Method for dyeing keratinous hair fibers comprising application of a particular composition T and application of a (poly)carbodiimide compound and a colorant

Abstract

The present invention relates to a method for dyeing keratin hair fibers, comprising: a) applying to the keratin hair fibers at least one composition T comprising at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant and less than 1% by weight of silicone relative to the total weight of composition T; then b) applying to the keratin hair fibers at least one composition C containing: at least one (poly)carbodiimide compound of formula (II); and at least one colorant chosen from pigments, direct dyes, and mixtures thereof.

Description

[Technical Field]

[0001] The present invention relates to a method for dyeing keratinous hair fibers, which comprises applying to the keratinous hair fibers a specific composition T, followed by application of a composition C comprising a (poly)carbodiimide compound and a colorant. [Background technology]

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

[0003] There are three basic processes for dyeing keratin hair fibers: a) "Permanent" dyeing: its action allows a significant modification of the original color, it uses oxidative dyes that penetrate the keratin hair fiber and form dyes through an oxidative condensation process; b) Non-permanent, semi-permanent or direct dyeing: without using the oxidative condensation process, and resistant to 4-5 shampoo washes. This involves dyeing keratin fibers with a dye composition containing a direct dye; c) Temporary dyeing: modifying the natural color of the keratin hair fiber, remaining from one shampoo wash to the next, and serving to enhance or correct the shade already obtained. This is sometimes associated with the "make-up" process. Summary of the Invention [Problem to be solved by the invention]

[0004] Another dyeing method consists in using pigments, specifically on the surface of the keratin fiber, which makes it possible to obtain a visible color on the generally dark keratin hair fiber, since the surface pigment masks the original color of the fiber. However, the coloration obtained by this dyeing method has the drawback of being less resistant to shampooing, as well as to external agents such as sebum, sweat, brushing and / or friction.

[0005] Therefore, there remains a need for a method for dyeing keratin hair fibers that has the advantage of obtaining a uniform colored coating on the keratin hair fibers and at the same time forming a coating that is durable against shampooing and the various stresses to which the keratin hair fibers may be subjected, such as brushing and / or rubbing, without compromising the cosmetic properties of the keratin hair fibers.

[0006] The object of the present invention is therefore to develop a method for dyeing keratin hair fibers which has the advantage of obtaining a smooth and uniform colored coating on the keratin hair fibers, while at the same time forming a coating which is durable against shampooing and the various stresses to which the keratin hair fibers may be subjected, such as brushing and / or rubbing, without damaging the keratin hair fibers. [Means for solving the problem]

[0007] Thus, one subject of the present invention is a) applying to keratin hair fibers at least one composition T comprising at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant and less than 1% by weight of silicone relative to the total weight of composition T; then b) at least one (poly)carbodiimide compound selected from compounds of formula (II) below, - applying to the keratinous hair fibres at least one composition C containing at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; A method for dyeing keratin hair fibers, comprising: DETAILED DESCRIPTION OF THE INVENTION

[0008] The method for dyeing keratin hair fibers according to the present invention allows obtaining a colored coating on the keratin hair fiber, which makes it possible to obtain a coloration that is visible on every keratin hair fiber, durable against shampooing, and at the same time, maintains the physical quality of the keratin hair fiber. Such a coating can withstand external stresses to which keratin hair fibers may be subjected, such as blow-drying and sweating. This allows obtaining a particularly uniform deposit.

[0009] For the purposes of the present invention, the term "coloration that is durable to shampooing" means that the color obtained persists after one shampooing, preferably after five shampooings.

[0010] The term "at least one" means one or more.

[0011] Unless otherwise specified, the boundaries of a range of values ​​are encompassed within that range, particularly expressions such as "between" and "ranging from."

[0012] The invention is not limited to the illustrated embodiments, and features of the various embodiments may in particular be combined in variations not illustrated.

[0013] For purposes of the present invention, unless otherwise specified: - "Alkyl" group refers to a straight or branched chain saturated group containing, for example, 1 to 20 carbon atoms; - an "aminoalkyl" group refers to an alkyl group as defined above, wherein said alkyl group contains an NH group; - a "hydroxyalkyl" group refers to an alkyl group as defined above, wherein said alkyl group contains an OH group; - an "alkylene" group refers to a linear or branched saturated C2-C4 hydrocarbon-based divalent group, such as methylene, ethylene, or propylene; - a "cycloalkyl" or "alicycloalkyl" group refers to a saturated monocyclic or polycyclic, preferably monocyclic, cyclic hydrocarbon-based group containing one to three rings, preferably two rings, and containing 3 to 24 carbon atoms, in particular 3 to 20 carbon atoms, more particularly 3 to 13 carbon atoms, even more particularly 3 to 12 carbon atoms, preferably 5 to 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, wherein the cycloalkyl group may be optionally substituted by one or more (C1-C4) alkyl groups, such as methyl, in which case it is understood that the cycloalkyl group is preferably an isobornyl group; - "Cycloalkylene" group refers to a group having the above-defined "cycloalkyl", preferably C3-C 12 refers to a divalent cycloalkyl group of the formula: - "aryl" group is a monocyclic, bicyclic or tricyclic, fused or unfused, unsaturated aromatic hydrocarbon-based ring group containing 6 to 14 carbon atoms, preferably 6 to 12 carbon atoms, preferably an aryl group containing one ring having 6 carbon atoms, such as phenyl, naphthyl, phenanthryl, it being understood that phenyl may be substituted with one or more (C1-C4) alkyl groups such as methyl, preferably tolyl, xylyl or methylnaphthyl, preferably an aryl group representing phenyl; - "arylene" group is a divalent aryl group with "aryl" as defined above, preferably arylene represents phenylene; - a "heterocyclic" group is a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based group containing one or more heteroatoms, preferably 1 to 5 atoms selected from O, S or N, and containing 3 to 20 ring members, preferably 5 to 10 ring members, such as, for example, imidazolyl, pyrrolyl, and furanyl; - a "heterocycloalkylene" group is a divalent heterocyclic group having the above-defined "heterocyclic" group; - an "aryloxy" group refers to an aryloxy group having an "aryl" as defined above; - an "alkoxy" group refers to an alkyl-oxy group with "alkyl" as defined above; an "acyloxy" group refers to an ester group RC(O)-O-, where R is an alkyl group as defined above; - A "reactive" group is a group that is capable of forming a covalent bond with another identical or different group by chemical reaction.

[0014] Unless otherwise specified, when a compound is referred to in this patent application, this also includes its optical isomers, its geometric isomers, its tautomers, or its salts, either alone or in mixtures.

[0015] The term "(hair) keratinous fibers" means keratinous hair fibers or hair. In other words, the expressions "(hair) keratinous fibers", "keratinous hair fibers", and "hair" are equivalent in the rest of the description.

[0016] For the purposes of the present invention, the term "keratinous hair fibers" refers to keratinous hair fibers of the head. This term does not correspond to body hair, eyebrows, or eyelashes.

[0017] For the purposes of the present invention, the term "silicone" means a compound containing at least one silicon atom, in particular a silicone polymer, such as dimethicone or amodimethicone.

[0018] Composition T As indicated above, the method according to the invention comprises a) applying to keratin hair fibres at least one composition T comprising at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant and less than 1% by weight of silicone relative to the total weight of the composition.

[0019] Preferably, composition T comprises not more than 0.5% by weight of silicone components relative to the total weight of the composition. More preferentially, composition T does not comprise silicones.

[0020] Composition T used in connection with the dyeing method according to the present invention comprises at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant. The total amount of the anionic and amphoteric surfactants is usually 1% to 50% by weight based on the total weight of composition T.

[0021] Anionic surfactants The term "anionic surfactant" means a surfactant that contains only anionic groups as ionic or ionizable groups.

[0022] As used herein, a chemical species is said to be "anionic" if it has at least one permanent negative charge or if it can be ionized to a negatively charged species under the conditions of use (e.g., medium or pH) of the compositions of the present invention and does not contain any cationic charges.

[0023] Preferably, the anionic surfactant is selected from sulfate-type anionic surfactants.

[0024] For purposes of the present invention, the term "sulfate-type anionic surfactant" refers to an anionic surfactant having one or more sulfate functional groups (-OSO3H or -OSO3 - ) means anionic surfactants containing

[0025] Such surfactants may advantageously be chosen from alkyl sulfates, alkyl ether sulfates, alkyl amido sulfates, alkyl amido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; and salts thereof and mixtures thereof; the alkyl groups of these compounds contain, in particular, from 8 to 30 carbon atoms, preferably from 8 to 26 and more preferentially from 10 to 22 carbon atoms; the aryl groups preferably represent phenyl or benzyl groups; these compounds are optionally polyoxyalkylenated, in particular polyoxyethylenated, and preferably contain from 1 to 50 ethylene oxide units, more preferentially from 2 to 10 ethylene oxide units.

[0026] Preferably, the sulfate-type anionic surfactant is - Alkyl sulfates, especially C8-C 26 , preferably C 10 ~C 22 alkyl sulfates; - alkyl ether sulfates, preferably containing 2 to 10 ethylene oxide units, in particular C8 to C 26 , preferably C 10 ~C 22 Alkyl ether sulfates; especially in the form of alkali metal, alkaline earth metal, ammonium, or amino alcohol salts; and It is selected from mixtures thereof.

[0027] When the anionic surfactants of the sulfate type are in salt form, the salts may be chosen from alkali metal salts such as sodium salts and potassium salts, ammonium salts, amine salts, in particular amino alcohol salts, and alkaline earth metal salts such as magnesium salts, and mixtures thereof.

[0028] Examples of amino alcohol salts that may be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1-propanol salts, 2-amino-2-methyl-1,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.

[0029] Alkali metal or alkaline earth metal salts, especially sodium or magnesium salts, are preferably used.

[0030] Preferably, the anionic surfactants of the sulfate type are sodium, triethanolamine, magnesium or ammonium (C ), oxyethylated with, for example, 1 or 2.2 mol of ethylene oxide. 10 ~C 22 ) alkyl sulfate, sodium, ammonium or magnesium (C 10 ~C 22 ) alkyl ether sulfates, and mixtures thereof.

[0031] Better still, the anionic surfactant of sulfate type is sodium, triethanolamine, ammonium or magnesium (C 10 ~C 22 ) alkyl sulfate, or sodium, triethanolamine, ammonium or magnesium (C 10 ~C 22 ) alkyl ether sulfates, for example the compound sold under the INCI name Sodium Lauryl Sulfate by BASF under the name Texapon Z95P, or the compound sold under the INCI name Sodium Laureth Sulfate by BASF under the name Texapon N701.

[0032] Even more preferentially, the anionic surfactant of sulfate type is (C 10 ~C 22) alkyl ether sulfates and their salts, in particular sodium, triethanolamine, ammonium or magnesium (C 10 ~C 22 ) alkyl ether sulfates.

[0033] According to a preferred embodiment, the anionic surfactant of sulfate type is chosen from sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, and mixtures thereof, more preferentially from sodium lauryl ether sulfate.

[0034] Advantageously, the anionic surfactants are present in a total content ranging from 1% to 50% by weight, preferably from 5% to 40% by weight, more preferentially from 10% to 30% by weight and even more preferentially from 12% to 20% by weight relative to the total weight of composition T.

[0035] Amphoteric or zwitterionic surfactants The amphoteric or zwitterionic surfactant used in Composition T may be an optionally quaternized secondary or tertiary aliphatic amine derivative whose aliphatic group is linear or branched and contains from 8 to 22 carbon atoms, said amine derivative containing at least one anionic group, such as a carboxylate, sulfonate, sulfate, phosphate, or phosphonate group.

[0036] Preferably, these surfactants are not silicone-based surfactants.

[0037] In particular, (C8~C 20 ) Alkyl betaine, (C8-C 20 ) Alkyl sulfobetaine, (C8-C 20 ) alkylamide (C3-C8) alkylbetaine, and (C8-C 20 ) alkylamido (C6-C8) alkylsulfobetaines, and mixtures thereof.

[0038] These compounds are classified in the CTFA Dictionary, 5th Edition (1993) under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid, and cocoamphodipropionic acid.

[0039] An example is cocoamphodiacetate, sold by Rhodia under the trade name Miranol® C2M Concentrate.

[0040] Among the compounds that may be used, mention may be made of the compound classified in the CTFA dictionary under the name diethylaminopropyl cocoaspartamide sodium and sold under the name Chimexane HB by the company Chimex.

[0041] These compounds can be used alone or in mixtures.

[0042] Advantageously, the amphoteric or zwitterionic surfactant is (C8-C 20 ) Alkyl betaine, (C8-C 20 ) Alkyl sulfobetaine, (C8-C20 ) Alkylamide (C3-C8) alkyl betaine, (C8-C 20 ) alkylamido (C6-C8) alkylsulfobetaines, and mixtures thereof, more preferentially (C8-C 20 ) Alkyl betaine, (C8-C 20 ) alkylamido (C3-C8) alkylbetaines, and mixtures thereof, more preferentially (C8-C 20 ) alkylamido (C3-C8) alkylbetaine and mixtures thereof.

