Process for dyeing keratin hair fibres, comprising applying composition comprising (poly) carbodiimide compound, applying heat and applying composition comprising (poly) carbodiimide compound

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; -at least one compound comprising at least one carboxyl function; and-at least one colorant selected from the group consisting of pigments, direct dyes and mixtures thereof; and then b) applying heat to the keratin hair fibres at a temperature greater than or equal to 30 DEG C; and then c) applying to the keratin hair fibres at least one composition G comprising:-at least one (poly) carbodiimide compound; -at least one compound comprising at least one carboxyl functional group.

Description

Technical field

[0001] The present invention relates to a method for dyeing keratinous hair fibers, which comprises applying composition C to the keratinous hair fibers, the composition comprising a (poly)carbodiimide compound, a compound comprising at least one carboxyl functional group, and a colorant, then applying heat at a temperature greater than or equal to 30 °C, and then applying composition G to the keratinous hair fibers, the composition comprising a (poly)carbodiimide compound and a compound comprising at least one carboxyl functional group. Background art

[0002] In the field of dyeing keratinous hair fibers, the known practice is 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 oxidation dyes that penetrate into the keratinous hair fibers and form a dye through an oxidative condensation process;

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

[0006] c) Temporary dyeing, which causes a change in the natural color of the keratinous hair fibers that is retained from one shampoo wash to the next and is used to enhance or correct the tones already obtained. It can also be likened to a "make-up" process.

[0007] Another dyeing method involves the use of pigments. Specifically, using pigments on the surface of keratin fibers generally enables coloring 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 disadvantage of poor tolerance to shampoo washes and also to external agents such as sebum, sweat, brushing and / or friction.

[0008] Therefore, 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 relative to shampoo washes and the various stresses (such as brushing and / or friction) that the keratinous hair fibers may undergo, without compromising the cosmetic properties of the keratinous hair fibers.

[0009] Accordingly, the object of the present invention is to develop a method for dyeing keratinous hair fibers, which has the following advantages: obtaining a smooth and uniform coloring coating on the keratinous hair fibers, while forming a coating that is durable with respect to shampoo washing and various stresses (such as brushing and / or friction) that the keratinous hair fibers may undergo, without damaging the keratinous hair fibers. Summary of the Invention

[0010] Accordingly, a subject of the present invention is a method for dyeing keratinous hair fibers, which comprises:

[0011] a) applying to the keratinous hair fibers at least one composition C, which comprises:

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

[0013] - at least one compound comprising at least one carboxyl functional group; and

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

[0015] b) applying heat to the keratinous hair fibers at a temperature greater than or equal to 30 °C; and then

[0016] c) applying to the keratinous hair fibers at least one composition G, which comprises:

[0017] - at least one (poly)carbodiimide compound;

[0018] - at least one compound comprising at least one carboxyl functional group; and then

[0019] d) optionally, applying heat to the keratinous hair fibers at a temperature greater than or equal to 30 °C.

[0020] By means of the method for dyeing keratinous hair fibers according to the present invention, coloring coatings are obtained on the keratinous hair fibers, which enable obtaining a coloring that is visible on all types of keratinous hair fibers and is durable with respect to shampoo washing, while preserving the physical qualities of the keratinous hair fibers. Such coatings can withstand external stresses that the keratinous hair fibers may undergo, such as blow-drying and sweating. The coatings particularly enable obtaining a uniform deposit.

[0021] For the purposes of the present invention, the term "coloring durable with respect to shampoo washing" means that the coloring obtained after one shampoo washing, preferably after five shampoo washings, is durable.

[0022] The term "at least one" means one or more.

[0023] Unless otherwise indicated, the limits of a range of values are included in the range, particularly in the expressions "between... and..." and "ranging from... to...".

[0024] The present invention is not limited to the examples shown. The features of different examples can be combined in particular in variants not shown.

[0025] For the purposes of the present invention and unless otherwise indicated:

[0026] - "Alkyl" denotes a straight-chain or branched-chain saturated group containing, for example, from 1 to 20 carbon atoms;

[0027] - "Aminoalkyl" denotes an alkyl as defined previously, which alkyl contains an NH2 group;

[0028] - "Hydroxyalkyl" denotes an alkyl as defined previously, which alkyl contains an OH group;

[0029] - "Alkylene" denotes a straight-chain or branched-chain divalent saturated C2-C4 hydrocarbon-based group, such as methylene, ethylene or propylene;

[0030] - "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 containing 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 can be substituted by one or more (C1-C4) alkyls such as methyl; preferably, the cycloalkyl is isobornyl;

[0031] - "Cycloalkylene" denotes a divalent cycloalkyl, where "cycloalkyl" is as defined previously, preferably C3-C 12 ;

[0032] - "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 can be substituted by one or more (C1-C4) alkyls such as methyl, preferably tolyl, xylyl or methylnaphthyl; preferably, the aryl represents phenyl;

[0033] - "Arylene" is a divalent aryl, where "aryl" is as defined previously; preferably, the arylene represents phenylene;

[0034] - The term "heterocyclic" group denotes a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based group which contains 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;

[0035] - "Heterocycloalkylene" is a divalent heterocyclic group, where "heterocyclic" is as defined previously;

[0036] - "Aryloxy" denotes aryl-oxy, where "aryl" is as defined previously;

[0037] - "Alkoxy" denotes alkyl-oxy, where "alkyl" is as defined previously;

[0038] - "Acetyloxy" denotes the ester group R-C(O)-O-, where R is an alkyl as defined previously;

[0039] - A "reactive" group is a group capable of forming a covalent bond with another identical or different group through a chemical reaction.

[0040] Unless otherwise indicated, when a compound is mentioned in this patent application, it also includes its optical isomers, its geometric isomers, its tautomers or its salts, either alone or as a mixture.

[0041] The term "keratin hair fiber" means a keratinous hair fiber or hair. In other words, the expressions "keratin hair fiber", "keratinous hair fiber" and "hair" are equivalent in the subsequent parts of the specification.

[0042] For the purposes of the present invention, the term "keratin hair fiber" means a keratinous hair fiber of the head. This term does not correspond to body hair, eyebrows or eyelashes.

[0043] Polycarbodiimide compound

[0044] The composition C used in the context of the method according to the invention contains at least one (poly)carbodiimide compound.

[0045] The composition may contain at least two different (poly)carbodiimide compounds, present as a mixture in the composition.

[0046] 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.

[0047] The term "carbodiimide group" means a divalent straight-chain triatomic moiety of the general formula -(N=C=N)-.

[0048] 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.

[0049] 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.

[0050] According to a specific embodiment, the (poly)carbodiimide compound is selected from the compounds of the following formula (I):

[0051]

[0052] wherein:

[0053] -X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0054] - 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;

[0055] - n indicates an integer ranging from 1 to 1000; and

[0056] - A is a monomer selected from the following compounds:

[0057]

[0058] According to another embodiment, the (poly)carbodiimide compound is selected from compounds of the following formula (I’):

[0059]

[0060] Wherein:

[0061] - X1 and X2 independently represent an oxygen atom O, a sulfur atom S, or an NH group;

[0062] - 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-terminal heteroatoms, such as nitrogen atoms, oxygen atoms, sulfur atoms, or combinations thereof;

[0063] - Z1 and Z2 independently represent a reactive end group or an inert end group;

[0064] - 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, wherein the aliphatic and aromatic groups optionally contain from 1 to 10 heteroatoms selected from nitrogen, oxygen, sulfur and combinations thereof, and the aliphatic or aromatic group can 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 carbamate group, a thiocarbamate group or a urea group;

[0065] - 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;

[0066] - Q represents an organic polymer or 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, carbamate or urea repeating bonds or combinations thereof;

[0067] - 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;

[0068] - r indicates an integer equal to 0 or 1;

[0069] - m indicates an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0070] - m' indicates an integer ranging from 0 to 1000, preferably equal to 0 or 1;

[0071] -n denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1, where m+(m’*n)≥2.

[0072] Preferably, Z1 and Z2 independently represent reactive end groups; more preferably, Z1 and Z2 independently represent 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.

[0073] Such (poly)carbodiimide compounds are sold, for example, by Stahl B.V under the names Permutex XR, or under the name RelcaLink10., or under the name Picassian XL, and compounds of Nisshinbo 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.

[0074] Preferably, the (poly)carbodiimide compound is selected from compounds of the following formula (II):

[0075]

[0076] where:

[0077] -X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0078] -R1 and R2 independently represent a hydrocarbon-based group optionally inserted with one or more heteroatoms;

[0079] -n and z denote integers ranging from 1 to 20, where n+z≥2 and w denotes an integer ranging from 1 to 3;

[0080] -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;

[0081] -E independently represents a group selected from the following:

[0082] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0083] wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms;

[0084] -R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms;

[0085] -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms.

[0086] 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.

[0087] The hydrocarbon-based group may contain one or more cyclic groups.

[0088] The hydrocarbon-based group may be interrupted by one or more heteroatoms especially selected from O, S or N, and / or substituted by 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 which can be introduced in the form of salts.

[0089] 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.

[0090] Preferably, X1 and X2 independently represent an oxygen atom.

[0091] Preferably, 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.

[0092] In a preferred embodiment, R1 and R2 independently are selected from the following groups (i) to (iv):

[0093] (i) A compound of the following formula (III):

[0094] R7-O-C(O)-C(R8)(H)-(III),

[0095] 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.

[0096] (ii) A compound of the following formula (IV):

[0097] R9-[O-CH2-C(H)(R 10 )] p -(IV),

[0098] 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 group, an ethyl group or a butyl group, R 10 is a hydrogen atom or a methyl group and p is equal to 1.

[0099] (iii) A compound of the following formula (V):

[0100] (R 11 )2N-CH2-C(H)(R 12 )-(V),

[0101] 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 group, an ethyl group or a butyl group, and R 12 is a hydrogen atom or a methyl group.

[0102] (iv) A compound of the following formula (VI):

[0103] R 13 -[O-CH2-C(H)(R 14 )] q -(VI),

[0104] 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 group, an ethyl group or a butyl group, and R 14 is a hydrogen atom or a methyl group.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl and q indicates an integer ranging from 4 to 30.

[0109] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), wherein R 13 represents a C1-C4 alkyl or phenyl group, preferably a C1-C4 alkyl group, more preferably methyl, 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.

[0110] Preferably, n indicates an integer ranging from 1 to 20, more preferably from 2 to 20.

[0111] Preferably, z indicates an integer ranging from 1 to 20, more preferably from 2 to 20.

[0112] Preferably, w is equal to 1.

[0113] Preferably, w is equal to 1, and n + z indicates an integer ranging from 4 to 10.

