are shampooed according to the shampooing protocol as previously described and the color is evaluated according to the shampooing protocol as previously described.

[0853] The results are collated in Table 7.

[0854] [Table 7]

[0855]

[0856] Tresses of keratin hair fibers treated by means of method P2’ according to the invention and shampooed five times have a very small color difference.

[0857] Thus, the colored coating obtained by means of the method according to the invention shows a very good persistence with respect to shampooing.

[0858] In both of these examples, there is also a very good cosmetic effect on the keratin hair fibers, with a smooth feeling when the fingers are run along the fibers, and the keratin hair fibers are made supple, such that the keratin hair fibers move in a manner similar to untreated keratin hair fibers.

Claims

1. A method for dyeing keratinous hair fibers, the method comprising: a) applying to the keratinous hair fibers at least one composition C, the composition comprising: - at least one (poly)carbodiimide compound; and - at least one colorant selected from pigments, direct dyes, and mixtures thereof; and then b) applying steam to the keratinous hair fibers in an amount greater than or equal to 0.5 g / min by means of a device capable of generating steam, and c) shaping the keratinous hair fibers at a temperature greater than or equal to 100 °C.

2. The method according to claim 1, wherein The (poly)carbodiimide compound is selected from compounds of the following formula (I): Wherein: - 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 hydrocarbon-based groups optionally inserted with one or more heteroatoms, preferably alkyl groups; a group selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidylalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl groups; and hydrocarbon-based groups, preferably alkyl groups, which are optionally inserted with one or more heteroatoms and one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloylalkylsilyl, methacryloylalkylsilyl, crotonoylalkylsilyl, carboxylic anhydride group alkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehyde group alkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidylalkylsilyl, sulfonylalkylsilyl, (meth)acryloylalkyl, crotonoylalkyl, alkyl epoxides such as propyl epoxide or butyl epoxide, and aziridinyl 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, wherein The (poly)carbodiimide compound is selected from compounds of the following formula (II): Wherein: - X1 and X2 independently represent an oxygen atom O, a sulfur atom S, or an NH group; - R1 and R2 independently represent hydrocarbon-based groups optionally inserted with one or more heteroatoms; - n and z indicate integers ranging from 1 to 20, where n + z ≥ 2 and w indicates an integer ranging from 1 to 3; -L1 independently represents C1-C 18 a divalent aliphatic hydrocarbon-based group, C3-C 15 a cycloalkanediyl, C3-C 12 a heterocycloalkanediyl or C6-C 14 an 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 -; Where R3 and R4 independently represent divalent hydrocarbon-based groups optionally inserted with one or more heteroatoms; -R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally inserted with one or more heteroatoms; -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally inserted with one or more heteroatoms.

4. The method according to claim 3, wherein The (poly)carbodiimide compound is selected from the compounds of the formula (II), wherein: -X1 and X2 independently represent an oxygen atom; -R1 and R2 independently are selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols in which the hydroxy group has 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 a divalent aliphatic hydrocarbon-based group, C3-C 15 a cycloalkylene, C3-C 12 a heteroalkylene or C6-C 14 an arylene, and mixtures thereof; -E independently represents a group selected from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; - When R5 is not a covalent bond, R5 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; and -R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear 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 the formula (II), wherein: -X1 and X2 independently represent an oxygen atom; -R1 and R2 independently are monoalkyl ethers of (poly)alkylene glycols in which the hydroxy group has 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 subcycloalkyl; -E independently represents a group selected from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; - When R5 is not a covalent bond, R5 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; and -R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear 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 the formula (II), wherein: -X1 and X2 independently represent an oxygen atom; -R1 and R2 independently represent compounds of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q -(VI), wherein R 13 represents a C1-C4 alkyl or 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 1 to 20, where the range of n + z is from 4 to 10 and w is equal to 1; -L1 is a C3-C 15 subcycloalkyl group, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4'-dicyclohexylmethane; and -E represents the group -O-R3-O-, where R3 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear 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 the formula (II), wherein: -X1 and X2 independently represent an oxygen atom; -R1 and R2 independently represent the compounds of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q -(VI), wherein R 13 represents a C1-C4 alkyl or 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 1 to 20, where the range of n + z is from 4 to 10 and w is equal to 1; -L1 is a C3-C 15 subcycloalkyl group, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylmethane, preferably 4,4-dicyclohexylmethane; and -E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C 18 alkylene group, such as methylene, propylene, butylene or ethylene.