[0043] Advantageously, the amphoteric or zwitterionic surfactants are present in a total content ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferentially from 0.75% to 15% by weight, even more preferentially from 1% to 10% by weight and even better still from 1.2% to 5% by weight relative to the total weight of composition T.

[0044] According to a preferred embodiment, composition T comprises one or more anionic surfactants and one or more amphoteric or zwitterionic surfactants.

[0045] Composition T may also comprise water in an amount of at least 60% by weight, better at least 65% by weight and even better at least 70% by weight relative to the total weight of the composition. In particular, it may comprise water in a total amount ranging from 60% to 98% by weight, preferably from 65% to 95% by weight, more preferentially from 70% to 90% by weight and even better from 70% to 85% by weight relative to the total weight of composition T.

[0046] additives The composition T used in connection with the dyeing method according to the invention may contain any adjuvant or additive normally used.

[0047] Among the additives that may be used, mention may be made of reducing agents, thickeners, emollients, moisturizers, UV filters, deflocculants, solubilizers, fragrances, proteins, vitamins, polymers, especially polymers other than silicone, preservatives, oils, waxes, and mixtures thereof.

[0048] Polycarbodiimide Compounds The composition C used in connection with the method according to the invention comprises at least one (poly)carbodiimide compound chosen from compounds of formula (II) below:

[0049] The composition may comprise at least two different (poly)carbodiimide compounds present as a mixture in the composition.

[0050] As shown above, the (poly)carbodiimide compound has the following formula (II): [ka] (In the formula, X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; R1 and R2 independently represent a hydrocarbon-based group optionally interrupted by one or more heteroatoms; n and z represent integers ranging from 1 to 20, with n+z≧2, and w represents an integer ranging from 1 to 3; L1 is independently a divalent C1 to C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 represents arylene groups and mixtures thereof, - E independently -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; - R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms).

[0051] This particular (poly)carbodiimide compound selected from compounds of formula (II) used in connection with the method according to the invention can improve substantivity to shampooing compared to some other (poly)carbodiimide compounds, such as, for example, in particular, those sold under the name Permutex XR.

[0052] The term "hydrocarbon-based group" means a saturated or unsaturated, linear or branched group containing 1 to 300 carbon atoms, preferably 1 to 250 carbon atoms, more preferentially 1 to 200 carbon atoms. Preferably, the hydrocarbon-based group is a saturated linear group.

[0053] The hydrocarbon-based group may contain one or more cyclic groups.

[0054] The hydrocarbon-based group may be interrupted by one or more heteroatoms selected from O, S or N, in particular, and / or may be substituted with one or more cations, anions or zwitterions, or cationic groups such as ammonium, anionic groups such as carboxylate, or zwitterionic groups, and / or may contain metal ions that can be incorporated in the form of a salt.

[0055] The term "heteroatom" means an oxygen O, sulfur S or nitrogen N atom as well as a halogen atom such as Cl, F, Br and I. If a heteroatom is contained in the chain of a hydrocarbon-based group, this heteroatom is preferably selected from an oxygen O, sulfur S or nitrogen N atom.

[0056] Preferably, X1 and X2 independently represent an oxygen atom.

[0057] Preferably, R1 and R2 are independently selected from dialkylamino alcohols from which the hydroxyl groups have been removed, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof.

[0058] In a preferred embodiment, R1 and R2 are independently selected from the following groups (i) to (iv): (i) a compound of formula (III): R7-OC(O)-C(R8)(H)- (III) (wherein R7 represents a C1 to C3 alkyl group, and R8 represents a hydrogen atom or a C1 to C3 alkyl group, and preferably R7 is methyl, and R8 is a hydrogen atom or methyl). (ii) a compound of formula (IV): R9-[O-CH2-C(H)(R 10 )] p - (IV) (wherein R9 represents a C1-C4 alkyl group, R 10 represents a hydrogen atom or a C1-C4 alkyl group, p represents an integer ranging from 1 to 3, preferably R9 is methyl, ethyl or butyl, and R 10 is a hydrogen atom or methyl, and p is equal to 1). (iii) a compound of formula (V): (R 11 )2N-CH2-C(H)(R 12 )- (V) (In the formula, R 11 represents a C1-C4 alkyl group, and R 12 represents a hydrogen atom or a C1-C4 alkyl group, and preferably, R 11 is methyl, ethyl or butyl, and R 12 is a hydrogen atom or methyl). (iv) a compound of formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) (In the formula, R 13 represents a C1-C4 alkyl group, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, q represents an integer ranging from 4 to 30, and preferably, R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl).

[0059] Preferably, R1 and R2 independently represent a compound of formula (VI), R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; and q represents an integer in the range of 4-30.

[0060] According to an alternative embodiment, R1 and R2 are different, and one of the R1 or R2 groups represents a compound of formula (IV) as described above, and the other of the R1 or R2 groups represents a compound of formula (VI) as described above.

[0061] Preferably, in formula (IV), R is methyl, ethyl or butyl, and R 10 is a hydrogen atom or methyl, and p is equal to 1.

[0062] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl, and q is an integer ranging from 4 to 30.

[0063] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; and q represents an integer in the range of 4-30.

[0064] Preferably, n represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0065] Preferably, z represents an integer ranging from 1 to 20, more preferentially from 2 to 20.

[0066] Preferably, w is equal to one.

[0067] Preferably, w is equal to 1 and n+z represents an integer ranging from 4 to 10.

[0068] Preferably, L1 is a divalent C1-C alkyl group such as methylene, ethylene, and propylene. 18 Aliphatic hydrocarbon groups, C3-C such as cyclopentylene, cycloheptylene, and cyclohexylene 15 C3-C such as cycloalkylene groups, imidazole, pyrrolene, and furanylene 12 C6-C such as heterocycloalkylene group or phenylene 14 The arylene group is selected from arylene groups and mixtures thereof.

[0069] For example, L1 may be selected from groups derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-1,3-dioctylcyclobutane, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-napthethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate and phenylene diisocyanate, and mixtures thereof.

[0070] Preferably, L1 is C3 to C 15 Cycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, such as those of the following formula (VII): [ka] The compound is selected from the group consisting of:

[0071] Preferably, L1 is represented by the following formula (VIII): [ka] The corresponding 4,4'-dicyclohexylenemethane is

[0072] According to another embodiment, L1 is C6 to C 14 When L1 is an arylene group, it is represented by the following formula (IX): [ka] It is not an m-tetramethylxylylene group represented by the formula:

[0073] As mentioned earlier, E is independently -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- represents a group selected from wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms.

[0074] Preferably, R3 and R4 are C6-C alkyl groups, such as phenylene, optionally interrupted by one or more heteroatoms. 14 C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 alkylene groups as well as mixtures thereof.

[0075] More preferentially, R3 and R4 are linear or branched C1-C6 alkylenes, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms. 18 alkylene groups.

[0076] Preferably, when R5 is not a covalent bond, R5 is a C6-C6 alkyl group, such as phenylene, optionally interrupted by one or more heteroatoms. 14C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 It is selected from alkylene groups as well as mixtures thereof.

[0077] Preferably, R6 is a C6-C, such as phenylene, optionally interrupted by one or more heteroatoms. 14 C3-C such as arylene groups, cyclopropylene and cyclobutylene 12 Cycloalkylene groups, straight or branched C1-C such as methylene and ethylene 18 It is selected from alkylene groups as well as mixtures thereof.

[0078] Preferably, E represents a -O-R3-O- group, where R3 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups, and mixtures thereof.

[0079] More preferentially, E represents a -O-R3-O- group, where R3 is a linear or branched C1-C6 alkyl group, such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms. 18 Represents an alkylene group.

[0080] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (X): [ka] (In the formula, R independently represents an alkyl group containing 1 to 24 carbon atoms, a cycloalkyl group containing 3 to 24 carbon atoms, or an aryl group containing 6 to 24 carbon atoms, and n represents an integer ranging from 2 to 100.) It is a copolymer derived from α-methylstyryl isocyanate.

[0081] In this embodiment, the term "alkyl group" is as defined above.

[0082] In this embodiment, the term "cycloalkyl group" is as defined above.

[0083] In this embodiment, n may represent an integer ranging from 2 to 50, preferably from 3 to 30, and even more preferentially from 5 to 10.

[0084] According to another particular embodiment, the (poly)carbodiimide compound has the following formula (XI): [ka] (wherein R independently represents an alkyl group containing 1 to 24 carbon atoms, a cycloalkyl group containing 3 to 24 carbon atoms, or an aryl group containing 6 to 24 carbon atoms).

[0085] The "alkyl group", "cycloalkyl group" and "aryl group" are as defined above.

[0086] According to a preferred embodiment, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein: X1 and X2 independently represent an oxygen atom; R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed, and more preferentially R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer ranging from 4 to 30, - when n and z are present, they represent integers ranging from 1 to 20, n+z≧2, and w is equal to 1; - If L1 is present, it is a divalent C1-C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, preferably C3-C 15 cycloalkylene groups; - If A is present, it is a divalent C1-C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 Arylene groups and mixtures thereof, preferably C3-C 15 cycloalkylene groups; - E, if present, is independently -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- wherein R3 and R4 independently represent a group selected from C6-C optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups, and mixtures thereof; - R5 is not a covalent bond, and if R5 is present, it is a C6-C6 bond optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups and mixtures thereof; - When R6 is present, it is a C-C bond optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 The alkylene groups are selected from alkylene groups and mixtures thereof.

[0087] Preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein X1 and X2 independently represent an oxygen atom; R1 and R2 are independently selected from dialkylamino alcohols from which the hydroxyl groups have been removed, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof; n and z represent integers ranging from 1 to 20, n+z≧2, and w is equal to 1; - L1 is divalent C1 to C 18 Aliphatic hydrocarbon group, C3-C 15 Cycloalkylene group, C3-C 12 Heterocycloalkylene group or C6-C 14 arylene groups and mixtures thereof; - E independently -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- wherein R3 and R4 independently represent a group selected from C6-C optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups, and mixtures thereof; When R5 is not a covalent bond, R5 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups, and mixtures thereof; R6 is a C-C group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups, and mixtures thereof.

[0088] More preferentially, the (poly)carbodiimide compound is chosen from compounds of formula (II), in which X1 and X2 independently represent an oxygen atom; R1 and R2 are independently a monoalkyl ether of a (poly)alkylene glycol from which a hydroxyl group has been removed; n and z represent integers ranging from 1 to 20, where n+z≧2 and w is equal to 1; - L1 is C3~C 15 is a cycloalkylene group, - E independently -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- wherein R3 and R4 independently represent a group selected from C6-C optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups, and mixtures thereof; When R5 is not a covalent bond, R5 is a C6-C6 alkyl group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups, and mixtures thereof; R6 is a C-C group optionally interrupted by one or more heteroatoms. 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups, and mixtures thereof.

[0089] Even more preferentially, the (poly)carbodiimide compound is chosen from compounds of formula (II), in which X1 and X2 independently represent an oxygen atom; R1 and R2 independently represent the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )]q - (VI) represents a compound of R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; q represents an integer ranging from 4 to 30; n and z represent integers ranging from 1 to 20, n+z ranging from 4 to 10, and w is equal to 1; - L1 is a C3-C alkyl group such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane. 15 is a cycloalkylene group, - E represents a -O-R-O- group, where R is a C-C alkyl group optionally interrupted by one or more heteroatoms; 14 Arylene group, C3-C 12 Cycloalkylene group, linear or branched C1-C 18 alkylene groups, and mixtures thereof.

[0090] Even more preferentially, the (poly)carbodiimide compound is chosen from compounds of formula (II), in which X1 and X2 independently represent an oxygen atom; R1 and R2 independently represent the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) wherein R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferentially methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; q represents an integer ranging from 4 to 30; n and z represent integers ranging from 1 to 20, n+z ranging from 4 to 10, and w is equal to 1; - L1 is a C3-C alkyl group such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane.15 a cycloalkylene group, preferably 4,4-dicyclohexylenemethane; E is a -O-R-O- group, where R is a linear or branched C-C alkylene such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms; 18 Represents an alkylene group.

[0091] According to a preferred embodiment, the (poly)carbodiimide compound has the following formula (XII): [ka] wherein L1 is 4,4-dicyclohexylenemethane, n and z represent integers ranging from 1 to 20, n+z is in the range of 4 to 10, E represents an -O-R3-O- group, R3 is a linear or branched C1-C alkyl group such as methylene, propylene, butylene, or ethylene, optionally interrupted by one or more heteroatoms. 18 represents an alkylene group, and r and s represent integers ranging from 4 to 30).

[0092] Advantageously, the total amount of (poly)carbodiimide compounds ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferentially from 0.2% to 10% by weight, even more preferentially from 0.5% to 8% by weight and better still from 1% to 6% by weight, relative to the total weight of composition C.

[0093] coloring agent Composition C used in connection with the method according to the invention comprises one or more colorants chosen from pigments, direct dyes and mixtures thereof.

[0094] Preferably, the composition C used in connection with the method according to the invention may comprise one or more pigments.