[0114] Preferably, L1 is selected from C1-C 18 divalent aliphatic hydrocarbon-based groups such as methylene, ethylene and propylene, C3-C 15 cycloalkyl groups such as cyclopentyl, cycloheptyl and cyclohexyl, C3-C 12 heterocycloalkyl groups such as imidazolyl, pyrrolyl and furyl, or C6-C 14 arylene groups such as phenylene, and mixtures thereof.

[0115] 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.

[0116] Preferably, L1 is selected from C3-C 15 subcycloalkyl or C6-C 14 arylene, and mixtures thereof, such as a compound of the following formula (VII):

[0117]

[0118] Preferably, L1 is 4,4-dicyclohexylenemethane corresponding to the following formula (VIII):

[0119]

[0120] According to another embodiment, when L1 is C6-C 14 arylene, L1 is not m-tetramethylxylylene represented by the following formula (IX):

[0121]

[0122] As previously noted, E independently represents a group selected from the following:

[0123] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0124] wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally inserted with one or more heteroatoms;

[0125] -R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally inserted with one or more heteroatoms; and

[0126] -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally inserted with one or more heteroatoms.

[0127] Preferably, R3 and R4 are independently selected from C6-C 14 arylene such as phenylene, C3-C 12Cycloalkylene groups such as cyclopropylidene and cyclobutylidene, linear or branched C 11 -C 18 alkylene groups such as methylene and ethylene, and mixtures thereof.

[0128] More preferably, R3 and R4 are independently selected from linear or branched C1-C optionally interrupted by one or more heteroatoms 18 alkylene groups, such as methylene, butylene, propylene or ethylene.

[0129] Preferably, when R5 is not a covalent bond, R5 is selected from C6-C optionally interrupted by one or more heteroatoms 14 arylene groups such as phenylene, C3-C 12 cycloalkylene groups such as cyclopropylidene and cyclobutylidene, linear or branched C1-C 18 alkylene groups such as methylene and ethylene, and mixtures thereof.

[0130] Preferably, R6 is selected from C6-C optionally interrupted by one or more heteroatoms 14 arylene groups such as phenylene, C3-C 12 cycloalkylene groups such as cyclopropylidene and cyclobutylidene, linear or branched C1-C 18 alkylene groups such as methylene and ethylene, and mixtures thereof.

[0131] Preferably, E represents the group -O-R3-O-, where R3 is selected from C6-C optionally interrupted by one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

[0132] More preferably, E represents the group -O-R3-O-, where R3 represents a linear or branched C1-C optionally interrupted by one or more heteroatoms 18 alkylene group, such as methylene, butylene, propylene or ethylene.

[0133] According to a specific embodiment, the (poly)carbodiimide compound is a copolymer derived from an α-methylstyryl isocyanate of the following formula (X):

[0134]

[0135] 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

[0136] n indicates an integer ranging from 2 to 100.

[0137] In this embodiment, the term "alkyl" is as defined previously.

[0138] In this embodiment, the term "cycloalkyl" is as previously defined.

[0139] 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.

[0140] According to another specific embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI):

[0141]

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

[0143] "Alkyl", "cycloalkyl" and "aryl" are as previously defined.

[0144] According to a preferred embodiment, the (poly)carbodiimide compound is selected from the compounds of formula (I) or formula (II), wherein:

[0145] - X1 and X2 independently represent an oxygen atom;

[0146] - R1 and R2 independently 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, preferably monoalkyl ethers of (poly)alkylene glycols in which the hydroxy group has been removed, more preferably the compound of formula (VI) 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;

[0147] - n and z (when they are present) denote integers ranging from 1 to 20, where n + z ≥ 2 and w is equal to 1;

[0148] - 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;

[0149] - A (when it is present) is selected from C1-C 18 divalent aliphatic hydrocarbon-based groups, C3-C 15 subcycloalkyls, C3-C12 Azaheterocycloalkyl or C6-C 14 Arylene, and mixtures thereof, preferably C3-C 15 Cycloalkylene;

[0150] -E (when present) independently represents a group selected from:

[0151] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0152] wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylene, and mixtures thereof;

[0153] -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, straight-chain or branched C1-C 18 Alkylene, and mixtures thereof; and

[0154] -R6 (when present) is selected from C6-C optionally inserted with one or more heteroatoms 14 Arylene, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylene, and mixtures thereof.

[0155] Preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein:

[0156] -X1 and X2 independently represent an oxygen atom;

[0157] -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;

[0158] -n and z indicate integers ranging from 1 to 20, where n + z ≥ 2 and w equals 1;

[0159] -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;

[0160] -E independently represents a group selected from:

[0161] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0162] 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 C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof;

[0163] - 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 C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof;

[0164] - 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 C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

[0165] More preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein:

[0166] - X1 and X2 independently represent an oxygen atom;

[0167] - R1 and R2 are independently a monoalkyl ether of (poly)alkylene glycol from which the hydroxyl group has been removed;

[0168] - n and z indicate integers ranging from 1 to 20, where n + z ≥ 2 and w equals 1;

[0169] - L1 is C3-C 15 cycloalkylene;

[0170] - E independently represents a group selected from:

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

[0172] 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 C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof;

[0173] - 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;14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof; and

[0174] -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.

[0175] Even more preferably, the (poly)carbodiimide compound is selected from the compounds of formula (II), wherein:

[0176] -X1 and X2 independently represent an oxygen atom;

[0177] -R1 and R2 independently represent the following compound of formula (VI):

[0178] R 13 -[O-CH2-C(H)(R 14 )] q -(VI),

[0179] 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;

[0180] -n and z indicate integers ranging from 1 to 20, where n + z ranges from 4 to 10 and w equals 1;

[0181] -L1 is C3-C 15 Cycloalkylene, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylmethane; and

[0182] -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.

[0183] Even more preferably, the (poly)carbodiimide compound is selected from the compounds of formula (II), wherein:

[0184] -X1 and X2 independently represent an oxygen atom;

[0185] -R1 and R2 independently represent the following compound of formula (VI):

[0186] R 13 -[O-CH2-C(H)(R 14 )] q -(VI)

[0187] 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;

[0188] -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;

[0189] -L1 is a C3-C 15 cycloalkanediyl group, such as cyclopentanediyl, cycloheptanediyl, cyclohexanediyl, and 4,4'-dicyclohexylmethanediyl, preferably 4,4'-dicyclohexylmethanediyl; and

[0190] -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.

[0191] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of the following formula (XII):

[0192]

[0193] wherein 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.

[0194] 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.

[0195] Compound containing at least one carboxyl functional group

[0196] 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.

[0197] Preferably, the compound containing at least one carboxyl functional group is selected from silicone compounds containing at least one carboxyl group, polyurethanes, acrylic polymers, and mixtures thereof.

[0198] Polyurethane and acrylic polymers

[0199] 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.

[0200] 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.

[0201] 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.

[0202] 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.

[0203] The aqueous dispersion of polymer particles may be selected from the aqueous dispersion of polyurethane particles.

[0204] More particularly, the polyurethane present in the aqueous dispersion used in the present invention is produced by the reaction of:

[0205] - a prepolymer of the following formula (A):

[0206]

[0207] Wherein:

[0208] - R1 represents a divalent group of a dihydroxylated compound;

[0209] - R2 represents a group of an aliphatic or cycloaliphatic polyisocyanate;

[0210] - R3 represents a group of a low molecular weight diol, which is optionally substituted by one or more ionic groups;

[0211] - n represents an integer ranging from 1 to 5, and

[0212] - m is greater than 1;

[0213] - at least one chain extender according to the following formula (B):

[0214] H2N-R4-NH2 (B),

[0215] Wherein R4 represents an alkylene or alkyleneoxy group not substituted by one or more ionic or potential ionic groups; and

[0216] - At least one chain extender according to the following formula (C):

[0217] H2N-R5-NH2 (C),

[0218] wherein R5 represents an alkylene group substituted by one or more ionic or potentially ionic groups.

[0219] 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.

[0220] The polyisocyanates that can be used according to the present invention are especially selected from organic diisocyanates having a molecular weight of from about 112 to 1000, and preferably from about 140 to 400.

[0221] 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 containing 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon-based group containing 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon-based group containing 7 to 15 carbon atoms, or a divalent aromatic hydrocarbon-based group containing 6 to 15 carbon atoms.

[0222] Preferably, R2 represents an organic diisocyanate. As examples of organic diisocyanates, the following may be especially selected: tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 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, 4,4'-diphenylmethane diisocyanate and mixtures with its isomers 2,4-diphenylmethane diisocyanate and optionally 2,2'-diphenylmethane diisocyanate, naphthalene 1,5-diisocyanate, and mixtures thereof.

[0223] Preferably, the diisocyanate is an aliphatic and cycloaliphatic diisocyanate, and more preferably selected from 1,6 - hexamethylene diisocyanate, 3 - isocyanatomethyl - 3,5,5 - trimethylcyclohexyl isocyanate, and mixtures thereof.

[0224] According to the present invention, the term "low - molecular - weight diol" refers to diols having a molecular weight ranging 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.

[0225] Preferably, R3 represents a low - molecular - weight diol containing more than 20 carbon atoms, and 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.

[0226] 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 dimethylolbutanoic acid, dimethylolpropionic acid, carboxyl - containing polycaprolactone diols, and mixtures thereof.

[0227] 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 / gram of polyurethane is present in the polyurethane dispersion.

[0228] The prepolymer is chain - extended by two families of chain - extenders. The first class of chain - extenders corresponds to compounds of the general formula (B).

[0229] The chain extender of formula (B) is preferably selected from alkylene diamines such as hydrazine, ethylenediamine, propylenediamine, 1,4 - butanediamine, piperazine; alkylene diamine 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), ether amines 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 - propanediol, dipropylamine 2 - methyl - 1,3 - propanediol, dipropylamine 1,4 - butanediol, dipropylamine 1,3 - butanediol, dipropylamine 1,6 - hexanediol and dipropylamine cyclohexane - 1,4 - dimethanol; and mixtures thereof.

[0230] The second type of chain extender corresponds to compounds of formula (C). Such compounds preferably have ionic or potentially ionic groups and two groups that can react with isocyanate groups. Such compounds may optionally contain two groups that can react with isocyanate groups and one group that is an ionic group or capable of forming an ionic group.

[0231] The ionic or potentially ionic groups can 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 the groups that can be converted into tertiary ammonium or quaternary ammonium group salts can be carried out before or during mixing with water.

[0232] 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.