8. The method according to any one of claims 3 to 7, characterized in that The (poly)carbodiimide compound is selected from the compounds of the following formula (XII): Wherein L1 is 4,4'-dicyclohexylmethane, n and z denote integers ranging from 1 to 20, where the range of n + z is from 4 to 10, E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C 18 alkylene group, such as methylene, propylene, butylene or ethylene, and r and s denote 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 compound 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, and still better from 1% to 6% by weight relative to the total weight of the composition C.

10. The method according to any one of the preceding claims, characterized in that, The total amount of the colorant selected from pigments, direct dyes, and mixtures thereof ranges from 0.001% to 20% by weight and preferably from 0.005% to 15% by weight relative to the total weight of the composition C.

11. The method according to any one of the preceding claims, characterized in that, The composition C contains at least one compound containing at least one carboxyl functional group, preferably selected from silicone compounds containing at least one carboxyl, polyurethanes, acrylic polymers, and mixtures thereof.

12. The method according to the preceding claim, characterized in that, The compound containing at least one carboxyl functional group is in the form of an aqueous dispersion of particles of a polymer selected from polyurethanes, acrylic polymers and mixtures thereof, preferably in the form of an aqueous dispersion of acrylic polymer particles, more preferably in the form of an aqueous dispersion of film-forming acrylic polymer particles.

13. The method according to claim 11 or 12, characterized in that, The total amount of the compound containing at least one carboxyl functional group ranges from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 1% to 15% by weight and still better from 2% to 10% by weight relative to the total weight of composition C.

14. The method according to any one of the preceding claims, characterized in that, The step b) of applying steam is separated from the step c) of shaping the keratin hair fibers; preferably, the step c) of shaping follows the step b) of applying steam.

15. The method according to any one of claims 1 to 13, characterized in that, The step b) of applying steam and the step c) of shaping the keratin hair fibers are carried out simultaneously.

16. The method according to any one of the preceding claims, characterized in that, The amount of steam ranges from 0.5 to 60 g / min, preferably from 0.5 to 20 g / min, more preferably from 0.5 to 10 g / min, even more preferably from 0.5 to 5 g / min and still better from 0.5 to 1 g / min.

17. The method according to any one of the preceding claims, characterized in that The temperature during step b) ranges from 100 °C to 250 °C, preferably from 150 °C to 250 °C, more preferably from 150 °C to 230 °C, even more preferably from 180 °C to 220 °C.

18. The method according to any one of the preceding claims, the method comprising a drying step between step a) and step b).

19. The method according to any one of claims 11 to 18, characterized in that, Step a) comprises instantaneously mixing at least two compositions A and B in use to obtain composition C and comprises applying composition C to the keratin hair fibers, wherein: - Composition A comprises at least one (poly)carbodiimide compound as defined in any one of claims 1 to 8; - Composition B comprises at least one compound containing at least one carboxyl functional group as defined in claim 11 or 12, Composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof as defined in claim 1.

20. The method according to any one of the preceding claims, the method comprising a further step after step c): d) applying to the keratin hair fibers at least one composition G comprising at least one (poly)carbodiimide compound as defined in any one of claims 1 to 8; and then e) drying the keratin hair fibers; and then f) optionally, applying steam to the keratin hair fibers in an amount greater than or equal to 0.5 g / min by means of a device capable of generating steam, and g) optionally, shaping the keratin hair fibers at a temperature greater than or equal to 100 °C, preferably between 150 °C and 230 °C.

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