[0095] The term "pigment" refers to any pigment that colors keratinous materials, the solubility of which in water at 25°C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, preferably less than 0.01% by weight.

[0096] Pigments that can be used are chosen in particular from organic and / or inorganic pigments known in the art, in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and Ullmann's Encyclopedia of Industrial Chemistry.

[0097] These may be natural products of natural origin or non-natural products.

[0098] These pigments may be in the form of pigment powder or paste. They may be coated or uncoated.

[0099] The pigments may be selected, for example, from inorganic pigments, organic pigments, special effect pigments such as lakes, pearlescent agents or glitter flakes, and mixtures thereof.

[0100] The pigment may be an inorganic pigment. The term "inorganic pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann's encyclopedia. Among the inorganic pigments useful in the present invention, mention may be made of iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium oxide.

[0101] The pigment may be an organic pigment. The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann's Encyclopedia.

[0102] The organic pigments may be chosen in particular from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal complexes, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

[0103] In particular, white or colored organic pigments are carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments classified in the Color Index under the reference numbers CI 42090, 69800, 69825, 74100, 74160, yellow pigments classified in the Color Index under the reference numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, green pigments classified in the Color Index under the reference numbers CI 61565, 61570, 74260, orange pigments classified in the Color Index under the reference numbers CI 11725, 45370, 71105, red ... The pigments may be selected from the red pigments classified under the reference numbers 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, and from the pigments obtained by oxidative polymerization of indole or phenol derivatives described in French Patent No. 2 679 771.

[0104] Examples of pigment pastes with organic pigments include those sold by Hoechst under the following names: -Cosmenyl Yellow 10G: Yellow 3 pigment (CI11710); -Cosmenyl Yellow G:Yellow 1 pigment (CI 11680); -Cosmenyl Orange GR: Orange 43 pigment (CI 71105); -Cosmenyl Red R: Red 4 pigment (CI 12085); -Cosmenyl Carmine FB: Red 5 pigment (CI 12490); -Cosmenyl Violet RL: Violet 23 pigment (CI 51319); -Cosmenyl Blue A2R; Blue 15.1 pigment (CI 74160); -Cosmenyl Green GG: Green 7 pigment (CI 74260); -Cosmenyl Black R: Black 7 pigment (CI 77266).

[0105] The pigments according to the invention may also be in the form of composite pigments, as described in EP 1 184 426. These composite pigments may in particular consist of particles comprising an inorganic core, at least one binder binding an organic pigment to the core, and at least one organic pigment covering at least a part of the core.

[0106] The organic pigment may be a lake, the term "lake" referring to a dye adsorbed onto insoluble particles so that the resulting composite remains insoluble during use.

[0107] The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

[0108] Among the dyes, mention may be made of carminic acid. Mention may also be made of products known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

[0109] An example of a lake is a product known as: D&C Red 7 (CI 15 850:1).

[0110] The pigments may also be special effect pigments. The term "special effect pigments" refers to pigments that generally produce a colored appearance (characterized by a particular hue, a particular vividness, and a particular level of brightness) that is not uniform and that varies depending on the conditions of observation (light, temperature, angle of observation, etc.), thereby differing from colored pigments that exhibit standard uniform opaque, translucent, or transparent shades.

[0111] There are several types of special effect pigments: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a high refractive index, such as pearlescent agents, interference pigments or glitter flakes.

[0112] Examples of special effect pigments that may be mentioned include pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxide, mica coated with iron oxide, mica coated with titanium, especially ferric blue or chromium oxide, mica coated with titanium and coated with the organic pigments defined above, and pearlescent pigments based on bismuth oxychloride. Pearlescent pigments that may be mentioned include 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.

[0113] Gold pearlescent agents, in particular those sold by BASF under the names Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite), and Monarch Gold 233X (Cloisonne); bronze pearlescent agents, in particular those sold by Merck under the names Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super bronze (Cloisonne); orange pearlescent agents, in particular those sold by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion Orange (Colorona) and Matte Orange (17449) (Microna); brown pearlescent agents, in particular those sold by BASF under the names Nu-antique Copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); copper-tinged pearlescent agents, in particular those sold by BASF under the name Copper 340A (Timica); red-tinged pearlescent agents, in particular those sold by Merck under the name Sienna Fine (17386) (Colorona); yellow-tinged pearlescent agents, in particular those sold by BASF under the name Yellow (4502) (Chromalite); golden-tinged red pearlescent agents, in particular those sold by BASF under the name Sunstone G012 (Gemtone); pink-tinged pearlescent agents, in particular those sold by BASF under the name Tan Opale those sold under the name G005 (Gemtone); black pearlescent agents with a golden tint, in particular those sold under the name Nu-Antique Bronze 240 AB (Timica) by BASF; blue pearlescent agents, in particular those sold under the name Matte Blue (17433) (Microna) by Merck; white pearlescent agents with a silvery tint, in particular those sold under the name Xirona Silver by Merck;Mention may also be made of gold, green, pink or orange pearlescent agents, in particular those sold under the name Indian Summer (Xirona) by Merck; and mixtures thereof.

[0114] Further examples of pearlescent agents include particles comprising a borosilicate substrate coated with titanium oxide.

[0115] Particles comprising a glass substrate coated with titanium oxide are sold in particular under the name Metashine MC1080RY by the company Toyal.

[0116] Finally, as examples of pearlescent agents, mention may be made of polyethylene terephthalate glitter flakes, in particular those sold under the name Silver 1P 0.004X0.004 (silver glitter flakes) by Meadowbrook Inventions, Inc. Multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate, and aluminum, may also be envisaged.

[0117] The special effect pigments can also be chosen from reflective particles, i.e. particles that, due to their size, structure, in particular the thickness of the layer of which they are composed, as well as their physical and chemical properties and surface condition, are able to reflect incident light. This reflection can, where appropriate, be strong enough to produce, when applied to the support to be made up, a bright spot visible to the naked eye on the surface of the composition or mixture, i.e. a brighter spot that appears to be noticeably brighter than its surroundings.

[0118] The reflective particles may be selected so as not to significantly alter the color effect produced by the colorant with which they are combined, and more particularly to optimize this effect in terms of color rendering, which may more particularly have yellow, pink, red, bronze, orange, brown, gold and / or copper colors or shades.

[0119] These particles may have various morphologies, in particular platelet or spherical morphology, in particular spherical morphology.

[0120] Regardless of their morphology, the reflective particles may or may not have a multi-layer structure, and if they do have a multi-layer structure, they may have at least one layer of a particularly reflective material, for example of uniform thickness.

[0121] If the reflective particles do not have a multilayer structure, they may consist of metal oxides, in particular synthetically obtained titanium oxide or iron oxide.

[0122] When the reflective particles have a multilayer structure, they may comprise, for example, a natural or synthetic substrate, in particular a synthetic substrate, at least partially coated with at least one layer of a reflective material, in particular at least one metal or metallic material. The substrate can be made from one or more organic and / or inorganic materials.

[0123] More particularly, it can be chosen from glass, ceramic, graphite, metal oxides, alumina, silica, silicates, especially aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, without being limited to this list.

[0124] The reflective material may include a metal or a layer of metallic material.

[0125] Reflective particles are described in particular in JP-A-09-188830A, JP-A-10-158450A, JP-A-10-158541A, JP-A-07-258460A and JP-A-05-017710A.

[0126] Further examples of reflective particles comprising an inorganic substrate coated with a metal layer may include particles comprising a borosilicate substrate coated with silver.

[0127] Silver-coated glass-based particles in platelet form are sold by Toyal under the name Microglass Metashine REFSX 2025 PS. Nickel / chromium / molybdenum alloy-coated glass-based particles are sold by the same company under the names Crystal Star GF 550 and GF 2525.

[0128] Particles comprising a metal substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium may also be utilized, said substrate being coated with at least one layer of at least one metal oxide such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxide and mixtures thereof.

[0129] Examples include SiO2 coated aluminum, bronze or copper powders sold under the name Visionaire by the company Eckart.

[0130] Also included are interference pigments that are not bound to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic bright flakes (Geometric Pigments or Spectra f / x from Spectratek).Special effect pigments also include fluorescent pigments (which are either materials that fluoresce in daylight or that exhibit ultraviolet fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments, and quantum dots, such as those sold by Quantum Dots Corporation.

[0131] The variety of pigments that can be used in the present invention makes it possible to obtain a wide range of colors, as well as specific optical effects such as metallic or interference effects.

[0132] The size of the pigments used in the composition according to the invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm, and more preferentially between 30 nm and 50 μm.

[0133] The pigment may be dispersed in the composition with a dispersant.

[0134] Dispersants serve to prevent the aggregation or flocculation of dispersed particles. They may be surfactants, oligomers, polymers, or mixtures of several of these, each containing one or more functional groups with a strong affinity for the surface of the particles to be dispersed. In particular, they can become physically or chemically bound to the pigment surface. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid, especially C8-C20 fatty acids, and polyols such as glycerol or diglycerol, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g / mol, such as the product sold by Avecia under the name Solsperse 21000, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold by Henkel under the trade name Dehymyls PGPH, or other polyhydroxystearic acids, such as the product sold by Uniqema under the trade name Arlacel P100, and mixtures thereof, are used.

[0135] Other dispersants that may be used in the compositions of the invention include quaternary ammonium derivatives of polycondensed fatty acids, such as Solsperse 17000 sold by Avecia, and polydimethylsiloxane / oxypropylene mixtures, such as those sold by Dow Corning under the references DC2-5185 and DC2-5225 C.

[0136] The pigment used in the composition may be surface-treated with an organic agent.

[0137] Thus, pre-surface-treated pigments useful in the present invention are pigments that have been completely or partially surface-treated with organic agents of a chemical, electronic, electrochemical, mechanochemical, or mechanical nature, such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, pp. 53-64, and then dispersed in the compositions of the present invention. These organic agents can be selected, for example, from waxes such as carnauba wax and beeswax; fatty acids, fatty alcohols, and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, and lauric acid and derivatives thereof; anionic surfactants; lecithin; sodium, potassium, magnesium, iron, titanium, zinc, or aluminum salts of fatty acids, such as aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, such as silicones, especially polydimethylsiloxane; organic fluorine compounds, such as perfluoroalkyl ethers; and fluorosilicone compounds.

[0138] The surface-treated pigments useful in the present compositions may be treated with mixtures of these compounds and / or may have been subjected to several surface treatments.

[0139] Surface-treated pigments useful in connection with the present invention may be prepared according to surface treatment techniques well known to those skilled in the art, or may be commercially available as is.

[0140] Preferably, the surface-treated pigment is coated with an organic layer.

[0141] The organic agent for treating the pigment may be deposited onto the pigment by evaporating the solvent, by chemical reaction between molecules of the surface treatment agent, or by forming a covalent bond between the surface treatment agent and the pigment.

[0142] Thus, the surface treatment can be carried out, for example, by chemically reacting a surface treatment agent with the pigment surface to form a covalent bond between the surface treatment agent and the pigment or filler, as described, inter alia, in U.S. Pat. No. 4,578,266.

[0143] Organic agents that are covalently bonded to the pigment are preferably used.

[0144] The agent used for the surface treatment can account for 0.1% to 50% by mass, preferably 0.5% to 30% by mass, and more preferentially 1% to 20% by mass of the total mass of the pigment to be surface treated.

[0145] Preferably, the surface treatment of the pigment is one of the following treatments: - PEG-silicone treatments, such as the AQ surface treatment sold by LCW; - methicone treatments, such as the SI surface treatment sold by LCW; - dimethicone treatments, such as Covasil 3.05 surface treatment sold by LCW; - dimethicone / trimethylsiloxysilicate treatments, such as Covasil 4.05 surface treatment sold by LCW; - magnesium myristate treatments, such as the MM surface treatment sold by LCW; - aluminum dimyristate treatments, such as the MI surface treatment sold by Miyoshi; - perfluoropolymethyl isopropyl ether treatments, such as the FHC surface treatment sold by LCW; - isostearyl sebacate treatment agents, such as the HS surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - perfluoroalkylphosphate treatment agents, such as the PF surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - acrylate / dimethicone copolymer and perfluoroalkylphosphate treatment agents, such as the FSA surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - polymethylhydrogenosiloxane / perfluoroalkylphosphate treatment agents, such as the FS01 surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - acrylate copolymer / dimethicone treatment agents, such as the ASC surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - isopropyl titanium triisostearate treatment agents, such as ITT surface treatment agents sold by Daito Chemical Industry Co., Ltd.; - acrylate copolymer treatment agents, such as the APD surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - Perfluoroalkylphosphate / isopropyl titanium triisostearate treatment agent, such as PF+ITT surface treatment agent sold by Daito Kasei Kogyo Co., Ltd. is selected from.

[0146] According to a particular embodiment of the present invention, the dispersant is present together with an organic or inorganic pigment in particulate form of submicron size.

[0147] The terms "submicron-sized" or "submicron" refer to pigments that have been micronized by a micronization process and have an average particle size of less than 1 micrometer (μm), particularly 0.1 to 0.9 μm, and preferably 0.2 to 0.6 μm.