[0233] The polyurethane that can be used according to the present invention may also optionally contain compounds (chain terminators) that are located at the chain ends and terminate the chains. Such compounds are particularly described in patents US 7 445 770 and / or US 7 452 770.

[0234] 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.

[0235] Also preferably, based on the weight of the dispersion, the aqueous polyurethane dispersion has a polyurethane (or active material, or solid) content of from 20% to 60% by weight, more preferably from 25% to 55% by weight and still 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 still better from 30% to 50% by weight relative to the total weight of the dispersion.

[0236] 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.

[0237] The polyurethane particles can have an average diameter ranging up to about 1000 nm, for example from about 50 nm to about 800 nm, still better from about 100 nm to about 500 nm. These particle sizes can be measured using a laser particle size analyzer (e.g., Brookhaven BI90).

[0238] 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).

[0239] Also mention may be made of the following aqueous polyurethane dispersions: 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).

[0240] According to a preferred embodiment, the aqueous dispersion of polyurethane particles can be selected from the aqueous dispersions of particles of a compound having the INCI name Polyurethane-35 or a compound having the INCI name Polyurethane-34.

[0241] Preferably, the compound containing at least one carboxyl functional group is in the form of an aqueous dispersion of particles of an acrylic polymer, more preferably in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0242] 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.

[0243] 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.

[0244] 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 esters and / or (meth)acrylamides.

[0245] The units of (meth)acrylic monomers derived from the polymer may optionally be in the form of salts, in particular alkali metal salts, alkaline earth metal salts or ammonium salts, or organic base salts.

[0246] (Meth)acrylic acid ester (also called (meth)acrylate) is advantageously selected from (meth)acrylic acid alkyl esters, especially C1 to C 30 alkyl esters, preferably C1 to C 20 alkyl esters and still better C1 to C 10 alkyl esters; (meth)acrylic acid aryl esters, especially C6 to C 10 aryl esters; and (meth)acrylic acid hydroxyalkyl esters, especially C2 to C6 hydroxyalkyl esters of (meth)acrylic acid.

[0247] Among the (meth)acrylic acid alkyl esters, 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.

[0248] Among the (meth)acrylic acid hydroxyalkyl esters, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0249] Among the (meth)acrylic acid aryl esters, mention may be made of benzyl acrylate and phenyl acrylate.

[0250] Particularly preferred (meth)acrylates are alkyl groups, preferably 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.

[0251] According to the invention, the alkyl group of the ester can be fluorinated or even perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms.

[0252] As (meth)acrylamides, examples that can be mentioned include (meth)acrylamide and also N-alkyl (meth)acrylamides, in particular N-(C2 to C 12 alkyl) (meth)acrylamides. Among the N-alkyl (meth)acrylamides that can be mentioned are N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide and N-undecylacrylamide.

[0253] The acrylic polymer according to the invention can be a homopolymer or a copolymer, advantageously a copolymer, even better a copolymer of (meth)acrylic acid and (meth)acrylate.

[0254] Preferably, the acrylic polymer according to the invention comprises one or more units derived from the following monomers:

[0255] a) (meth)acrylic acid; and

[0256] 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.

[0257] Preferably, the aqueous dispersion of acrylic polymer particles does not contain any surfactant.

[0258] The term "surfactant" refers to any reagent capable of changing the surface tension between two surfaces.

[0259] Among the acrylic polymers according to the present 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.

[0260] The acrylic polymer may optionally comprise one or more additional monomers other than (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylamide monomers.

[0261] As additional monomers, mention will be made, for example, of styrene monomers, in particular styrene and α-methylstyrene, and preferably styrene.

[0262] In particular, the acrylic polymer may be a styrene / (meth)acrylate copolymer and in particular a copolymer resulting from the polymerization of at least one styrene monomer and at least one C1 to C 20 alkyl ester of (meth)acrylic acid, preferably C1 to C 10 alkyl ester monomers.

[0263] (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.

[0264] 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.

[0265] Preferably, composition C comprises an aqueous dispersion of at least one acrylic polymer particle.

[0266] 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:

[0267] a) (Meth)acrylic acid; and

[0268] b) C1 to C 30 , more preferably C1 to C 20 , even more preferably C1 to C 10 , and even more particularly C1 to C4 alkyl (meth)acrylate.

[0269] 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 more preferably from 25% to 50% by weight.

[0270] Silicone acrylate copolymer

[0271] According to a specific embodiment, the silicone compound containing at least one carboxyl group is selected from silicone acrylic copolymers.

[0272] Thus, according to a specific embodiment, the compound containing at least one carboxyl functional group is selected from silicone acrylic copolymers.

[0273] Preferably, the silicone acrylic copolymer comprises:

[0274] - at least one acrylic acid or methacrylic acid or crotonic acid unit; and

[0275] - at least one polydimethylsiloxane (PDMS) unit.

[0276] For the purposes of the present invention, according to what is commonly accepted, the term "polydimethylsiloxane" (also abbreviated as PDMS) refers to any organosilicon polymer or oligomer having a linear structure with a 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-), and contains methyl groups directly attached to said silicon atoms via carbon atoms.

[0277] The PDMS chain that can be used to obtain the copolymer used in the present invention contains at least one polymerizable group, which is preferably located at at least one end of the chain, i.e., the PDMS can contain polymerizable groups, for example, 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.

[0278] 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.

[0279] Preferably, the polymerizable group contains at least one vinyl group.

[0280] 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.

[0281] As previously indicated, the silicone acrylate copolymer preferably contains at least one acrylic acid or methacrylic acid or crotonic acid unit, i.e., at least one unit containing a carboxyl group.

[0282] The term "carboxyl group" means COOH or COO - functional group, COO - The counterion of the group is preferably selected from alkali metals, alkaline earth metals, and quaternary ammonium.

[0283] Preferably, the silicone acrylate copolymer contains:

[0284] - at least one acrylic acid or methacrylic acid or crotonic acid unit, and at least one acrylate or methacrylate or vinyl ester unit; and

[0285] - at least one polydimethylsiloxane (PDMS) unit.

[0286] More preferably, the composition contains one or more silicone acrylate copolymers, which contain:

[0287] - at least one crotonic acid unit and at least one unit selected from the following: crotonic acid alkyl ester unit, where the alkyl is a straight-chain or branched-chain saturated group containing from 1 to 20 carbon atoms; vinyl acetate unit; vinyl alkyl ester unit, where the alkyl is a straight-chain or branched-chain saturated group containing from 2 to 20 carbon atoms; and mixtures thereof; and

[0288] - at least one polydimethylsiloxane (PDMS) unit.

[0289] The term "crotonic acid unit" means a unit derived from a crotonic acid monomer or its salt.

[0290] The term "crotonic acid alkyl ester unit" means a unit derived from a crotonic acid ester monomer, which contains a saturated straight-chain or branched-chain alkyl group containing from 1 to 20 carbon atoms.

[0291] The term "vinyl alkyl ester unit" means a unit derived from a vinyl ester monomer, which contains a saturated straight-chain or branched-chain alkyl group containing from 2 to 20 carbon atoms.

[0292] The term "vinyl acetate unit" means a unit derived from a vinyl acetate monomer.

[0293] According to a preferred embodiment, the silicone acrylic copolymer comprises:

[0294] - at least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (the alkyl being a saturated straight-chain or branched-chain group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms), and

[0295] - at least one polydimethylsiloxane (PDMS) unit, which preferably comprises at least one polymerizable group containing at least one vinyl.

[0296] According to a particularly preferred embodiment, the silicone acrylic copolymer comprises:

[0297] - at least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (the alkyl being a straight-chain or branched-chain saturated group containing from 6 to 16 carbon atoms), and

[0298] - at least one polydimethylsiloxane (PDMS) unit, which comprises at least one polymerizable group containing at least one vinyl.

[0299] More preferably, the composition comprises one or more silicone acrylic copolymers, which comprise:

[0300] - at least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (the alkyl being a saturated straight-chain or branched-chain group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms); and

[0301] - at least one polydimethylsiloxane (PDMS) unit, which comprises at least one polymerizable group containing at least one vinyl.

[0302] Even more preferably, the composition comprises one or more silicone acrylic copolymers, which comprise:

[0303] - at least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (the alkyl being a saturated straight-chain or branched-chain group containing from 6 to 16 carbon atoms); and

[0304] - at least one polydimethylsiloxane (PDMS) unit, which comprises at least one polymerizable group containing at least one vinyl.

[0305] Among the silicone acrylic copolymers that can be used in the context of the present invention, mention may be made of those marketed by Wacker Chemie AG under the trade name The compound sold as P1101 has the INCI name Crotonic Acid / Ethylene Vinyl C8-12 Isalkyl Ester / VA / Bis-Vinyl Dimethicone Crosspolymer.

[0306] 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.

[0307] The total amount of the aqueous dispersion of particles of polymers 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.

[0308] 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.

[0309] 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.

[0310] Colorant

[0311] 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.

[0312] Preferably, composition C used in the context of the method according to the invention comprises one or more pigments.

[0313] 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% by weight.

[0314] The 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.

[0315] They can be natural, of natural origin or non-natural.

[0316] These pigments can be in the form of pigment powder or paste. They can be coated or uncoated.

[0317] The pigments can be selected, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as mother-of-pearl or glitter flakes, and mixtures thereof.

[0318] The pigments can be mineral pigments. The term "mineral pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann’s encyclopaedia. Among the mineral pigments available in the present invention, iron oxide, chromium oxide, manganese violet, ultramarine, chromium hydrate, iron blue and titanium oxide can be mentioned.

[0319] The pigments can be organic pigments. The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann’s encyclopaedia.

[0320] The 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.

[0321] In particular, the white or colored organic pigments may be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments numbered with Color Index (CI) numbers CI 42090, 69800, 69825, 74100, 74160, yellow pigments numbered with Color Index numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, green pigments numbered with Color Index numbers CI 61565, 61570, 74260, orange pigments numbered with Color Index numbers CI 11725, 45370, 71105, red pigments numbered with Color Index numbers CI12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, such as pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.

[0322] Examples that may also be mentioned include pigment pastes of organic pigments, such as products sold by Hoechst under the following names:

[0323] - Cosmenyl Yellow 10G: Pigment Yellow 3 (CI 11710);

[0324] - Cosmenyl Yellow G: Pigment Yellow 1 (CI 11680);

[0325] - Cosmenyl Orange GR: Pigment Orange 43 (CI 71105);

[0326] - Cosmenyl Red R: Pigment Red 4 (CI 12085);

[0327] - Cosmenyl Carmine FB: Pigment Red 5 (CI 12490);

[0328] - Cosmenyl Violet RL: Pigment Violet 23 (CI 51319);

[0329] - Cosmenyl Blue A2R: Pigment Blue 15.1 (CI 74160);

[0330] - Cosmenyl Green GG: Pigment Green 7 (CI 74260);

[0331] - Cosmenyl Black R: Pigment Black 7 (CI 77266).