[0148] According to one embodiment, the dispersant and the pigment are present in an amount (dispersant:pigment) of 1:4 to 4:1, in particular 1.5:3.5 to 3.5:1 or better still 1.75:3 to 3:1, by weight ratio.

[0149] Thus, the dispersant may be an aminosilicone type dispersant other than the aminosilicones described below, which has a silicone backbone, such as a silicone polyether. Suitable dispersants may include: aminosilicones, i.e. silicones containing one or more amino groups, such as those sold by BYK under the name and reference BYK LPX 21879 and by Genesee Polymers under the names and references GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1; silicone acrylates, such as Tego® RC 902, Tego® RC 922, Tego® RC 1041 and Tego® RC 1043 sold by Evonik; - polydimethylsiloxane (PDMS) silicones with carboxyl groups, such as X-22162 and X-22370 from Shin-Etsu Chemical Co., Ltd., epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682 and GP-695 from Genesee Polymers, or Tego® RC1401, Tego® RC1403, Tego® RC1412 from Evonik.

[0150] According to a particular embodiment, the dispersant is of the aminosilicone type other than the aminosilicones described below, and is cationic.

[0151] Preferably, the pigment is selected from inorganic pigments, mixed inorganic-organic pigments or organic pigments.

[0152] In one variant of the invention, the pigment is an organic pigment, preferentially an organic pigment surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment is an inorganic pigment.

[0153] Preferably, the pigment is selected from iron oxides, in particular red, brown or black iron oxides, such as those sold by Sun Chemical under the name SunPuro® Red Iron Oxide.

[0154] direct dye Composition C used in connection with the method according to the invention may comprise one or more direct dyes.

[0155] The term "direct dyes" refers to natural and / or synthetic dyes other than oxidation dyes. These are dyes that diffuse superficially onto the fiber.

[0156] These may be ionic or non-ionic, preferably cationic or non-ionic.

[0157] Examples of suitable direct dyes include azo direct dyes, either alone or in mixtures; (poly)methine dyes such as cyanine, hemicyanine and styryl; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes; and natural direct dyes.

[0158] The direct dyes are preferably cationic direct dyes, and mention may be made of hydrazonocationic dyes of the following formulae (XIX) and (XX) and azocationic dyes of the following formulae (XXI) and (XXII): Het + -N(Ra)-N=C(Rb)-Ar,Q- (XIII) Het + -C(Ra)=NN(Rb)-Ar,Q (XIV) Het + -N=N-Ar,Q- (XV) Ar + -N=N=Ar'',Q- (XVI) (In the formulas (XIII) to (XVI), - Het + represents a cationic heteroaryl group, preferentially having an intracyclic cationic charge, such as imidazolium, indolium or pyridinium, which may be optionally substituted, preferentially with at least one (C1-C8) alkyl group, such as methyl, - Ar +represents an aryl group such as phenyl or naphthyl bearing an exocyclic cationic charge, preferentially ammonium, in particular tri(C1-C8)alkylammonium such as trimethylammonium; - Ar preferentially represents an aryl group optionally substituted by one or more electron-donating groups, in particular phenyl, such as i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8)(alkyl)amino, in which the alkyl group is optionally substituted by a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) optionally substituted N—(C1-C8) alkyl-N-aryl(C1-C8) alkylamino, or alternatively Ar represents a julolidine group; Ar" represents an optionally substituted (hetero)aryl group, such as preferentially phenyl or pyrazolyl, optionally substituted with one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups; Ra and Rb may be the same or different and represent a hydrogen atom or a (C1-C8) alkyl group which may be optionally substituted (preferentially by a hydroxyl group); Or else, Het + the substituents Ra together with the substituents of Ar and / or Rb together with the substituents of Ar together with the atoms carrying them form a (hetero)cycloalkyl; in particular, Ra and Rb represent a (C1-C4) alkyl group optionally substituted with a hydrogen atom or a hydroxyl group; - Q- represents an organic or inorganic anionic counterion such as a halide or alkyl sulfate).

[0159] Mention may be made in particular of azo and hydrazono direct dyes having a cationic charge in the ring of the formulae (XIII) to (XVI) defined above, more particularly the cationic direct dyes having a cationic charge in the ring described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954, preferentially the following direct dyes: [ka] (In formulas (XVII) and (XVIII), -R 1 represents a (C1-C4) alkyl group such as methyl; -R 2 and R 3 may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl; -R 4 represents a hydrogen atom or an electron-donating group, such as optionally substituted (C1-C8) alkyl, optionally substituted (C1-C8) alkoxy, or (di)(C1-C8)(alkyl)amino, wherein the alkyl group is optionally substituted with a hydroxyl group; in particular, R 4 is a hydrogen atom; Z represents a CH group or a nitrogen atom, preferentially CH; Q- is an anionic counterion as defined above, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl).

[0160] In particular, the dyes of formula (XV) and (XVI) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof, and Q′ is an anionic counterion as defined above, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0161] The direct dye may be selected from anionic direct dyes. The anionic direct dyes of the present invention are dyes commonly referred to as "acid" direct dyes due to their affinity for alkaline substances. The term "anionic direct dye" refers to a direct dye containing at least one COR or SOR substituent in its structure, where R represents a hydrogen atom or a cation or ammonium ion derived from a metal or amine. The anionic dye may be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes, and natural acid dyes.

[0162] Acid dyes useful in the present invention include dyes of the following formulae (XIX), (XIX'), (XX), (XX'), (XXI), (XXI'), (XXII), (XXII'), (XXIII), (XXIV), (XXV) and (XXVI).

[0163] a) diaryl anionic azo dyes of formula (XIX) or (XIX'): [ka] (In formulas (XIX) and (XIX'), - R7, R8, R9, R 10 , R'7, R'8, R'9 and R' 10 may be the same or different and represent a hydrogen atom, or - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be the same or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M +(In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above); - R"-S(O)2-, where R" represents a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group, preferentially a phenylamino or phenyl group; - R'''-S(O)2-X'-, where R''' represents an optionally substituted alkyl or aryl group, and X' is as defined above; - (di)(alkyl)amino; - i) nitro; ii) nitroso; iii) (O)2S(O - )-, M + and iv) optionally substituted with one or more groups selected from alkoxy; M + aryl(alkyl)amino, wherein: - optionally substituted heteroaryl; preferentially a benzothiazolyl group; - cycloalkyl, in particular cyclohexyl; - Ar-N=N- (wherein Ar is an optionally substituted aryl group; preferentially one or more alkyl, (O)S(O - )-,M + or phenyl optionally substituted by a phenylamino group) or represents a group selected from - two adjacent groups R7 and R8 or R8 and R9 or R9 and R 10 together form a fused benzo group A'; R'7 and R'8 or R'8 and R'9 or R'9 and R' 10 together form a fused benzo group B'; A' and B' are i) nitro; ii) nitroso; iii) (O)S(O - )-,M +iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N-; and xi) optionally substituted aryl(alkyl)amino, wherein M + , R°, X, X′, X″ and Ar are as defined above; - W represents a sigma bond σ, an oxygen atom or a sulfur atom or a divalent radical: i) -NR-, where R is as defined above, or ii) methylene-C(Ra)(Rb)-, where Ra and Rb, which may be the same or different, represent a hydrogen atom or an aryl group, or alternatively Ra and Rb, together with the carbon atom to which they are attached, form a spirocycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl; Formulas (XIX) and (XIX') contain at least one sulfonate group (O)S(O) on one of the rings A, A', B, B' or C. - )-,M + or one carboxylate group (O)CO - -,M + ; it is understood that it preferentially comprises sodium sulfonate).

[0164] Examples of dyes of formula (XIX) are Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or Sunset Yellow, Examples of dyes of formula (XIX') include Acid Red 111, Acid Red 134, and Acid Yellow 38;

[0165] b) Pyrazolone anionic azo dyes of formula (XX) and (XX'): [ka] (In formulas (XX) and (XX'), -R 11 , R 12 and R 13 may be the same or different and are hydrogen or halogen atoms, alkyl groups or -(O)S(O - ), M+ (In the formula, M + is as defined above); -R 14 represents a hydrogen atom, an alkyl group, or -C(O)O - ,M + group (in the formula, M + is as defined above); -R 15 represents a hydrogen atom; -R 16 represents an oxo group, in which case R' 16 does not exist, or instead, R 15 is R 16 together with and form a double bond; -R 17 and R 18 may be the same or different and represent a hydrogen atom, or - (O)2S(O - )-,M + (In the formula, M + is as defined above); - Ar-OS(O)2-, where Ar represents an optionally substituted aryl group, and preferentially a phenyl group, optionally substituted with one or more alkyl groups. represents a group selected from: -R 19 and R 20 together form either a double bond or an optionally substituted benzo group D'; - R' 16 , R' 19 , and R' 20 may be the same or different and represent a hydrogen atom, an alkyl group, or a hydroxyl group; -R 21 represents a hydrogen atom, an alkyl group, or an alkoxy group; Ra and Rb, which may be the same or different, are as defined above, and preferentially, Ra represents a hydrogen atom and Rb represents an aryl group; Y represents either a hydroxyl group or an oxo group; - [ka] represents a single bond when Y is an oxo group; represents a double bond when Y is a hydroxyl group; Formulas (XX) and (XX') contain at least one sulfonate group (O)S(O) on one of the rings D or E. - )-,M + or one carboxylate group -C(O)O - ,M + ; it is understood that it preferentially comprises sodium sulfonate).

[0166] Examples of dyes of formula (XX) include Acid Red 195, Acid Yellow 23, Acid Yellow 27, and Acid Yellow 76; examples of dyes of formula (XXVI') include Acid Yellow 17;

[0167] c) Anthraquinone dyes of formula (XXI) and (XXI'): [ka] (In formulas (XXI) and (XXI'), -R 22 , R 23 , R 24 , R 25 , R 26 and R 27 may be the same or different and represent a hydrogen atom or a halogen atom, or - alkyl; - hydroxyl, mercapto; - alkoxy, alkylthio; - Alkyl and (O)2S(O - ),M + Optionally substituted aryloxy or arylthio, which are preferentially substituted by one or more groups selected from + is as defined above); - Alkyl and (O)2S(O- )-,M + (M + is as defined above); - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino; - (O)2S(O - )-,M + (In the formula, M + is as defined above) represents a group selected from: Z' is a hydrogen atom or a group NR 28 R 29 represents R 28 and R 29 may be the same or different and represent a hydrogen atom, or - alkyl; - polyhydroxyalkyl, such as hydroxyethyl; one or more groups, in particular i) alkyl, such as methyl, n-dodecyl, n-butyl; ii) (O)S(O - )-, M + (In the formula, M + is as defined above; iii) aryl optionally substituted with R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above and preferentially R° represents an alkyl group); - cycloalkyl; especially cyclohexyl represents a group selected from: - Z is hydroxyl and NR' 28 R' 29 R' represents a group selected from 28 and R' 29 may be the same or different, and R 28 and R 29 represents the same atom or group as Formulas (XXI) and (XXI') contain at least one sulfonate group (O)S(O - )-,M +or one carboxylate group -C(O)O - ,M + ; it is understood that it preferentially comprises sodium sulfonate).

[0168] Examples of dyes of formula (XXI) include Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2, and an example of dyes of formula (XXI') includes Acid Black 48;

[0169] d) Nitro dyes of formula (XXII) and (XXII'): [ka] (In formulas (XXII) and (XXII'), -R 30 , R 31 and R 32 may be the same or different and represent a hydrogen or halogen atom, or - alkyl; - alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups; - hydroxyl, mercapto; - Nitro, nitroso; - polyhaloalkyl; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R°, X, X' and X'' are as defined above); - (O)2S(O - )-,M + (In the formula, M + is as defined above); - (O)CO- -,M + (In the formula, M + is as defined above); - (di)(alkyl)amino; - (di)(hydroxyalkyl)amino; heterocycloalkyl, such as piperidino, piperazino or morpholino In particular, R 30 , R 31 and R 32 represents a hydrogen atom; Rc and Rd may be the same or different and represent a hydrogen atom or an alkyl group; - W is as defined above; W represents, in particular, an -NH- group; - ALK represents a linear or branched divalent C1-C6 alkylene group, in particular ALK represents a -CH2-CH2- group; - n is 1 or 2; - p represents an integer between 1 and 5 (inclusive); - q represents an integer between 1 and 4 (inclusive); - u is 0 or 1; - when n is 1, J represents a nitro or nitroso group, in particular nitro; - when n is 2, J represents an oxygen or sulfur atom or a divalent -S(O)m- group, where m represents an integer 1 or 2, and preferentially J represents a -SO2- group; M' represents a hydrogen atom or a cationic counterion; - [ka] is a group consisting of one or more R 30 represents a benzo group optionally substituted with a group; Formulas (XXII) and (XXII') contain at least one sulfonate group (O)S(O - )-,M + or one carboxylate group -C(O)O - ,M +, and it is understood that it preferentially comprises sodium sulfonate.

[0170] Examples of dyes of formula (XXII) include Acid Brown 13 and Acid Orange 3, and examples of dyes of formula (XXII') include Acid Yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4'-N,N-2''-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7;

[0171] e) Triarylmethane dyes of formula (XXIII): [ka] (In formula (XXIII), -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 arylalkyl; in particular alkyl groups and optionally (O) m S(O - )-, M + group (in the formula, M + and m is as defined above) represents a benzyl group optionally substituted; -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 - alkyl; - alkoxy, alkylthio; - (di)(alkyl)amino; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be the same or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above) or represents a group selected from - two adjacent groups R 41 and R 42 or R 42 and R 43 or R 43 and R 44 together form a fused benzo group: I'; I' is i) nitro; ii) nitroso; iii) (O)S(O - )-,M + iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; and ix) R°-X'-C(X)-X''-; M + , R°, X, X′, and X″ are as defined above; In particular, R 37 ~R 40 represents a hydrogen atom, and R 41 ~R 44 may be the same or different and are a hydroxyl group or (O)S(O - )-,M + represents;R 43 and R 44 together form a benzo group, this is preferentially (O)S(O -)-group; At least one of the rings G, H, I, or I′ contains at least one sulfonate group (O)S(O - )- or one carboxylate group C(O)O - -; it is understood that it preferentially comprises sulfonates).

[0172] Examples of dyes of formula (XXIII) include Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid Green 3, Acid Green 5 and Acid Green 50.

[0173] f) Xanthene dyes of formula (XXIV): [ka] (In formula (XXIV), -R 45 , R 46 , R 47 and R 48 may be the same or different and represent a hydrogen or halogen atom; -R 49 , R 50 , R 51 and R 52 may be the same or different and represent a hydrogen or halogen atom, or - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above) represents a group selected from: In particular, R 49 , R50 , R 51 and R 52 represents a hydrogen or halogen atom; G represents an oxygen or sulfur atom or an NRe group, where Re is as defined above, in particular G represents an oxygen atom; - L is alkoxide O - , M + , thioalkoxide S - , M + or an NRf group (wherein Rf represents a hydrogen atom or an alkyl group, and M + is as defined above, and M + is in particular sodium or potassium); L' is an oxygen or sulfur atom or an ammonium group: N + RfRg, where Rf and Rg may be the same or different and represent a hydrogen atom or an optionally substituted alkyl or aryl group; L' represents, in particular, an oxygen atom or one or more alkyl or (O) m S(O - )-, M + Groups (wherein m and M + represents a phenylamino group optionally substituted with (as defined above); Q and Q', which may be the same or different, represent an oxygen or sulfur atom; in particular, Q and Q' represent an oxygen atom; -M + is as defined above.)

[0174] Examples of dyes of formula (XXIV) include Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; and Acid Violet 9.

[0175] g) Indole dyes of formula (XXV): [ka] (In formula (XXV), -R53 , 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 - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - Nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° represents a hydrogen atom or an alkyl or aryl group, X, X' and X'' may be the same or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); - (O)2S(O - )-,M + (In the formula, M + represents a hydrogen atom or a cationic counterion); - (O)CO - -,M + (In the formula, M + is as defined above) represents a group selected from: G represents an oxygen or sulfur atom or an NRe group, where Re is as defined above, in particular G represents an oxygen atom; Ri and Rh may be the same or different and represent a hydrogen atom or an alkyl group; Formula (XXIII) contains at least one sulfonate group (O)S(O - )-,M + or one carboxylate group -C(O)O - , M + ; it is understood that it preferentially comprises sodium sulfonate).

[0176] An example of a dye of formula (XXV) is Acid Blue 74.

[0177] h) Quinoline dyes of formula (XXVI): [ka] (In formula (XXVI), -R 61 represents a hydrogen atom, a halogen atom, or an alkyl group; -R 62 , R 63 and R 64 may be the same or different and are a hydrogen atom or (O)S(O - )-, M + group (in the formula, M + represents a hydrogen atom or a cationic counterion), or Instead, R 61 and R 62 or R 61 and R 64 together form one or more (O)S(O - )-, M + group (in the formula, M + represents a hydrogen atom or a cationic counterion), forming a benzo group optionally substituted with Formula (XXVI) contains at least one sulfonate group (O)S(O - )-,M + , which is understood to preferentially include sodium sulfonates).

[0178] Examples of dyes of formula (XXVI) include Acid Yellow 2, Acid Yellow 3, and Acid Yellow 5.

[0179] Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or decoctions containing these natural dyes may also be used, in particular poultices or extracts based on henna dye.

[0180] Preferably, the direct dye is selected from anionic direct dyes.

[0181] The colorants may be present in a total amount ranging from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, relative to the total weight of composition C; preferably, the colorants are chosen from pigments.

[0182] The pigments may be present in a total amount ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight, and even better still from 0.5% to 10% by weight relative to the total weight of composition C.

[0183] The direct dyes may be present in a total amount ranging from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight, relative to the total weight of composition C.

[0184] Compounds containing at least one carboxyl functional group Composition C used in connection with the method according to the invention may also comprise at least one compound containing at least one carboxyl function.

[0185] Preferably, composition C used in connection with the method according to the invention comprises at least one compound containing at least one carboxyl function.

[0186] Preferably, the compound containing at least one carboxyl functional group is selected from silicone compounds, polyurethanes, acrylic polymers, and mixtures thereof, all containing at least one carboxyl group.

[0187] Polyurethane and acrylic polymers According to a preferred embodiment, composition C comprises at least one compound containing at least one carboxyl function chosen from polyurethanes, acrylic polymers, and mixtures thereof.

[0188] Preferably, the compound containing at least one carboxyl functional group is in the form of an aqueous dispersion of particles of a polymer selected from polyurethanes, acrylic polymers, and mixtures thereof.

[0189] Preferably, composition C comprises at least one compound containing at least one carboxyl functional group in the form of an aqueous dispersion of particles of polyurethanes, acrylic polymers, and mixtures thereof.

[0190] The dispersion may be a simple dispersion of the cosmetic composition in an aqueous medium. A particular example of a dispersion is a latex.

[0191] The aqueous dispersion of polymer particles may be selected from aqueous dispersions of polyurethane particles.

[0192] More specifically, the polyurethane present in the aqueous dispersion used in the present invention is - the following formula (A) [ka] (In the formula, R1 represents a divalent radical of a dihydroxylated compound, R2 represents the radical of an aliphatic or cycloaliphatic polyisocyanate, R3 represents the radical of a low molecular weight diol optionally substituted with one or more ionic groups, - n represents an integer ranging from 1 to 5; - m is greater than 1) a prepolymer of - the following formula (B): H2N-R4-NH2(B) wherein R4 represents an alkylene or alkylene oxide group that is not substituted with one or more ionic or potentially ionic groups. and at least one chain extender according to - the following formula (C): H2N-R5-NH2(C) wherein R5 represents an alkylene group substituted with one or more ionic or potentially ionic groups. with at least one chain extender.

[0193] Among the dihydroxylated compounds that can be used according to the present invention, mention may be made in particular of compounds containing two hydroxyl groups and having a number average molecular weight of about 700 to about 16,000, preferably about 750 to about 5,000. Examples of dihydroxylated compounds having high molecular weights include polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadiene, polyhydroxylated polythioethers, and mixtures thereof. Preferably, the hydroxylated compound is selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0194] The polyisocyanates that can be used according to the invention are chosen in particular from organic diisocyanates having a molecular weight of about 112 to 1000, preferably about 140 to 400.

[0195] Preferably, the polyisocyanate is selected from diisocyanates, more particularly from those represented by the general formula R2(NCO)2, where R2 represents a divalent aliphatic hydrocarbon group containing 4 to 18 carbon atoms, a divalent alicyclic hydrocarbon group containing 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group containing 7 to 15 carbon atoms, or a divalent aromatic hydrocarbon group containing 6 to 15 carbon atoms.

[0196] Preferably, R2 represents an organic diisocyanate. Examples of organic diisocyanates may be selected in particular from: tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)methane, isomers of toluene diisocyanate (TDI), such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, diphenylmethane 4,4'-diisocyanate and mixtures of its isomer diphenylmethane 2,4-diisocyanate with, optionally, diphenylmethane 2,2'-diisocyanate, naphthalene 1,5-diisocyanate, and mixtures thereof.

[0197] Preferably, the diisocyanates are aliphatic and cycloaliphatic diisocyanates, more preferentially chosen from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate and mixtures thereof.

[0198] The term "low molecular weight diols" according to the present invention refers to diols having a molecular weight of about 62 to 700, preferably 62 to 200. These diols may contain aliphatic, cycloaliphatic or aromatic groups. Preferably, they contain only aliphatic groups.

[0199] Preferably, R3 represents a low molecular weight diol containing more than 20 carbon atoms and is more preferentially selected from ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, neopentyl glycol, butylethylpropanediol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane) and mixtures thereof.

[0200] The low molecular weight diols may optionally contain ionic or potentially ionic groups. Examples of low molecular weight diols containing ionic or potentially ionic groups are described, inter alia, in patent US 3,412,054. Compounds of this type are preferably selected from dimethylol butanoic acid, dimethylol propionic acid, polycaprolactone diols containing carboxyl groups, and mixtures thereof.

[0201] When low molecular weight diols containing ionic or potentially ionic groups are used, they are preferably used in an amount such that less than 0.30 meq of COOH per gram of polyurethane is present in the polyurethane dispersion.

[0202] The prepolymers are chain extended by two families of chain extenders: The first group of chain extenders corresponds to compounds of general formula (B):

[0203] The chain extender of formula (B) is preferably an alkylenediamine, such as hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine; an alkylenediamine oxide, such as 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine (also known as dipropylamine diethylene glycol or DPA-DEG, available from Tomah Products, Milton, Wis.), 2-methyl-1,5-pentanediamine (Dytec A from DuPont), hexanediamine, isophoronediamine, 4,4-methylenedi(cyclohexylamine), Tomah and mixtures thereof.

[0204] The second group of chain extenders corresponds to compounds of general formula (C). Compounds of this type preferably have an ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Compounds of this type may optionally contain two groups that react with isocyanate groups and one group that is ionic or capable of forming an ionic group.

[0205] The ionic or potentially ionic groups may preferably be selected from tertiary or quaternary ammonium groups or groups that can be converted into such groups, carboxyl groups, carboxylate groups, sulfonic acid groups and sulfonate groups. Conversion of at least a portion of the groups that can be converted into salts of tertiary or quaternary ammonium groups may be carried out before or during mixing with water.

[0206] The chain extender of formula (C) is preferably selected from diaminosulfonates, such as the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid, and mixtures thereof.

[0207] The polyurethanes that can be used according to the invention can also optionally contain compounds (chain terminators) located at each chain end to terminate said chains, such compounds being described in particular in US Pat. No. 7,445,770 and / or US Pat. No. 7,452,770.

[0208] Preferably, the viscosity of the aqueous dispersion of polyurethane particles is less than 2000 mPa.s at 23°C, more preferentially less than 1500 and better still less than 1000. Even more preferably, the glass transition temperature of the aqueous dispersion of polyurethane particles is less than 0°C.

[0209] Also preferably, the polyurethane (or active substance or solids) content of the aqueous polyurethane dispersion is from 20% to 60% by weight, more preferentially from 25% to 55% by weight, and even better still from 30% to 50% by weight, based on the weight of the dispersion. This is intended to mean that the polyurethane content (dry matter) of the aqueous dispersion is preferably from 20% to 60% by weight, more preferentially from 25% to 55% by weight, and even better still from 30% to 50% by weight, relative to the total weight of the dispersion.

[0210] Also preferably, the glass transition temperature (Tg) of the aqueous dispersion of polyurethane particles is lower than or equal to -25°C, preferably lower than -35°C and more preferentially lower than -40°C.

[0211] The average size of the polyurethane particles may be up to about 1000 nm, for example, in the range of about 50 nm to about 800 nm, and even better, about 100 nm to about 500 nm. These particle sizes can be measured using a laser particle size distribution analyzer (e.g., Brookhaven BI90).

[0212] Non-limiting examples of aqueous polyurethane dispersions include those sold by Bayer under the Baycusan® name, such as Baycusan® C1000 (INCI name: Polyurethane-34), Baycusan® C1001 (INCI name: Polyurethane-34), Baycusan® C1003 (INCI name: Polyurethane-32), Baycusan® C1004 (INCI name: Polyurethane-35) and Baycusan® C1008 (INCI name: Polyurethane-48).

[0213] Mention may also be made of aqueous polyurethane dispersions of isophthalic acid / adipic acid copolymer / hexylene glycol / neopentyl glycol / dimethylol acid / isophorone diisocyanate (INCI name: Polyurethane-1, for example Luviset® PUR from BASF), polyurethanes of polycarbonate, polyurethanes of aliphatic polyesters and aliphatic polyurethanes (for example the Neorez® or DSM series, for example Neorez® R989 and Neorez® R-2202).

[0214] According to a preferred embodiment, the aqueous dispersion of polyurethane particles may be chosen from aqueous dispersions of particles of a compound having the INCI name Polyurethane-35 or of a compound having the INCI name Polyurethane-34.