[0332] 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 include an inorganic core, at least one binder for attaching the organic pigment to the core and at least one organic pigment which at least partly covers the core.

[0333] The organic pigment can also be a lake. The term "lake" means a dye adsorbed on insoluble particles, and the assembly thus obtained remains insoluble during use.

[0334] The inorganic substrate on which the dye is adsorbed is for example alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.

[0335] 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 45425), 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 77002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42090).

[0336] Examples of lakes that can be mentioned are products known under the following names: D&C Red 7 (CI 15 850:1).

[0337] 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.

[0338] There are several types of special effect pigments: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacre, interference pigments or glitter flakes.

[0339] 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 coated 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.

[0340] Mention may also be made of nacre having a gold color, 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); nacre having 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); nacre having 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); nacre having a brown color, sold in particular by BASF under the names Nu-antique Copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); nacre having a copper color tone, sold in particular by BASF under the name Copper 340A (Timica); nacre having a red color tone, sold in particular by Merck under the name Sienna Fine (17386) (Colorona); nacre having a yellow color tone, sold in particular by BASF under the name Yellow (4502) (Chromalite); nacre having a red color with a gold color tone, sold in particular by BASF under the name Sunstone G012 (Gemtone); nacre having a pink color, sold in particular by BASF under the name Tan Opale G005 (Gemtone); nacre having a black color with a gold color tone, sold in particular by BASF under the name Nu antique Bronze 240AB (Timica); nacre having a blue color, sold in particular by Merck under the name Matte Blue (17433) (Microna); nacre having a white color with a silver color tone, sold in particular by Merck under the name Xirona Silver; and nacre having a golden green pink orange color, sold in particular by Merck under the name Indian Summer (Xirona); and mixtures thereof.

[0341] Still as an example of nacre, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

[0342] Particles comprising a glass substrate coated with titanium oxide are in particular sold by Toyal under the name Metashine MC1080RY.

[0343] 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.

[0344] 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 their surface state allow them to reflect incident light. If appropriate, when they are 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 look shiny and brighter in contrast to their surroundings.

[0345] Reflective particles can be chosen so as not to significantly alter the coloring effect produced by the colorants combined with them, and more specifically 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.

[0346] These particles can have different forms and can in particular be in the form of flakes or spheres, especially in the spherical form.

[0347] 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 of a reflective material.

[0348] When the reflective particles do not have a multilayer structure, they can be constituted by for example metal oxides, in particular titanium or iron oxides obtained synthetically.

[0349] 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.

[0350] 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, this list not being restrictive.

[0351] The reflective material may include a metal layer or a layer of a metallic material.

[0352] Reflective particles are described in particular in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0353] Furthermore, 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.

[0354] Particles having a silver-coated glass substrate in flake form 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.

[0355] Particles comprising a metallic substrate may also be used, said metallic substrate such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, said at least one metal oxide such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxide, and mixtures thereof.

[0356] 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.

[0357] 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.

[0358] 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.

[0359] 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.

[0360] The pigments can be dispersed in the composition by means of a dispersant.

[0361] The dispersant serves to protect the dispersed particles from agglomeration or flocculation. The dispersant can be a surfactant, oligomer, polymer or a mixture of several of these, carrying one or more functional groups having a strong affinity for the surface of the particles to be dispersed. In particular, they can become physically or chemically attached to the surface of the pigment. These dispersants also contain at least one functional group compatible with or soluble in the continuous medium. In particular, esters of 12 - hydroxystearic acid and esters of C8 - C20 fatty acids and esters of polyols such as glycerol or diglycerol are used, for example poly(12 - hydroxystearic acid) stearate with a molecular weight of approximately 750 g / mol, such as the product sold by Avecia under the name Solsperse 21 000, the polyglyceryl - 2 dimer hydroxystearate (CTFA name) sold by Henkel under the index number Dehymyls PGPH, or polyhydroxystearic acid such as the product sold by Uniqema under the index number Arlacel P100, and mixtures thereof.

[0362] As other dispersants which 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 Avecia, and polydimethylsiloxane / oxypropylene mixtures, such as those sold by Dow Corning under the index numbers DC2 - 5185 and DC2 - 5225 C.

[0363] The pigments used in the composition can be surface - treated with an organic reagent.

[0364] 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 can for example be selected 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.

[0365] The surface-treated pigments that can be used in the composition can also have been treated with a mixture of these compounds and / or may have undergone several surface treatments.

[0366] 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.

[0367] Preferably, the surface-treated pigments are coated with an organic layer.

[0368] The organic reagent for treating the pigments can be attached to the pigments by evaporation of the solvent, chemical reaction between the molecules of the surfactant or formation of a covalent bond between the surfactant and the pigments.

[0369] The surface treatment can thus be carried out for example by a chemical reaction of the surfactant with the surface of the pigment and formation of a covalent bond between the surfactant and the pigment or filler. This method is in particular described in patent US 4 578 266.

[0370] Preferably, an organic reagent that is covalently bonded to the pigment is used.

[0371] The reagent for surface treatment can be present in an amount by weight from 0.1% to 50%, preferably by weight from 0.5% to 30% and even more preferably by weight from 1% to 20% relative to the total weight of the surface-treated pigment.

[0372] Preferably, the surface treatment agent for the pigments is selected from the following treatment agents:

[0373] - PEG - silicone treatment agents, such as the AQ surface treatment agent sold by LCW;

[0374] - Polymethylsiloxane treatment agents, such as the SI surface treatment agent sold by LCW;

[0375] - Polydimethylsiloxane treatment agents, such as the Covasil 3.05 surface treatment agent sold by LCW;

[0376] - Polydimethylsiloxane / trimethylsilyl silicate treatment agents, such as the Covasil 4.05 surface treatment agent sold by LCW;

[0377] - Magnesium myristate treatment agents, such as the MM surface treatment agent sold by LCW;

[0378] - Aluminum dimyristate treatment agents, such as the MI surface treatment agent sold by Miyoshi;

[0379] - Perfluoropoly(methyl isopropyl ether) treatment agents, such as the FHC surface treatment agent sold by LCW;

[0380] - Isostearyl sebacate treatment agents, such as the HS surface treatment agent sold by Miyoshi;

[0381] - Perfluoroalkyl phosphate treatment agents, such as the PF surface treatment agent sold by Daito;

[0382] - Acrylate / polydimethylsiloxane copolymer and perfluoroalkyl phosphate treatment agents, such as the FSA surface treatment agent sold by Daito;

[0383] - Polymethylhydrosiloxane / perfluoroalkyl phosphate treatment agents, such as the FS01 surface treatment agent sold by Daito;

[0384] - Acrylate copolymer / polydimethylsiloxane treatment agents, such as the ASC surface treatment agent sold by Daito;

[0385] - Isopropyl triisostearoyl titanate treatment agents, such as the ITT surface treatment agent sold by Daito;

[0386] - Acrylate copolymer treatment agents, such as the APD surface treatment agent sold by Daito;

[0387] - Perfluoroalkyl phosphate / isopropyl triisostearoyl titanate treatment agents, such as the PF + ITT surface treatment agent sold by Daito.

[0388] According to a specific embodiment of the present invention, the dispersant is present together with organic or mineral pigments in the form of sub - micron - sized particles in Composition B.

[0389] The term "submicron-sized" or "submicron" 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), in particular between 0.1 and 0.9 μm and preferably between 0.2 and 0.6 μm.

[0390] 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, in particular between 1.5:3.5 and 3.5:1 or even better between 1.75:3 and 3:1.

[0391] 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:

[0392] - 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,

[0393] - Silicone acrylates, such as those sold by Evonik RC 902, RC 922, RC 1041, and RC 1043,

[0394] - 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.

[0395] According to a specific embodiment, the dispersant is cationic.

[0396] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments, or organic pigments.

[0397] 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.

[0398] Preferably, the pigment is selected from iron oxides, especially 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.

[0399] Direct dyes

[0400] The composition C used in the context of the process according to the invention may comprise one or more direct dyes.

[0401] The term "direct dye" means natural and / or synthetic dyes, other than oxidation dyes. These are dyes which spread superficially on the fibre.

[0402] They may be ionic or non-ionic, preferably cationic or non-ionic.

[0403] Examples of suitable direct dyes which may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryl types; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, individually or in the form of a mixture.

[0404] The direct dyes are preferably cationic direct dyes. Mention may be made of hydrazinium cationic dyes of the following formulae (XIII) and (XIV) and azo cationic dyes of the formulae (XV) and (XVI):

[0405] Het + -N(Ra)-N=C(Rb)-Ar,Q-(XIII),

[0406] Het + -C(Ra)=N-N(Rb)-Ar,Q(XIV),

[0407] Het + -N=N-AR,Q-(XV),

[0408] AR + -N=N-AR”,Q-(XVI),

[0409] In formulae (XIII) to (XVI):

[0410] -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 such as methyl;

[0411] -Ar +An aryl carrying a cationic charge outside the ring, preferably an ammonium, especially a tri(C1-C8)alkylammonium such as trimethylammonium, such as phenyl or naphthyl;

[0412] -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;

[0413] -Ar” represents an optionally substituted (hetero)aryl, such as phenyl or pyrazolyl, which is optionally preferably substituted by one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl;

[0414] -Ra and Rb may be the same or different and represent a hydrogen atom or a (C1-C8)alkyl optionally preferably substituted by a hydroxyl group;

[0415] 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 a (C1-C4)alkyl optionally substituted by a hydroxyl group;

[0416] -Q- represents an organic or inorganic anionic counterion, such as a halide ion or an alkyl sulfate.

[0417] 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 714 954, are preferably the following direct dyes:

[0418]

[0419] In formulas (XVII) and (XVIII):

[0420] -R 1 represents a (C1-C4)alkyl such as methyl;

[0421] -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

[0422] -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;

[0423] -Z represents a CH group or a nitrogen atom, preferably CH;

[0424] -Q- is an anion counterion as previously defined, in particular a halide ion such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0425] In particular, the dyes of formula (XV) and (XVI) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof, where Q’ is an anion counterion as previously defined, in particular a halide ion such as chloride, or an alkyl sulfate such as methyl sulfate or mesyl.

[0426] 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.

[0427] As acid dyes that can be used in the present invention, mention may be made of the dyes of the following formulae (XIX), (XIX’), (XX), (XX’), (XXI), (XXI’), (XXII), (XXII’), (XXIII), (XXIV), (XXV) and (XXVI):

[0428] a) Diaryl anionic azo dyes of formula (XIX) or (XIX’):

[0429]

[0430] In formulae (XIX) and (XIX’):

[0431] -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:

[0432] -alkyl;

[0433] -Alkoxy, alkylthio;

[0434] -Hydroxy, mercapto;

[0435] -Nitro, nitroso;

[0436] -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;

[0437] -(O)2S(O - )-, M + where M + represents a hydrogen atom or a cationic counterion;

[0438] -(O)CO - -, M + where M + is as previously defined;

[0439] -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;

[0440] -R”’-S(O)2-X’-, where R”’ represents an optionally substituted alkyl or aryl group and X’ is as previously defined;

[0441] -(Di)(alkyl)amino;

[0442] -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;

[0443] -Optionally substituted heteroaryl; preferably benzothiazolyl;

[0444] -Cycloalkyl, especially cyclohexyl;

[0445] -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;

[0446] -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;

[0447] -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, or alternatively, Ra and Rb together with the carbon atom carrying them form a spiroalkyl; preferably, W represents a sulfur atom or Ra and Rb together form a cyclohexyl;

[0448] 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.

[0449] 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;

[0450] And, as examples of the dyes of formula (XIX'), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38;

[0451] b) Pyrazolone anion azo dyes of formula (XX) and (XX’):

[0452]

[0453] In formula (XX) and (XX’):

[0454] -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;

[0455] -R 14 represents a hydrogen atom, an alkyl group or the group -C(O)O - ,M + , where M + is as previously defined;

[0456] -R 15 represents a hydrogen atom;

[0457] -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;

[0458] -R 17 and R 18 may be the same or different and represent a hydrogen atom or a group selected from:

[0459] -(O)2S(O - ),M + , where M + is as previously defined;

[0460] -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;

[0461] -R 19 and R 20 together form a double bond, or an optionally substituted benzoyl group D’;

[0462] -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;

[0463] -R 21represents a hydrogen atom, an alkyl group or an alkoxy group;

[0464] - Ra and Rb may be the same or different, as previously defined; preferably, Ra represents a hydrogen atom and Rb represents an aryl group;

[0465] - Y represents a hydroxyl group or an oxo group;

[0466] - represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;

[0467] It should be understood that formulae (XX) and (XX’) contain at least one sulfonate group (O)2S(O - )-, M + or a carboxylate group -C(O)O - , M + ; preferably sodium sulfonate.

[0468] 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;

[0469] c) Anthraquinone dyes of formulae (XXI) and (XXI’):

[0470]

[0471]

[0472] In formulae (XXI) and (XXI’):

[0473] - 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:

[0474] - alkyl;

[0475] - hydroxyl, mercapto;

[0476] - alkoxy, alkylthio;

[0477] - 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;

[0478] -aryl(alkyl)amino, optionally substituted by one or more groups selected from alkyl and (O)2S(O - )-, M + as previously defined; + as previously defined;

[0479] -(di)(alkyl)amino;

[0480] -(di)(hydroxyalkyl)amino;

[0481] -(O)2S(O - )-, M + as previously defined; + as previously defined;

[0482] -Z’ represents a hydrogen atom or a group NR 28 R 29 wherein R 28 and R 29 may be the same or different and represent a hydrogen atom or a group selected from the following:

[0483] -alkyl;

[0484] -polyhydroxyalkyl such as hydroxyethyl;

[0485] -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 + as previously defined; iii) R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”, wherein R°, X, X’ and X” are as previously defined, preferably R° represents alkyl; + as previously defined;

[0486] -cycloalkyl, especially cyclohexyl;

[0487] -Z represents a group selected from hydroxy and NR’ 28 R’ 29 wherein R’ 28 and R’ 29 may be the same or different and represent an atom or a group the same as R 28 and R 29 as previously defined;

[0488] 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.

[0489] 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;

[0490] d) Nitro dyes of formula (XXII) and (XXII’):

[0491]

[0492] In formulae (XXII) and (XXII'):

[0493] -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:

[0494] -alkyl;

[0495] -alkoxy optionally substituted by one or more hydroxyl groups, alkylthio optionally substituted by one or more hydroxyl groups;

[0496] -hydroxyl, mercapto;

[0497] -nitro, nitroso;

[0498] -polyhaloalkyl;

[0499] -R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”, where R°, X, X’ and X” are as previously defined;

[0500] -(O)2S(O - )-,M + where M + is as previously defined;

[0501] -(O)CO - -,M + where M + is as previously defined;

[0502] -(di)(alkyl)amino;

[0503] -(di)(hydroxyalkyl)amino;

[0504] -heterocycloalkyl, such as piperidino, piperazino or morpholino; In particular, R 30 、R 31and R 32 represents a hydrogen atom;

[0505] -Rc and Rd may be the same or different and represent a hydrogen atom or an alkyl group;

[0506] -W is as previously defined; W particularly represents an -NH- group;

[0507] -ALK represents a straight-chain or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group;

[0508] -n is 1 or 2;

[0509] -p represents an integer between 1 and 5 inclusive;

[0510] -q represents an integer between 1 and 4 inclusive;

[0511] -u is 0 or 1;

[0512] -When n is 1, J represents a nitro or nitroso group; in particular, nitro;

[0513] -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;

[0514] -M’ represents a hydrogen atom or a cationic counterion;

[0515] - may be present or absent and represents an optionally substituted benzogroup by one or more groups R as previously defined 30 substituted;

[0516] 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.

[0517] 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);

[0518] e) Triarylmethane dyes of formula (XXIII):

[0519]

[0520] In formula (XXIII):

[0521] -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;

[0522] -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:

[0523] -alkyl;

[0524] -alkoxy, alkylthio;

[0525] -(di)(alkyl)amino;

[0526] -hydroxy, mercapto;

[0527] -nitro, nitroso;

[0528] -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;

[0529] -(O)2S(O - )-,M + where M + represents a hydrogen atom or a cationic counterion;

[0530] -(O)CO - -,M + where M + is as defined previously;

[0531] -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;

[0532] In particular, R 37 to R 40 represents a hydrogen atom, 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 a (O)2S(O - )- group;

[0533] 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 sulfonic acid.

[0534] 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.

[0535] f) Xanthene-based dyes of formula (XXIV):

[0536]

[0537] In formula (XXIV):

[0538] -R 45 、R 46 、R 47 and R 48 can be the same or different and represent a hydrogen or halogen atom;;

[0539] -R 49 、R 50 、R51 and R 52 may be the same or different and represent a hydrogen or halogen atom, or a group selected from:

[0540] -alkyl;

[0541] -alkoxy, alkylthio;

[0542] -hydroxy, mercapto;

[0543] -nitro, nitroso;

[0544] -(O)2S(O - )-, M + where M + represents a hydrogen atom or a cationic counterion;

[0545] -(O)CO - -, M + where M + is as previously defined;

[0546] In particular, R 49 , R 50 , R 51 and R 52 represent a hydrogen or halogen atom;

[0547] -G represents an oxygen or sulfur atom or the group NRe, where Re is as previously defined; in particular, G represents an oxygen atom;

[0548] -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;

[0549] -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;

[0550] -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;

[0551] -M + is as previously defined.

[0552] 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;

[0553] g) indole-based dyes of formula (XXV):

[0554]

[0555] In formula (XXV):

[0556] -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:

[0557] -alkyl;

[0558] -alkoxy, alkylthio;

[0559] -hydroxy, mercapto;

[0560] -nitro, nitroso;

[0561] -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;

[0562] -(O)2S(O - )-,M + where M + represents a hydrogen atom or a cationic counterion;

[0563] -(O)CO - -,M + where M + is as previously defined;

[0564] -G represents an oxygen or sulfur atom or the group NRe, where Re is as previously defined; in particular, G represents an oxygen atom;

[0565] -Ri and Rh may be the same or different and represent a hydrogen atom or an alkyl group;

[0566] It should 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.

[0567] As examples of the dyes of formula (XXV), mention may be made of: Acid Blue 74;

[0568] h) quinoline-based dyes of formula (XXVI):

[0569]

[0570] In formula (XXVI):

[0571] -R 61 represents a hydrogen or halogen atom or an alkyl group;

[0572] -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;

[0573] Alternatively, R 61 and R 62 , or R 61 and R 64 together form a benzoyl group which is optionally substituted by one or more groups (O)2S(O - ), -M + , where M + represents a hydrogen atom or a cationic counterion;

[0574] It should be understood that formula (XXVI) contains at least one sulfonate group (O)2S(O - ), -M + , preferably sodium sulfonate.

[0575] As examples of the dyes of formula (XXVI), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0576] Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, 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.

[0577] Preferably, the direct dyes are selected from anionic direct dyes.

[0578] 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, based on the total weight of composition C; preferably, the colorant is selected from pigments.

[0579] 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, based on the total weight of composition C.

[0580] 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, based on the total weight of composition C.

[0581] Non-carboxylic acid anionic thickener

[0582] Composition C used in the context of the method according to the invention may also comprise at least one non-carboxylic acid anionic thickener.

[0583] 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 - )

[0584] For the purposes of the present invention, the term "thickener" means a compound that, 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, based on 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.).

[0585] Preferably, the non-carboxylic acid anionic thickener is selected from non-carboxylic acid anionic polymers, and more preferably from anionic polymers carrying sulfonic acid groups.

[0586] For the purposes of the present invention, the term "anionic polymer" means a polymer that contains one or more anionic or anionizable groups and does not contain any cationic or cationizable groups.

[0587] Advantageously, the non-carboxylic acid anionic thickener is selected from anionic polymers comprising at least one ethylenically unsaturated monomer carrying a sulfonic acid group, in free form or in partially or fully neutralized form.

[0588] These polymers may be crosslinked or non-crosslinked. They are preferably crosslinked.

[0589] These polymers can be associative or non-associative, preferably non-associative.

[0590] It is to be understood that "associative polymers" are polymers capable of associating reversibly with each other or with other molecules in an aqueous medium.

[0591] Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.

[0592] The term "hydrophobic group" means a group or polymer having 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.

[0593] 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, dodecanol or decanol. It can also denote a hydrocarbon-based polymer, such as polybutadiene.

[0594] The ethylenically unsaturated monomer carrying a sulfonic acid group is particularly selected from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(C1-C 22 )alkylsulfonic acid, N-(C1-C 22 )alkyl(meth)acrylamido(C1-C 22 )alkylsulfonic acid such as undecylacrylamidomethanesulfonic acid and also its partially or fully neutralized forms.