[0215] Preferably, the compound containing at least one carboxyl function is in the form of an aqueous dispersion of particles of an acrylic polymer, more preferentially in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0216] For the purposes of the present invention, the term "polymer" means a compound corresponding to the repetition of one or more units, which are derived from compounds known as monomers, where this or these units are repeated at least twice, preferably at least three times.

[0217] The term "film-forming polymer" refers to a polymer that is capable of forming a macroscopically continuous film, preferably a coherent film, on a substrate, in particular on keratinous materials such as keratinous hair fibers, either alone or in the presence of an auxiliary film-forming agent.

[0218] For the purposes of the present invention, the term "acrylic polymer" means a polymer synthesized from at least one monomer selected from (meth)acrylic acid and / or (meth)acrylic acid esters and / or (meth)acrylic acid amides.

[0219] The units of the polymer derived from (meth)acrylic acid monomers may optionally be in the form of a salt, in particular an alkali metal salt, an alkaline earth metal salt or an ammonium salt, or an organic base salt.

[0220] The (meth)acrylic acid esters (also known as (meth)acrylates) are advantageously alkyl (meth)acrylates, in particular C1-C 30 , preferably C1 to C 20 , and even better C1~C 10 Alkyl (meth)acrylates, aryl (meth)acrylates, especially C6-C 10 It is selected from aryl (meth)acrylates and hydroxyalkyl (meth)acrylates, in particular C2 to C6 hydroxyalkyl (meth)acrylates.

[0221] Among the alkyl (meth)acrylates, mention may be made of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and cyclohexyl (meth)acrylate.

[0222] Among the hydroxyalkyl(meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0223] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0224] Particularly preferred (meth)acrylic acid esters are alkyl, preferably C1-C 30 , and more preferentially C1~C 20 , and even better C1 to C 10 and even more particularly C1 to C4 alkyl (meth)acrylates.

[0225] According to the present invention, the alkyl group of the ester may be fluorinated or even perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms.

[0226] Examples of (meth)acrylic acid amides include (meth)acrylamides as well as N-alkyl(meth)acrylamides, particularly N-(C-C 12 Mention may also be made of N-alkyl(meth)acrylamides. Among the N-alkyl(meth)acrylamides, mention may be made of N-ethylacrylamide, Nt-butylacrylamide, Nt-octylacrylamide and N-undecylacrylamide.

[0227] The acrylic polymer according to the invention may be a homopolymer or a copolymer, advantageously a copolymer, even better a copolymer of (meth)acrylic acid and a (meth)acrylic acid ester.

[0228] Preferably, the acrylic polymer according to the present invention comprises the following monomers: a) (meth)acrylic acid; and b) C1~C 30 , and more preferentially C1~C 20 , and even better C1~C 10 , more particularly C1-C4 alkyl (meth)acrylates; It contains one or more units derived from

[0229] Preferably, the aqueous dispersion of acrylic polymer particles is surfactant-free.

[0230] The term "surfactant" refers to any agent that can modify the surface tension between two surfaces.

[0231] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and ethyl acrylate, such as the compound sold by BASF under the trade name Luvimer MAE, or the compound sold by Lubrizol under the trade name Fixate Superhold Polymer, such as polyacrylate-2 crosspolymer, or the compound sold by Daito Chemical Industry Co., Ltd. under the trade name Daitosol 3000VP3, or the compound sold by Daito Chemical Industry Co., Ltd. under the trade name Daitosol 3000 SLPN-PE1, such as acrylate copolymer.

[0232] The acrylic polymer may optionally contain one or more additional monomers other than (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide monomers.

[0233] Additional monomers include, for example, styrene monomers, particularly styrene and α-methylstyrene, preferably styrene.

[0234] In particular, the acrylic polymer is a styrene / (meth)acrylate copolymer, in particular a copolymer of at least one styrene monomer and at least one C1-C6 (meth)acrylate copolymer. 20 , preferably C1 to C 10 The polymer may be a copolymer selected from copolymers obtained by polymerizing alkyl (meth)acrylate monomers.

[0235] C1~C 10 The alkyl (meth)acrylate monomer may be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate.

[0236] Among the acrylic polymers, mention may be made of styrene / (meth)acrylate copolymers sold under the names Joncryl 77 by BASF, Yodosol GH41F by Akzo Nobel and Syntran 5760 CG by Interpolymer.

[0237] Preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles.

[0238] More preferentially, composition C comprises the following monomers: a) (meth)acrylic acid, and b) C1~C 30 , and more preferentially C1~C 20 , and even better C1~C 10 , more particularly C1-C4 alkyl (meth)acrylates; The composition comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more units derived from:

[0239] Preferably, the acrylic polymer (or active substance or solids) content of the aqueous dispersion of acrylic polymer particles is from 20% to 60% by weight, more preferentially from 22% to 55% by weight, and even better from 25% to 50% by weight, based on the weight of the dispersion.

[0240] Silicone Acrylic Copolymer According to a particular embodiment, the silicone compound comprising at least one carboxyl group is chosen from silicone acrylic copolymers.

[0241] Thus, according to a particular embodiment, the compound comprising at least one carboxyl function is chosen from silicone acrylic copolymers.

[0242] Preferably, the silicone acrylic copolymer comprises: at least one acrylic or methacrylic or crotonic unit, - at least one polydimethylsiloxane (PDMS) unit, Includes.

[0243] For the purposes of the present invention, the term "polydimethylsiloxane" (also abbreviated as PDMS) means, according to the generally accepted definition, any organosilicon polymer or oligomer with a linear structure of variable molecular weight, obtained by polymerization and / or polycondensation of appropriately functionalized silanes, essentially consisting of repeating main units in which silicon atoms are linked together through oxygen atoms (siloxane bond Si-O-Si), and which contain methyl groups bonded directly to said silicon atoms through carbon atoms.

[0244] The PDMS chains that can be used to obtain the copolymers used in accordance with the present invention preferably contain at least one polymerizable radical group located at at least one of the chain ends, i.e., the PDMS can have, for example, a polymerizable radical group at each of the two chain ends, or one polymerizable radical group at one end of the chain and one trimethylsilyl end group at the other end of the chain.

[0245] The term "polymerizable radical group" means a radical that can polymerize with other polymerizable radical groups or monomers. Preferably, the polydimethylsiloxane unit comprises at least one polymerizable radical group.

[0246] Preferably, the polymerizable radical group comprises at least one vinyl group.

[0247] Preferably, the polydimethylsiloxane (PDMS) unit comprises at least one polymerizable radical group comprising at least one vinyl group, preferably at least two polymerizable radical groups comprising at least one vinyl group, preferably located at at least one of the chain ends.

[0248] As mentioned above, the silicone acrylic copolymer preferably comprises at least one acrylic or methacrylic or crotonic unit, i.e., at least one unit containing a carboxyl group.

[0249] The term "carboxyl group" refers to COOH or COO - It means functional group, COO - The counterions of the groups can be selected from alkali metals, alkaline earth metals, and quaternary ammonium.

[0250] Preferably, the silicone acrylic copolymer comprises: at least one acrylic or methacrylic or crotonic unit and at least one acrylic or methacrylic or vinyl ester unit; and - at least one polydimethylsiloxane (PDMS) unit; Includes.

[0251] More preferentially, the composition comprises: - at least one unit selected from at least one croton unit and an alkyl crotonate unit, wherein the alkyl group is a linear or branched saturated group containing 1 to 20 carbon atoms; a vinyl acetate unit; a vinyl alkyl ester unit, wherein the alkyl group is a linear or branched saturated group containing 2 to 20 carbon atoms; and mixtures thereof; and - at least one polydimethylsiloxane (PDMS) unit; The silicone-acrylic copolymer contains one or more silicone acrylic copolymers including:

[0252] The term "crotonic unit" means a unit derived from a crotonic acid monomer or a salt thereof.

[0253] The term "alkyl crotonate unit" means a unit derived from a crotonic acid ester monomer containing a saturated, linear or branched alkyl group containing from 1 to 20 carbon atoms.

[0254] The term "vinyl alkyl ester unit" means a unit derived from a vinyl ester monomer containing a saturated, linear or branched alkyl group containing from 2 to 20 carbon atoms.

[0255] The term "vinyl acetate units" means units derived from vinyl acetate monomers.

[0256] According to a preferred embodiment, the silicone acrylic copolymer comprises: - at least one croton unit, at least one vinyl acetate unit, and at least one vinyl alkyl ester unit, the alkyl group being a saturated, linear or branched group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms, and at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable radical group, preferably containing at least one vinyl group, Includes.

[0257] According to a particularly preferred embodiment, the silicone acrylic copolymer comprises - at least one croton unit, at least one vinyl acetate unit, and at least one vinyl alkyl ester unit, the alkyl group being a linear or branched saturated group containing 6 to 16 carbon atoms, and - at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable radical group containing at least one vinyl group, Includes.

[0258] More preferentially, the composition comprises: - at least one croton unit, at least one vinyl acetate unit, and at least one vinyl alkyl ester unit, the alkyl group being a saturated, linear or branched group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms, and - at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable radical group containing at least one vinyl group, The silicone acrylic copolymer comprises one or more silicone acrylic copolymers including:

[0259] Even more preferentially, the composition comprises: - at least one croton unit, at least one vinyl acetate unit, and at least one vinyl alkyl ester unit, the alkyl group being a saturated, linear or branched group containing from 6 to 16 carbon atoms; and - at least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable radical group containing at least one vinyl group, The silicone acrylic copolymer comprises one or more silicone acrylic copolymers including:

[0260] Among the silicone acrylic copolymers that may be used in the context of the present invention, mention may be made of the compound sold by Wacker Chemie AG under the trade name Belsil® P1101, which has the INCI name Crotonic acid / vinyl C8-12 isoalkyl ester / VA / bis-vinyl dimethicone crosspolymer.

[0261] The total amount of compounds containing at least one carboxyl function preferably ranges from 0.1% to 30% by weight, more preferentially from 0.5% to 20% by weight, even better from 1% to 15% by weight and even more preferentially from 2% to 10% by weight relative to the total weight of composition C.

[0262] The total amount of aqueous dispersion of polymer particles chosen from polyurethanes, acrylic polymers and mixtures thereof preferably ranges from 0.1% to 40% by weight, more preferentially from 0.5% to 30% by weight, even better from 1% to 25% by weight and even more preferentially from 2% to 20% by weight relative to the total weight of composition C.

[0263] According to a particular embodiment, the total amount of aqueous dispersion of acrylic polymer particles preferably ranges from 0.1% to 40% by weight, more preferentially from 0.5% to 30% by weight, even better from 1% to 25% by weight and even more preferentially from 2% to 20% by weight relative to the total weight of composition C.

[0264] Advantageously, the total amount of silicone acrylic copolymer ranges from 0.1% to 30% by weight, more preferentially from 0.5% to 20% by weight, even better from 1% to 15% by weight and even more preferentially from 2% to 10% by weight relative to the total weight of composition C.

[0265] Non-carboxyl anionic thickener Composition C used in connection with the method according to the invention may also comprise at least one non-carboxylic anionic thickener.

[0266] For purposes of the present invention, the term "non-carboxylic agent" refers to a non-carboxylic agent that does not contain a carboxylic acid functional group (-COOH) or a carboxylate functional group (-COO - ) means a drug that does not contain

[0267] For the purposes of the present invention, the term "thickener" means a thickener that, when present at a concentration of 0.05% by weight relative to the total weight of the composition, thickens the composition into which it is incorporated at room temperature (25°C) and atmospheric pressure at a shear rate of 1 s -1 (Viscosity can be measured using a cone and plate viscometer such as a Haake R600 rheometer).

[0268] Preferably, the non-carboxylic anionic thickener is chosen from non-carboxylic anionic polymers, more preferentially from anionic polymers containing sulfonic groups.

[0269] For purposes of the present invention, the term "anionic polymer" means a polymer that contains one or more anionic or anionizable groups and no cationic or cationizable groups.

[0270] Advantageously, the non-carboxylic anionic thickener is chosen from anionic polymers comprising at least one ethylenically unsaturated monomer bearing a sulfonic group, in free form or in partially or completely neutralized form.

[0271] These polymers may be crosslinked or not, they are preferably crosslinked.

[0272] These polymers may be associative or non-associative, preferably non-associative.

[0273] Recall that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0274] Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0275] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon chain containing at least 8 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms, more preferentially 18 to 30 carbon atoms.

[0276] Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol, or decyl alcohol. It may also refer to a hydrocarbon-based polymer (e.g., polybutadiene).

[0277] The ethylenically unsaturated monomer having a sulfonic acid group is, in particular, vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylamide (C1-C 22 ) Alkyl sulfonic acid, N-(C1-C 22 ) Alkyl (meth)acrylamide (C1-C 22 ) alkyl sulfonic acids (such as undecylacrylamido methane sulfonic acid) and also partially or fully neutralized forms thereof.