[0595] More preferably, (meth)acrylamido(C1-C 22 )alkylsulfonic acid 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 its partially or fully neutralized forms.

[0596] More particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and also its partially or fully neutralized forms are used.

[0597] Among the copolymers of 2-acrylamido-2-methylpropanesulfonic acid, mention may be made of the partially or fully neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide; the product described in Example 1 of EP 503 853 may be particularly mentioned, and reference may be made to the said document regarding these polymers.

[0598] Mention may also be made of copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts and hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT 10 by SEPPIC (INCI name: hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer).

[0599] The associative AMPS polymers can be selected in particular from 22 Statistical associative AMPS polymers modified by reaction with n-mono- or di-n-alkylamines, and as described in patent application WO 00 / 31154, forming an integral part of the content of the specification. These polymers may also contain other ethylenically unsaturated hydrophilic monomers selected, for example, from (meth)acrylic acid derivatives, such as their esters with monohydric alcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, or mixtures of these compounds.

[0600] Preferred polymers of this family are selected from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0601] These same copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acid derivatives, especially their esters with monohydric alcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, or mixtures of these compounds.

[0602] These copolymers are described in particular in patent application EP-A 750 899, patent US 5 089 578 and in the following publication by Yotaro Morishima:

[0603] -Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40, (2000), 323-336;

[0604] -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;

[0605] -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;

[0606] -Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers, Polym. Preprint, Div. Polym. Chem. 40(2), (1999), 220 - 221.

[0607] Among these polymers, mention may be made of:

[0608] -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;

[0609] - Terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C6-C 18 )alkylacrylamide units, such as those described in patent US-5089 578.

[0610] 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-dodecyl methacrylamide, such as those described in the Morishima article mentioned above.

[0611] Preferably, the non-carboxylic acid anionic thickener is selected from the sodium 2-acrylamido-2-methylpropane sulfonate / hydroxyethyl acrylate copolymer (INCI name: Hydroxyethyl Acrylate / Acryl Dimethyl Taurate Copolymer) sold by SEPPIC.

[0612] 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.

[0613] Associative polymer

[0614] 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.

[0615] It is to be understood that "associative polymer" is a polymer capable of associating reversibly with each other or with other molecules in an aqueous medium.

[0616] Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.

[0617] 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.

[0618] 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.

[0619] Associative polymers can have nonionic, anionic, cationic or amphoteric properties.

[0620] Preferably, the associative polymers are selected from anionic associative polymers.

[0621] Among the associative polymers of the anionic type, mention may be made of:

[0622] -(a) Those comprising at least one hydrophilic unit and at least one aliphatic allyl ether unit, more particularly those in which the 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.

[0623] 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 aliphatic 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.

[0624] Among the latter polymers, those which are most particularly preferred are crosslinked terpolymers of methacrylic acid, ethyl acrylate and polyethylene glycol (10EO) stearyl ether (steareth-10), in particular those sold by Ciba under the names 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);

[0625] -(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.

[0626] In the present invention, the (C 10 -C 30 ) alkyl esters of unsaturated carboxylic acids 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.

[0627] For example, anionic polymers of this type are described and prepared according to patents US 3 915 921 and US 4 509 949.

[0628] Among anionic associative polymers of this type, those which will be used more particularly are those consisting of 95% to 60% by weight of acrylic acid (hydrophilic units), 4% to 40% by weight of acrylic C 10 -C 30 alkyl esters (hydrophobic units) and 0% to 6% by weight of crosslinkable polymerizable monomers, or alternatively those consisting of 98% to 96% by weight of acrylic acid (hydrophilic units), 1% to 4% by weight of acrylic C 10 -C 30 alkyl esters (hydrophobic units) and 0.1% to 0.6% by weight of crosslinkable polymerizable monomers, such as those previously described.

[0629] Among the polymers described above, those which are most particularly preferred according to the invention are those sold by Goodrich under the trade name Pemulen Pemulen Carbopol and even more preferably Pemulen and also those sold by Ciba under the name Coatex products.

[0630] Also mention may be made of the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer sold by ISP under the name Acrylidone LM.

[0631] -(c) maleic anhydride / C 30 -C 38 α-olefin / maleic acid alkyl ester terpolymers, such as the product sold by Newphase Technologies under the name Performa V (maleic anhydride / C 30 -C 38 α-olefin / isopropyl maleate copolymer).

[0632] -(d) acrylic acid terpolymers which comprise:

[0633] i) approximately 20% to 70% by weight of an α,β-monoethylenically unsaturated carboxylic acid [A],

[0634] ii) approximately 20% to 80% by weight of an α,β-monoethylenically unsaturated non-surfactant monomer other than [A],

[0635] (iii) from about 0.5% to 60% by weight of a non-ionic mono-carbamate which is the reaction product of a mono-surfactant and a mono-ethylenically unsaturated mono-isocyanate,

[0636] such as those described in patent application EP-A-0 173 109 and more particularly the terpolymer described in Example 3, namely a methacrylic acid / methyl acrylate / behenyl dimethyl-m-isopropenyl benzyl isocyanate ethoxylated (40 EO) terpolymer, as a 25% aqueous dispersion.

[0637] -(e) a copolymer which among its monomers comprises an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkyleneated fatty alcohol.

[0638] Preferably, these compounds further comprise, as monomers, an ester of an α,β-monoethylenically unsaturated carboxylic acid and a C1-C4 alcohol.

[0639] Examples of compounds of this type which may be mentioned are Aculyn sold by Rohm & Haas, which is a methacrylic acid / ethyl acrylate / oxyalkyleneated stearyl methacrylate terpolymer; and also Aculyn 88, also sold by Rohm & Haas.

[0640] Advantageously, the associative polymers which are different from the 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.

[0641] Particularly preferably, the associative polymers which are different from the compounds containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickeners described previously are selected from copolymers which among their monomers include an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkyleneated fatty alcohol.

[0642] Advantageously, the total amount of the associative polymers which are different from the 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.

[0643] Organic solvent

[0644] The composition C according to the invention may comprise one or more organic solvents.

[0645] 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.

[0646] The organic solvent may be present in a total amount, relative to the total weight of composition C, by weight between 0.01% and 60%, preferably by weight between 0.05% and 50% and more preferably by weight between 0.1% and 45% and including the end values.

[0647] 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.

[0648] Additive

[0649] Composition C used in the context of the method according to the invention may contain any auxiliaries or additives commonly used.

[0650] Among the additives that may be included in the composition, mention may be made of reducing agents, softening agents, defoaming agents, humectants, UV screening agents, peptizing agents, fragrances, anionic, cationic, non-ionic 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.

[0651] Composition C used in the context of the method according to the invention may in particular be in the form of a suspension, dispersion, gel, emulsion, especially 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, mousse, stick, vesicle dispersion, especially an ionic or non-ionic lipid vesicle dispersion, or a two-phase or multi-phase lotion.

[0652] A person skilled in the art can, based on their general knowledge, first consider the nature of the ingredients used, especially their solubility in the carrier, and secondly the intended application of the composition, to select a suitable presentation form, as well as its preparation method.

[0653] Applying heat to keratinous hair fibers

[0654] According to step b) of the method according to the invention, heat is applied to the keratinous hair fibers at a temperature of greater than or equal to 30 °C.

[0655] The heat application step of the method of the present invention can be carried out using a hood, a hair dryer, a straightener, or a Climazon hood.

[0656] Preferably, the heat application step of the method of the present invention is carried out using a hair dryer and, optionally, a straightener.

[0657] During step b) of applying heat to the keratin hair fibers, a mechanical action such as combing, brushing, or passing fingers through can be applied to the tresses.

[0658] Preferably, in addition to using heat supply, the keratin hair fibers are dried with an air stream. This air stream during drying enables improved separation of the coated tresses.

[0659] During drying, a mechanical action such as combing, brushing, or passing fingers through can be applied to the tresses.

[0660] Advantageously, the temperature range during step b) is from 30°C to 250°C, preferably from 50°C to 220°C.

[0661] Advantageously, step b) includes a step of drying the keratin hair fibers at a temperature in the range from 30°C to 150°C, preferably from 30°C to 110°C, more preferably from 50°C to 110°C.

[0662] Advantageously, step b) includes a step of straightening with a straightener at a temperature in the range from 100°C to 250°C, preferably from 150°C to 220°C, more preferably from 180°C to 220°C.

[0663] When using a hood or a hair dryer during step b) of applying heat to the keratin hair fibers, the temperature is preferably between 30°C and 110°C, preferably between 50°C and 110°C.

[0664] When using a straightener during step b) of applying heat to the keratin hair fibers, the temperature is preferably between 100°C and 250°C, more preferably between 150°C and 220°C.

[0665] In a specific variant, the method of the present invention involves a step (b1) of applying heat using a hood, a hair dryer, or a Climazon hood, preferably a hair dryer, and a step (b2) of applying heat using a straightener or a curler, preferably a straightener.

[0666] Step (b1) can be carried out before step (b2). Preferably, step (b1) is carried out before step (b2).

[0667] During step (b1), the keratin hair fibers can be dried using a hood or a hair dryer, for example, at a temperature of greater than or equal to 30°C, preferably between 30°C and 110°C, more preferably between 50°C and 110°C.

[0668] During step (b2), the passage of a straightener or a curler, preferably a straightener, can be carried out at a temperature ranging from 100°C to 250°C, preferably between 150°C and 220°C, more preferably from 180°C to 220°C.

[0669] Composition G

[0670] The dyeing method according to the invention comprises c) applying at least one Composition G to the keratin hair fibers. Composition G comprises:

[0671] - at least one (poly)carbodiimide compound;

[0672] - at least one compound comprising at least one carboxyl functional group.

[0673] The (poly)carbodiimide compound is as previously defined and has the same preferences as those indicated for Composition C.

[0674] The (poly)carbodiimide compound used in Composition G is the same as or different from, preferably the same as, that used in Composition C.

[0675] 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.

[0676] The compound comprising at least one carboxyl functional group is as previously defined and has the same preferences as those indicated for Composition C.

[0677] The compound comprising at least one carboxyl functional group used in Composition G is the same as or different from, preferably the same as, that used in Composition C.

[0678] 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.

[0679] Composition G may further comprise at least one colorant selected from the pigments, direct dyes, and mixtures thereof as described above.

[0680] Preferably, composition G does not contain any colorants selected from pigments, direct dyes, and mixtures thereof.

[0681] Composition G may further contain a non-carboxylic acid anionic thickener and / or an associative polymer as defined above.

[0682] 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 colorants.

[0683] Applying heat to keratin hair fibers

[0684] According to step d) of the method according to the invention, heat can be applied to keratin hair fibers at a temperature greater than or equal to 30 °C. When carried out, this step can be carried out in the same manner as envisaged in step b) described below.

[0685] Advantageously, the temperature range during step d) is from 30 °C to 250 °C, preferably from 50 °C to 220 °C.

[0686] Scheme

[0687] The composition C described above can be used on wet or dry keratin hair fibers, and also on any type of keratin hair fibers that are golden or brown, natural or dyed, permanently waved, bleached or relaxed.

[0688] According to a specific embodiment of the invention, the keratin hair fibers are washed before applying composition C.

[0689] The washing, rinsing or draining step can be carried out after applying composition C to the keratin hair fibers and before the heat application step b).

[0690] Application to the keratin 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.

[0691] Application of composition C to the keratin hair fibers is usually carried out at room temperature (between 15 °C and 25 °C).

[0692] After applying composition C to the keratin 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, the washing, rinsing or draining step and / or step b).

[0693] After applying composition C, according to step b), heat is applied to the keratin hair fibers at a temperature greater than or equal to 30 °C.

[0694] The method according to the invention thus comprises step b) of applying heat to the keratinous hair fibers using a heating tool as described above.

[0695] Next, according to step d), the above-mentioned composition G is applied to the keratinous hair fibers, and then optionally heat is applied to the keratinous hair fibers at a temperature greater than or equal to 30 °C.

[0696] Preferably, the present invention is a method for dyeing keratinous hair fibers, the method comprising the following steps:

[0697] i) applying to the keratinous hair fibers at least one composition C which comprises:

[0698] - at least one (poly)carbodiimide compound as previously described;

[0699] - at least one compound containing at least one carboxyl functional group as previously described; and

[0700] - at least one colorant selected from pigments, direct dyes and mixtures thereof as previously described; and then

[0701] ii) optionally allowing the composition C to remain on these keratinous hair fibers for a retention time of from 1 minute to 30 minutes, preferably from 1 to 20 minutes; and then

[0702] iii) optionally washing, rinsing or draining the keratinous hair fibers; and then

[0703] iv) applying heat to the keratinous hair fibers at a temperature greater than or equal to 30 °C; and then

[0704] v) applying to the keratinous hair fibers at least one composition G which comprises:

[0705] - at least one (poly)carbodiimide compound as previously described; and

[0706] - at least one compound containing at least one carboxyl functional group as previously described; and then

[0707] vi) optionally allowing the composition G to remain on these keratinous hair fibers for a retention time of from 1 minute to 30 minutes, preferably from 1 to 20 minutes; and then

[0708] vii) optionally washing, rinsing or draining the keratinous hair fibers;

[0709] and then

[0710] viii) Optionally, heat is applied to the keratinous hair fibers at a temperature greater than or equal to 30 °C.

[0711] Preferably, the heat application step b) includes a step of drying the keratinous hair fibers as previously described, optionally followed by a step of straightening with a straightener as previously described.

[0712] Preferably, composition C further comprises at least one non-carboxylic acid anionic thickener as previously described.

[0713] Preferably, composition C further comprises at least one associative polymer as described above that is different from the compound containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickener as previously defined.

[0714] Advantageously, the step of applying composition C to the keratinous hair fibers is repeated several times.

[0715] Preferably, composition G does not contain any colorants selected from pigments, direct dyes, and mixtures thereof as previously described.

[0716] Composition G may further comprise at least one non-carboxylic acid anionic thickener as previously described.

[0717] Preferably, composition G further comprises at least one associative polymer as described above that is different from the compound containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickener as previously defined.

[0718] The step of applying composition G to the keratinous hair fibers may be repeated several times.

[0719] Advantageously, in the dyeing method according to the invention, step a) includes instantaneously mixing at least two compositions A and B at the time of use to obtain composition C and includes applying composition C to the keratinous hair fibers, wherein:

[0720] - Composition A comprises at least one (poly)carbodiimide compound as previously defined;

[0721] - Composition B comprises at least one compound containing at least one carboxyl functional group as previously defined,

[0722] Composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof as previously defined.

[0723] Advantageously, in the dyeing method according to the invention, step c) includes instantaneously mixing at least two compositions E and F at the time of use to obtain composition G and includes applying composition G to the keratinous hair fibers, wherein:

[0724] - Composition E comprises at least one (poly)carbodiimide compound as defined previously;

[0725] - Composition F comprises at least one compound containing at least one carboxyl functional group as defined previously.

[0726] According to a preferred embodiment, the dyeing method according to the invention is a method for dyeing keratinous hair fibers, which method comprises:

[0727] a) Immediately mixing at least two compositions A and B in use to obtain composition C and including applying composition C to said keratinous hair fibers, wherein:

[0728] - Composition A comprises at least one (poly)carbodiimide compound as defined previously;

[0729] - Composition B comprises at least one compound containing at least one carboxyl functional group as defined previously,

[0730] Composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof as defined previously; and then

[0731] b) Applying heat to the keratinous hair fibers at a temperature greater than or equal to 30 °C; and then

[0732] c) Immediately mixing at least two compositions E and F in use to obtain composition G and including applying composition G to said keratinous hair fibers, wherein:

[0733] - Composition E comprises at least one (poly)carbodiimide compound as defined previously;

[0734] - Composition F comprises at least one compound containing at least one carboxyl functional group as defined previously; and then

[0735] d) Optionally, applying heat to the keratinous hair fibers at a temperature greater than or equal to 30 °C.

[0736] Composition A and / or composition B may optionally comprise at least one non-carboxylic acid anionic thickener as described previously and / or 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 defined previously.

[0737] Preferably, composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof as described previously.

[0738] Preferably, composition A does not comprise at least one colorant selected from pigments, direct dyes and mixtures thereof as described previously.

[0739] According to this embodiment, compositions A and B are preferably mixed less than 15 minutes, more preferably less than 10 minutes, still more preferably less than 5 minutes before being applied to the keratinous hair fibers.

[0740] The weight ratio between composition A and composition B preferably ranges from 0.1 to 10, preferably from 0.2 to 5, still more preferably 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.

[0741] Composition E and / or composition F may optionally comprise at least one non-carboxylic acid anionic thickener as described previously and / or 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 defined previously.

[0742] Preferably, compositions E and F do not contain any colorant in an amount sufficient to dye keratinous hair fibers as defined previously, selected from pigments, direct dyes and mixtures thereof. According to a preferred method, compositions E and F do not contain any colorant.

[0743] According to this embodiment, compositions E and F are preferably mixed less than 15 minutes, more preferably less than 10 minutes, still more preferably less than 5 minutes before being applied to the keratinous hair fibers.

[0744] The weight ratio between composition E and composition F preferably ranges from 0.1 to 10, preferably from 0.2 to 5, still more preferably from 0.5 to 2, or even from 0.6 to 1.5. In a specific embodiment, the weight ratio between composition E and composition F is equal to 1.

[0745] 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 more preferably 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.

[0746] 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 more preferably from 1% to 30% by weight, and even more preferably from 2% to 20% by weight relative to the total weight of composition B.

[0747] The total amount of the aqueous dispersion of the particles of the polymer selected from polyurethane, 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.

[0748] 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.

[0749] 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 E.

[0750] 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 F.

[0751] The total amount of the aqueous dispersion of the particles of the polymer selected from polyurethane, 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 F.

[0752] 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 F.

[0753] Multi-compartment device (kit)

[0754] The present invention also relates to a device for dyeing keratinous hair fibers, which comprises a plurality of compartments containing:

[0755] * Composition A in a first compartment, which comprises:

[0756] (1) at least one (poly)carbodiimide compound as previously described;

[0757] *Composition B in the second compartment, which comprises:

[0758] (2) at least one compound containing at least one carboxyl functional group as described previously,

[0759] Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof as described above;

[0760] *Composition E in the third compartment, which comprises:

[0761] (3) at least one (poly)carbodiimide compound as described previously;

[0762] *Composition F in the fourth compartment, which comprises:

[0763] (4) at least one compound containing at least one carboxyl functional group as described previously.

[0764] The present invention also relates to a system for dyeing keratinous hair fibers, which system comprises a first device and a second device,

[0765] - The first device comprises:

[0766] *Composition A in the first compartment, which comprises:

[0767] (1) at least one (poly)carbodiimide compound as described previously;

[0768] *Composition B in the second compartment, which comprises:

[0769] (2) at least one compound containing at least one carboxyl functional group as described previously,

[0770] Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof as described above;

[0771] - The second device comprises:

[0772] *Composition E in the first compartment, which comprises:

[0773] (3) at least one (poly)carbodiimide compound as described previously;

[0774] *Composition F in the second compartment, which comprises:

[0775] (4) at least one compound containing at least one carboxyl functional group as described previously.

[0776] The present invention will now be described more specifically by way of examples, which do not limit the scope of the invention in any way. However, these examples enable the support of specific features, variants, and preferred embodiments of the present invention. Detailed Description

[0777] Examples

[0778] The (poly)carbodiimides of the present invention are obtainable from commercial products or reagents that 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 may 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.

[0779] More specifically, the method for preparing the (poly)carbodiimides of the present invention involves a diisocyanate reagent (1) in a first step:

[0780] O=C=N - L1 - N=C=O (1),

[0781] In formula (1), L1 is as previously defined, which in the presence of a carboimidation catalyst (2) (such as those described in US4 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, reacts to obtain a carbodiimide diisocyanate compound (3):

[0782] O=C=N - L1 - (N=C=N - L1) n - N=C=O (3),

[0783] In formula (3), L1 and n are as previously defined. Benzoyl halides such as benzoyl chloride can be added to deactivate the catalyst.

[0784] 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 the nucleophilic reagent R1-X1-H and then with 0.5 equivalent of the reagent H-E-H, where R1, X1, and E are as defined previously, to obtain the "symmetric" compound (4) according to the invention:

[0785] [R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)]2-E (4),

[0786] In formula (4), R1, X1, L1, n, and E are as defined previously. According to a variant of obtaining compound (4) from (3), 0.5 equivalent of the reagent H-E-H can be added first and then 1 equivalent of the reagent R1-X1-H.

[0787] 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):

[0788] R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-E-H (5),

[0789] In formula (5), R1, X1, L1, n, and E are as defined previously.

[0790] According to a 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.

[0791] During the third step, compound (5) is reacted with 1 equivalent of compound (6)

[0792] R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O(6), which is prepared from compound (3') in advance:

[0793] O=C=N-L1-(N=C=N-L1) z -N=C=O(3'),

[0794] In formula (3'), L1 and z are as defined previously, which 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):

[0795] 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),

[0796] In formula (7), R1, X1, L1, R2, X2, n, z and E are as defined previously.