[0278] More preferentially, (meth)acrylamides (C1-C 22 ) Alkyl sulfonic acids, such as acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid, or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and their partially or fully neutralized forms are used.

[0279] More particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or fully neutralized forms are used.

[0280] Among the 2-acrylamido-2-methylpropanesulfonic acid copolymers, mention may be made of partially or completely neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide, and particular mention may be made of the products described in Example 1 of EP 503853, to which reference may be made with regard to these polymers.

[0281] 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 EMT10 by SEPPIC (INCI name: Hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer).

[0282] Associative AMPS polymers are particularly suitable for C6-C 22 They can be selected from statistically associative AMPS polymers modified by reaction with n-mono- or di-n-alkylamines, such as those described in patent application WO 00 / 31154, the content of which forms an integral part. These polymers can also contain other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acid derivatives, (meth)acrylamides, vinylpyrrolidones or mixtures of these compounds, such as monoalcohols or their esters obtained with mono- or polyalkylene glycols.

[0283] Preferred polymers of this family are selected from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0284] These same copolymers may also contain one or more ethylenically unsaturated monomers not containing a fatty chain, such as (meth)acrylic acid derivatives, in particular their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.

[0285] These copolymers are described in particular in EP-A-750899, U.S. Pat. No. 5,089,578 and the following publications from Yotaro Morishima: - Self-assembling amphiphilic polyelectrolytes and their nanostructures,Chinese Journal of Polymer Science,Vol.18,No.40,(2000),323-336; - Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering-Macromolecules,Vol.33,No.10(2000),3694-3704; - Solution properties of micelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte::salt effects on rheological behavior-Langmuir,Vol.16,No.12,(2000)5324-5332; - Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers-Polym.Preprint, Div.Polym.Chem.40(2), (1999), 220-221.

[0286] Among these polymers, mention may be made of: - 15% to 60% by mass of AMPS units and 40% to 85% by mass of (C8 to C9 16 ) alkyl (meth) acrylamide or (C8-C 16 ) alkyl (meth)acrylate units, crosslinked or non-crosslinked, neutralized or non-neutralized copolymers, such as those described in EP-A-750899; - 10 mol% to 90 mol% of acrylamide units, 0.1 mol% to 10 mol% of AMPS units, and 5 mol% to 80 mol% of n-(C6 to C 18 ) terpolymers containing alkylacrylamide units, such as those described in U.S. Pat. No. 5,089,578.

[0287] Mention may also be made of fully neutralized copolymers of AMPS and dodecyl methacrylate and also crosslinked and non-crosslinked copolymers of AMPS and n-dodecyl methacrylamide, such as those described in the Morishima paper mentioned above.

[0288] Preferably, the non-carboxylic anionic thickener is chosen from sodium 2-acrylamido-2-methylpropanesulfonate / hydroxyethyl acrylate copolymer sold by SEPPIC (INCI name Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer).

[0289] Advantageously, the total amount of non-carboxylic anionic thickeners ranges from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even better from 0.1% to 5% by weight and even better still from 0.1% to 3% by weight relative to the total weight of composition C.

[0290] Associative Polymers Composition C according to the invention may also comprise at least one associative polymer different from the compound containing at least one carboxyl function and from the non-carboxylic anionic thickeners defined above.

[0291] Recall that "associative polymers" are polymers that are capable of reversibly associating with each other or with other molecules in aqueous media.

[0292] Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

[0293] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, linear or branched hydrocarbon-based chain containing at least 10 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms, more preferentially 18 to 30 carbon atoms.

[0294] Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also represent a hydrocarbon-based polymer (e.g., polybutadiene).

[0295] Associative polymers can be nonionic, anionic, cationic, or amphoteric.

[0296] Preferably, the associative polymer is selected from anionic associative polymers.

[0297] Among the anionic associative polymers, mention may be made of: (a) those comprising at least one hydrophilic unit and at least one fatty-chain allyl ether unit, more particularly those in which the hydrophilic unit is formed from an anionic ethylenically unsaturated monomer, more particularly those formed from a vinyl carboxylic acid, most particularly those formed from acrylic acid or methacrylic acid or a mixture thereof.

[0298] Among these anionic associative polymers, particularly preferred according to the present invention are polymers formed from 20% to 60% by weight of acrylic acid and / or methacrylic acid, 5% to 60% by weight of lower alkyl (meth)acrylate, 2% to 50% by weight of aliphatic allyl ether, and 0 to 1% by weight of a crosslinking agent (a well-known copolymerizable unsaturated polyethylene monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, or methylbisacrylamide).

[0299] Among the latter polymers, the most preferred are crosslinked terpolymers of methacrylic acid, ethyl acrylate and polyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), in particular the aqueous 30% emulsion of crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10 allyl ether (40 / 50 / 10) sold by Ciba under the names Salcare SC 80® and Salcare SC 90®.

[0300] - (b) comprising i) at least one hydrophilic unit of the unsaturated olefinic carboxylic acid type, and ii) at least one hydrophobic unit of the type (C10-C30) alkyl ester of an unsaturated carboxylic acid, etc.

[0301] The unsaturated carboxylic acids useful in the present invention (C 10 ~C 30) Alkyl esters include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, and dodecyl acrylate, and the corresponding methacrylic acid esters, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

[0302] Anionic polymers of this type are described and prepared, for example, in US Pat. No. 3,915,921 and US Pat. No. 4,509,949.

[0303] Among this type of anionic associative polymer, more specifically, 95% to 60% by weight of acrylic acid (hydrophilic unit) and 4% to 40% by weight of C 10 ~C 30 alkyl acrylate (hydrophobic unit) and 0 to 6% by mass of a cross-linkable polymerizable monomer, or 98% to 96% by mass of acrylic acid (hydrophilic unit) such as those described above and 1% to 4% by mass of C 10 ~C 30 A composition consisting of alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of a cross-linking polymerizable monomer will be used.

[0304] Among the above-mentioned polymers, the most particularly preferred according to the invention are Pemulen TR1®, Pemulen TR2®, Carbopol 1382®, and even more preferentially the product sold by Goodrich under the trade name Pemulen TR1® and the product sold by SEPPIC under the name Coatex SX®.

[0305] Mention may also be made of the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer sold under the name Acrylidone LM by the company ISP.

[0306] - (c) Maleic anhydride / C 30 ~C 38α-olefin / alkyl maleate terpolymers, such as those sold under the trademark Performa V1608® by Newphase Technologies (maleic anhydride / C 30 ~C 38 α-olefin / isopropyl maleate copolymer).

[0307] (d) Acrylic terpolymers, including: i) approximately 20% by mass to 70% by mass of an α,β-monoethylenically unsaturated carboxylic acid [A]; ii) approximately 20% to 80% by weight of an α,β-monoethylenically unsaturated non-surfactant monomer other than [A]; iii) approximately 0.5% to 60% by weight of a nonionic monourethane that is the reaction product of a monohydric surfactant and a monoethylenically unsaturated monoisocyanate; For example, the terpolymer described in EP-A-0 173 109, more particularly in Example 3, namely a 25% aqueous dispersion of the terpolymer methacrylic acid / methyl acrylate / behenyl alcohol dimethyl-meta-isopropenyl benzyl isocyanate ethoxylate (40 EO).

[0308] (e) copolymers comprising, among these monomers, α,β-monoethylenically unsaturated carboxylic acids and esters of α,β-monoethylenically unsaturated carboxylic acids with oxyalkylenated fatty alcohols.

[0309] Preferentially, these compounds further comprise, as monomers, esters of α,β-monoethylenically unsaturated carboxylic acids and of C1-C4 alcohols.

[0310] Examples of this type of compound include Aculyn 22® sold by Roehm & Haas, which is a terpolymer of methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate, and Aculyn 88 sold by Roehm & Haas.

[0311] Advantageously, the associative polymer, which is different from the compound containing at least one carboxyl function and from the non-carboxyl anionic thickeners mentioned above, is chosen from acrylic associative polymers, more preferentially carboxyl acrylic associative polymers.

[0312] Particularly preferably, the associative polymers, which differ both from the compounds containing at least one carboxyl function and from the non-carboxylic anionic thickeners mentioned above, are chosen from copolymers which contain among their monomers α,β-monoethylenically unsaturated carboxylic acids and esters of α,β-monoethylenically unsaturated carboxylic acids with oxyalkylenated fatty alcohols.

[0313] Advantageously, the total amount of said associative polymers, different from the compound containing at least one carboxyl function and different from said non-carboxyl anionic thickeners, ranges from 0.05% to 15% by weight, preferably from 0.05% to 10% by weight, more preferentially from 0.1% to 5% by weight and even more preferentially from 0.1% to 1% by weight relative to the total weight of composition C.

[0314] organic solvents Composition C according to the invention may comprise one or more organic solvents.

[0315] Examples of organic solvents that may be mentioned include lower C1-C4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and aromatic alcohols, especially aromatic monoalcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

[0316] The organic solvent may be present in a total amount of 0.01% to 60% by weight, preferably 0.05% to 50% by weight and more preferentially 0.1% to 45% by weight (both inclusive), relative to the total weight of composition C.

[0317] The composition C used in connection with 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 preferentially from 20% to 75% by weight, relative to the total weight of the composition C.

[0318] additives Composition C used in connection with the method according to the invention may contain any adjuvant or additive normally used.

[0319] Among the additives that may be contained in composition C, mention may be made of reducing agents, emollients, antifoaming agents, moisturizing agents, UV filters, deflocculants, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than those mentioned above, preservatives, silicones other than those mentioned above, oils, waxes and mixtures thereof.

[0320] The composition C used in connection with the method according to the invention may in particular be in the form of a suspension, a dispersion, a gel, an emulsion, in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion or a multiphase emulsion (W / O / W or polyol / O / W or O / W / O), in the form of a cream, a mousse, a stick, a dispersion of vesicles, in particular of ionic or non-ionic lipids, or in the form of a two-phase or multiphase lotion.

[0321] A person skilled in the art will be able, based on his general knowledge, to select a suitable presentation form as well as a method for preparing it, taking into account first the nature of the components used, in particular their solubility in the carrier, and then the intended use of the composition.

[0322] protocol Composition T as defined above can be used on wet or dry keratinous hair fibres, as well as on any type of light or dark, natural or dyed, permed, bleached or straightened keratinous hair fibre.

[0323] Preferably, the application of composition T as defined above is followed by a rinsing step.

[0324] This rinsing step may be followed by a spin-drying and / or drying step.

[0325] Composition T can be applied at room temperature (15°C to 25°C).

[0326] After applying composition T, it may be left for 1 minute to 12 hours, in particular 1 minute to 10 hours, more particularly 1 minute to 7 hours, and more preferentially 1 minute to 6 hours, before applying composition C to the keratin hair fibres.

[0327] Composition C described above can be used on wet or dry keratinous hair fibers, as well as on any type of light or dark, natural or dyed, permed, bleached or straightened keratinous hair fiber.

[0328] Preferably, a washing, rinsing, dewatering or drying step is carried out after applying composition C to the keratinous hair fibre.

[0329] More preferentially, a drying step is carried out after applying composition C to the keratinous hair fibres.

[0330] The application of composition C to the keratinous hair fibres can be carried out by any standard means, in particular with a comb, a fine-toothed brush, a wide-toothed brush, a sponge or the fingers.

[0331] The application of composition C to keratin hair fibers is usually carried out at room temperature (15-25°C).

[0332] After application of composition C to keratinous hair fibers, it can be left for 1 minute to 6 hours, in particular 1 minute to 2 hours, more particularly 1 minute to 1 hour, and more preferentially 1 minute to 30 minutes, for example before the washing, rinsing, dewatering and / or drying steps.

[0333] After applying composition C, the keratinous hair fibres may be allowed to dry naturally or may be dried at a temperature of, for example, 30° C. or higher.

[0334] Thus, the method according to the invention may comprise the step of applying heat to the keratinous hair fibres using a heating appliance.

[0335] The heat application step of the method of the present invention can be carried out using a hood dryer, a hair dryer, a straightener, a curling iron, a Climazon hood, or the like.

[0336] Preferably, the step of applying heat of the method of the present invention is carried out using a hair dryer.

[0337] When the method of the present invention includes the step of applying heat to the keratin hair fibers, the step of applying heat to the keratin hair fibers is carried out after applying composition C to the keratin hair fibers.

[0338] During the process of applying heat to the keratinous hair fibers, the hair strands may be subjected to mechanical action such as combing, brushing or hand combing.

[0339] If the step of applying heat to the keratinous hair fibres is carried out using a hood dryer or a hair dryer, the temperature is preferably between 30°C and 110°C, preferentially between 50°C and 90°C.

[0340] If the step of applying heat to the keratin hair fibres is carried out using a straightening iron, the temperature is preferably between 110°C and 220°C, preferably between 140°C and 200°C.

[0341] In a particular variant, the method of the invention comprises a step (c1) of applying heat using a hood dryer, a hair dryer or a crimson hood, preferably a hair dryer, and a step (c2) of applying heat using a straightening iron or curling iron, preferably a straightening iron.

[0342] Step (c1) may be carried out before step (c2).