[0797] One 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):

[0798] H-[E-C(O)-NH-L1-(N=C=N-L1) z w -NH-C(O)-X2-R2 (8),

[0799] 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.

[0800] This last compound (8) can then be reacted with 1 equivalent of the compound (4’):

[0801] R1-X1-C(O)-NH-L1-(N=C=N-L1) n -N=C=O (4’), (the compound (4’) can be synthesized by the reaction of 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:

[0802] 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 -NHC(O)-X2-R2 (9),

[0803] In formula (9), L1, R1, X1, R2, X2, n, z, w and E are as defined previously.

[0804] (Poly)carbodiimide compounds and similarly all reaction intermediates and reagents can be purified via 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. ​​

[0805] Example 1: Method for synthesizing (poly)carbodiimide compounds

[0806] 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.

[0807] The reaction medium was heated at 140 °C for 4 hours under nitrogen, 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.

[0808] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol was introduced into the reaction medium under stirring. The temperature 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.

[0809] After cooling to room temperature, the reaction medium was poured dropwise into a 500 mL glass beaker containing 85 g of distilled water under vigorous stirring to obtain the desired product in the form of a translucent yellow liquid.

[0810] Example 2

[0811] 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 materials as obtained / 100 g.

[0812] [Table 1]

[0813]

[0814]

[0815] (1) Synthesis was carried out according to the synthesis method described in Example 1 (containing 40% active material in water),

[0816] (2) Sold by Ciba under the name Sepinov EMT10 (containing 90% active material),

[0817] (3) Sold by Wacker under the name Belsil ADM LOG 1 (containing 15% active material).

[0818] [Table 2]

[0819]

[0820] (4) Sold by Daito Kasei Kogyo Co., Ltd. under the trade name Daitosol 3000SLPN-PE1 (aqueous dispersion containing 30% active material)

[0821] (5) Sold by Rohm and Haas Company under the trade name Aculyn (alkylene oxide-methylated methacrylic acid / ethyl acrylate / stearyl methacrylate terpolymer containing 30% active material)

[0822] Then, Composition A and Composition B were mixed at a mass ratio of 50 / 50 to obtain Composition C according to the present invention.

[0823] Compositions E and F as described in Tables 3 and 4 below were prepared: Unless otherwise mentioned, the amounts are expressed as g of starting material as obtained / 100 g.

[0824] [Table 3]

[0825]

[0826] [Table 4]

[0827]

[0828] Then, Composition E and Composition F were mixed at a mass ratio of 50 / 50 to obtain Composition G according to the present invention.

[0829] Scheme

[0830] Three application methods were used.

[0831] 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 / tress using a brush. Then, the tress of keratin hair fibers was untangled and dried with a hair dryer, and then combed. Drying with the hair dryer was carried out at a temperature of 100 °C.

[0832] Therefore, this is a comparative method.

[0833] 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 / tress using a brush. Then, the tress of keratin hair fibers was untangled and dried with a hair dryer, and then combed. Drying with the hair dryer was carried out at a temperature of 100 °C.

[0834] Next, the composition G is manually applied to a tress of dry natural keratin hair fibers containing 90% white keratin hair fiber tresses at a rate of 0.8 g of composition per gram of tress using a brush. The tress of keratin hair fibers is then detangled and dried with a hair dryer, and then combed. Drying with the hair dryer is carried out at a temperature of 100 °C.

[0835] Thus, this is the method according to the present invention.

[0836] The methods applied are tabulated in Table 5 below:

[0837] [Table 5]

[0838] Method P1 (comparison) P2 (the present invention) Application of composition C Yes Yes Applying heat Yes Yes Application of composition G - Yes Applying heat - Yes

[0839] Then, tresses of keratin hair fibers treated by methods P1 and P2 are subjected to a test comprising several repeated shampoo washes in order to evaluate the tolerance (persistence) of the obtained coloration with respect to shampoo washes according to the shampoo wash protocol described below.

[0840] Shampoo washing scheme:

[0841] The tresses of dyed keratin hair fibers are combed, wetted with water at 35 °C and then passed through the fingers five times for 5 seconds. Then the tresses of keratin hair fibers are squeezed dry between two fingers.

[0842] A standard shampoo (Garnier Ultra Doux) is uniformly applied to the dyed tresses at a rate of 0.4 g of standard shampoo per gram of tress, and the tresses of keratin hair fibers are gently massaged for 15 seconds along the length from the roots to the ends (6 passes).

[0843] Then the tresses of keratin hair fibers are placed on a watch glass and left to stand for 1 minute.

[0844] Next, the tresses are rinsed with water while passing the tresses of keratin hair fibers through the fingers (15 passes). Then the tresses of keratin hair fibers are squeezed dry between two fingers and then subjected to the next shampoo wash.

[0845] After the test of several shampoo washes, the tresses of keratin hair fibers are combed and dried with a hair dryer.

[0846] Results

[0847] The persistence of the color of the tresses is evaluated using a Minolta CM3610A spectrophotometer (light source D65, angle 10°, including specular reflection component) in the CIE L*a*b* system.

[0848] 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.

[0849] The persistence of the coloring is evaluated by the color difference ΔE between measurements carried out on a tress of hair that has been dyed before shampooing and then after undergoing five shampoo washes, according to the protocol described above. The lower the ΔE value, the more persistent the color is with respect to shampoo washing.

[0850] The ΔE value is calculated according to the following equation:

[0851]

[0852] In this equation, L*, a* and b* represent the values measured after dyeing the keratin hair fibers and after shampoo washing, and L0*, a0* and b0* represent the values measured after dyeing the keratin hair fibers but before shampoo washing.

[0853] [Table 6]

[0854]

[0855] Tresses of keratin hair fibers that have been washed by means of the method P2 according to the invention and washed with five shampoo washes have a significantly lower color difference than tresses of keratin hair fibers treated by the comparative method P1.

[0856] Thus, the coloring coating obtained by means of the method according to the invention shows an improved tolerance to shampoo washing.

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; - at least one compound comprising at least one carboxyl functional group; and - at least one colorant selected from pigments, direct dyes, and mixtures thereof; and then b) applying heat to the keratinous hair fibers at a temperature greater than or equal to 30 °C; and then c) applying to the keratinous hair fibers at least one composition G, the composition comprising: - at least one (poly)carbodiimide compound; - at least one compound comprising at least one carboxyl functional group; and then d) optionally, applying heat to the keratinous hair fibers at a temperature greater than or equal to 30 °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 cycloalkylene group, C3-C 12 a heterocycloalkylene group or C6-C 14 an arylene group, and mixtures thereof; -E independently represents a group selected from the following: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; -R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms.

4. The method according to claim 3, wherein The (poly)carbodiimide compound is selected from the compounds of formula (II), wherein: -X1 and X2 independently represent an oxygen atom; -R1 and R2 independently 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; -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 cycloalkylidene, C3-C 12 a heterocycloalkylidene or C6-C 14 an arylidene, and mixtures thereof; -E independently represents a group selected from the following: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, straight-chain 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 formula (II), wherein: -X1 and X2 independently represent an oxygen atom; -R1 and R2 independently are monoalkyl ethers of (poly)alkylene glycols from 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 the following: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from C6-C 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 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; and -E represents the group -O-R3-O-, where R3 is selected from C6-C optionally interrupted by one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, straight-chain or branched C1-C 18 alkylene, and mixtures thereof.

7. The method according to any one of claims 3 to 6, characterized in that The (poly)carbodiimide compound is selected from the compounds of formula (II), wherein: -X1 and X2 independently represent an oxygen atom; -R1 and R2 independently represent the 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 composition C.

10. 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 composition G.

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

12. The method according to any one of the preceding claims, characterized in that, 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, 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 the preceding claim, characterized in that, The acrylic polymer comprises one or more units derived from the following monomers: a) (Meth)acrylic acid; and b) C1 to C 30 , more preferably C1 to C 20 , still better C1 to C 10 , and even more particularly C1 to C4 alkyl (meth)acrylates.

14. The method according to any one of the preceding claims, characterized in that, 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 C.

15. The method according to any one of the preceding claims, characterized in that, 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.

16. The method according to claim 12 or 13, characterized in that, The total amount of the aqueous dispersion of polymer particles selected from polyurethanes, acrylic polymers, and mixtures thereof 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.

17. The method according to any one of claims 12, 13 and 16, characterized in that, The total amount of the aqueous dispersion of polymer particles selected from polyurethanes, acrylic polymers, and mixtures thereof 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 G.

18. 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 composition C.

19. The method according to any one of the preceding claims, characterized in that, Step b) includes drying the keratin hair fibers at a temperature in the range from 30°C to 150°C, preferably from 30°C to 110°C, and more preferably from 50°C to 110°C.

20. The method according to any one of the preceding claims, characterized in that, Step b) includes straightening with a straightener at a temperature in the range from 100°C to 250°C, preferably from 150°C to 220°C, more preferably from 180°C to 220°C.

21. The method according to any one of the preceding claims, characterized in that, Composition G does not contain any colorant selected from pigments, direct dyes, and mixtures thereof.

22. The method according to any one of the preceding claims, characterized in that, The temperature range during step d) is from 30°C to 250°C, preferably from 50°C to 220°C.

23. The method according to any one of the preceding claims, characterized in that Step a) includes instantaneously mixing at least two compositions A and B during use to obtain composition C and includes applying composition C to the keratin hair fibers, wherein: - Composition A contains 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 any one of claims 1 and 11 to 13. Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof as defined in claim 1.

24. The method according to any one of the preceding claims, characterized in that, Step c) comprises instantaneously mixing at least two compositions E and F in use to obtain Composition G and comprises applying Composition G to the keratinous hair fibers, wherein: - Composition E comprises at least one (poly)carbodiimide compound as defined in any one of claims 1 to 8. - Composition F comprises at least one compound containing at least one carboxyl functional group as defined in any one of claims 1 and 11 to 13.

25. A device for dyeing keratinous hair fibers, the device comprising a number of compartments containing: * Composition A in a first compartment, which comprises: (1) at least one (poly)carbodiimide compound as defined in any one of claims 1 to 8. * Composition B in a second compartment, which comprises: (2) at least one compound containing at least one carboxyl functional group as defined in any one of claims 1 and 11 to 13. Composition A and / or Composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof as defined in claim 1. * Composition E in a third compartment, which comprises: (3) at least one (poly)carbodiimide compound as defined in any one of claims 1 to 8. * Composition F in a fourth compartment, which comprises: (4) at least one compound containing at least one carboxyl functional group as defined in any one of claims 1 and 11 to 13.

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