[0343] During the implementation of step (c1), also referred to as the drying step, the keratinous hair fibers can be dried, for example, at a temperature of at least 30° C. According to a particular embodiment, this temperature is greater than 40° C. According to a particular embodiment, this temperature is greater than 45° C. and less than 110° C.

[0344] Preferably, when drying the keratinous hair fibers, in addition to the supply of heat, the drying is carried out by using an air current, which thus makes it possible to improve the separation of the coating of the hair strands.

[0345] During drying, the hair strands can be subjected to mechanical action such as combing, brushing or hand combing.

[0346] The temperature at which the straightening iron or curling iron is slid in the drying step (c2) may preferably be in the range of 110°C to 220°C, more preferably 140°C to 200°C.

[0347] After the heating step, a shaping step may be carried out using, for example, a straightening iron, and the temperature in the shaping step is 110°C to 220°C, preferably 140°C to 200°C.

[0348] Preferably, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis. i) applying to keratin hair fibers a composition T comprising at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant as described above and less than 1% by weight of silicone relative to the total weight of composition T, preferably a silicone-free composition T; ii) rinsing, dehydrating, and / or drying the keratinous hair fibers; and iii) - at least one (poly)carbodiimide compound as defined above, - applying to the keratinous hair fibres at least one composition C containing at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; then iv) optionally leaving said composition C on the keratin hair fibres for 1 minute to 30 minutes, preferably 1 to 20 minutes; then v) optionally washing, rinsing, dewatering and / or drying the keratinous hair fibers; A method for dyeing keratin hair fibers, comprising:

[0349] Preferably, Composition T comprises at least one anionic surfactant.

[0350] Advantageously, composition T comprises at least one anionic surfactant and at least one amphoteric or zwitterionic surfactant.

[0351] Preferably, composition C also contains at least one compound containing at least one carboxyl functional group as described above.

[0352] Preferably, composition C comprises (meth)acrylamides (C1 to C 22 ) also includes at least one non-carboxylic anionic thickener as previously described selected from alkyl sulfonic acids.

[0353] Preferably, composition C also comprises at least one associative polymer, as defined above, preferably an acrylate-based associative polymer, different from the compound containing at least one carboxyl function and different from the non-carboxyl anionic thickener defined above.

[0354] Advantageously, the step of applying composition C to the keratinous fibers is repeated several times.

[0355] According to a preferred embodiment, step b) comprises extemporaneously mixing at least two compositions A and B at the time of use to obtain composition C, and applying composition C to keratinous fibers, composition A comprises at least one (poly)carbodiimide compound as defined above, Composition A and / or Composition B comprise at least one colorant selected from pigments, direct dyes and mixtures thereof as defined above.

[0356] Advantageously, composition C or composition B comprises at least one compound containing at least one carboxyl functional group, preferably chosen from silicone compounds, polyurethanes, acrylic polymers, and mixtures thereof, containing at least one carboxyl group.

[0357] Preferably, composition B comprises at least one compound containing at least one carboxyl functional group, preferably selected from silicone compounds, polyurethanes, acrylic polymers, and mixtures thereof, containing at least one carboxyl group.

[0358] According to a preferred embodiment, step b) comprises extemporaneously mixing at least two compositions A and B at the time of use to obtain composition C, and applying composition C to keratinous fibers, composition A comprises at least one (poly)carbodiimide compound as defined above, composition B comprises at least one compound containing at least one carboxyl function as defined above, Composition A and / or Composition B comprise at least one colorant selected from pigments, direct dyes and mixtures thereof as defined above.

[0359] Composition A and / or Composition B may optionally comprise at least one non-carboxylic anionic thickener as defined above and / or an associative polymer as defined above that is different from the compound containing at least one carboxyl functional group as defined above and from the non-carboxylic anionic thickener.

[0360] Advantageously, composition A comprises at least one non-carboxylic anionic thickener as defined above.

[0361] Advantageously, composition B may optionally comprise at least one compound comprising at least one carboxyl function as defined above and / or at least one associative polymer as defined above, different from the compound comprising at least one carboxyl function as defined above and different from the non-carboxyl anionic thickener.

[0362] Preferably, composition B comprises at least one colorant selected from the aforementioned pigments, direct dyes and mixtures thereof, and composition A does not comprise, or comprises in an amount that does not make it possible to dye keratin hair fibers, a colorant selected from the aforementioned pigments, direct dyes and mixtures thereof, and more preferentially does not comprise, a colorant selected from the aforementioned pigments, direct dyes and mixtures thereof.

[0363] According to this embodiment, compositions A and B are preferably mixed within 15 minutes before application to the keratinous hair fibre, more preferentially within 10 minutes before application, and even better still within 5 minutes before application.

[0364] The weight ratio of composition A to composition B is preferably in the range of 0.1 to 10, preferentially 0.2 to 5, better still 0.5 to 2, and even better still 0.6 to 1.5. In a particular embodiment, the weight ratio of composition A to composition B is equal to 1.

[0365] The total amount of the (poly)carbodiimide compounds is preferably in the range of 0.01% by mass to 40% by mass, more preferentially 0.1% by mass to 30% by mass, even better 0.5% by mass to 20% by mass, and even more preferentially 1% by mass to 12% by mass, relative to the total mass of composition A.

[0366] The total amount of compounds containing at least one carboxyl group is preferably in the range of 0.2% to 60% by weight, more preferentially 1% to 40% by weight, even better still 1% to 30% by weight, and even more preferentially 2% to 20% by weight, relative to the total weight of composition B.

[0367] The total amount of aqueous dispersion of particles of polymer chosen from polyurethanes, acrylic polymers and mixtures thereof preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 50% by weight, even better from 1% to 40% by weight and even more preferentially from 2% to 30% by weight relative to the total weight of composition B.

[0368] According to a particular embodiment, the total amount of aqueous dispersion of acrylic polymer particles preferably ranges from 0.2% to 60% by weight, more preferentially from 1% to 50% by weight, even better from 1% to 40% by weight and even more preferentially from 2% to 30% by weight relative to the total weight of composition B.

[0369] The present invention will now be explained in more detail by means of examples, which in no way limit the scope of the invention, but which make it possible to support certain features, variants and preferred embodiments of the invention. [Example]

[0370] The (poly)carbodiimides of the present invention can be obtained via synthetic methods known to those skilled in the art, starting from commercially available products or reagents that can be synthesized according to chemical reactions known to those skilled in the art, for example, in the book Sciences of Synthesis - Houben-Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag KG, Rüdigerstrasse 14, D-70469 Stuttgart, or in U.S. Pat. No. 4,284,730 or Canadian Patent Application No. 2,509,861.

[0371] More specifically, the process for preparing the (poly)carbodiimide of the present invention comprises, in a first step, reacting a diisocyanate reagent (1): O=C=N-L1-N=C=O (1) (wherein L1 is as defined above) in the presence of a carbodiimidization catalyst (2) such as those described in U.S. Pat. No. 4,284,730, particularly a phosphorus-based catalyst, particularly one selected from phospholene oxides and phospholene sulfoxides, diaza- and oxaza-phosphoranes, preferably in an inert atmosphere (nitrogen or argon), particularly preferably in an aprotic polar solvent such as THF, glyme, diglyme, 1,4-dioxane or DMF, at a temperature between room temperature and the reflux temperature of the solvent, preferably about 140° C., to produce a carbodiimide diisocyanate compound (3): O=C=N-L1-(N=C=N-L1) n -N=C=O (3) (wherein L1 and n are as defined above) To deactivate the catalyst, a benzoyl halide such as benzoyl chloride may be added.

[0372] In the second step of this preparation process, to obtain a "symmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 eq.) of the nucleophilic reagent R1-X1-H, followed by 0.5 equivalents of the reagent HEH (wherein R1, X1 and E are as defined above), to give the "symmetric" compound (4) according to the invention: [R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)]2-E (4) (wherein R1, X1, L1, n and E are as defined above) is obtained. According to a variant to obtain compound (4) from (3), it is possible to first add 0.5 equivalents of the reagent HEH, followed by 1 equivalent of the reagent R1-X1-H.

[0373] In the second step of this preparation process, to obtain an "unsymmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 eq.) of the nucleophilic reagent R1-X1-H, followed by reaction with an equivalent of the reagent HEH, where R1, X1 and E are as defined above, to give compound (5): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EH (5) (wherein R1, X1, L1, n and E are as defined above) is obtained.

[0374] According to one variant to obtain compound (5) from (3), it is possible to first add 1 equivalent of the reagent R1-X1-H, followed by 0.5 equivalents of the reagent HEH.

[0375] In the third step, compound (5) is reacted with 1 equivalent of compound (6): R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O (6) The compound (6) is reacted with the compound (3'): O=C=N-L1-(N=C=N-L1) z -N=C=O(3') (wherein L and z are as defined above) which is reacted with one equivalent of a nucleophile R-X-H having L, R, X and z as defined above to give the asymmetric compound (7): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EC(O)-NH-L1-(N=C=N-L1) z -NH-C(O)-X2-R2(7) (In formula (7), R1, X1, L1, R2, X2, n, z and E are as defined above.)

[0376] 1 molar equivalent of the compound O=C=N-L1-(N=C=N-L1) z-N=C=O(3') was reacted with 1 / w molar equivalent of HEH followed by 1 equivalent of nucleophile R2-X2-H to give compound (8): H-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NH-C(O)-X2-R2(8) (wherein L1, R2, X2, z and E are as defined above, and w is an integer of 1 to 3; more preferentially, w=1) can also be obtained.

[0377] This final compound (8) is then reacted with 1 equivalent of compound (4'): R1-X1~C(O)-NH-L1-(N=C=N-L1) n -N=C=O(4') (The compound (4') can be synthesized by reacting 0.5 equivalents of a nucleophilic reagent R1-X1-H with 1 equivalent of compound (3)) to obtain the (poly)carbodiimide (9) of the present invention: R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NHC(O)-X2-R2(9) (In formula (9), L1, R1, X1, R2, X2, n, z, w and E are as defined above.)

[0378] The (poly)carbodiimide compounds and all reaction intermediates and reagents as well may be purified by conventional methods known to those skilled in the art, such as extraction with water and water-immiscible organic solvents, precipitation, centrifugation, filtration and / or chromatography.

[0379] Example 1: Process for synthesizing (poly)carbodiimide compounds Into a 500 mL three-necked round-bottom flask equipped with a thermometer, a stirrer and a reflux condenser, 50 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphole 1-oxide were placed with stirring.

[0380] 2200-2300 cm by infrared spectroscopy -1 The reaction medium was heated under nitrogen at 140°C for 4 hours, and then cooled to 120°C, while the reaction was monitored by the absorption of isocyanate groups.

[0381] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol is introduced into the reaction medium with stirring. -1 The temperature is monitored and maintained at 120°C until the isocyanate groups have completely disappeared, and then cooled to room temperature.

[0382] After cooling to room temperature, the reaction medium is added dropwise, with vigorous stirring, to a 500 mL glass beaker containing 85 g of distilled water, to give the desired product in the form of a translucent yellow liquid.

[0383] Example 2 Compositions T1 and T2 were prepared as described in Table 1 below: amounts are expressed as g / 100g of starting material obtained unless otherwise stated.

[0384] [Table 1]

[0385] Compositions A and B described in Tables 2 and 3 below were also prepared: amounts are expressed as g / 100g of starting material obtained unless otherwise stated.

[0386] [Table 2]

[0387] [Table 3]

[0388] Composition A is then mixed with composition B in a 50 / 50 weight ratio to obtain composition C according to the invention.

[0389] protocol First, composition T1 or T2 was applied to a stratum of keratinous hair fibers with some sensitivity (20% alkali solubility). Each of these compositions was applied to the stratum of keratinous hair fibers at a rate of 0.8 grams of composition per gram of stratum. The stratum was then rinsed, detangled, and dried with a hair dryer.

[0390] Composition C was then applied to the hair tresses pretreated with Composition T1 or Composition T2 at a rate of 0.8 grams of composition per gram of hair tress, after which the keratin hair fiber tresses were detangled and dried with a hair dryer.

[0391] The process using composition T1 followed by composition C is a comparative process, hereafter referred to as process P1.

[0392] The process of using composition T2 followed by composition C is a process according to the invention, hereinafter referred to as process P2.

[0393] The process applied is summarized in Table 4 below:

[0394] [Table 4]

[0395] The keratin hair fibre tresses treated with processes P1 and P2 were then subjected to a test consisting of multiple repeated shampoo washes to assess the resistance (durability) of the resulting colour to shampoo washes, according to the shampoo wash protocol described below.

[0396] Shampoo Wash Protocol: The dyed keratin hair fiber strands are combed, moistened with water at 35°C, and then passed through the fingers 5 times for 5 seconds. The keratin hair fiber strands are then squeezed between two fingers to dry.

[0397] A standard shampoo (Garnier Ultra Doux) was applied evenly to the dyed hair tresses at a rate of 0.4 g of standard shampoo per gram of tress, and the keratin hair fiber tresses were gently massaged longitudinally from root to tip for 15 seconds (6 times).

[0398] The keratin hair fiber strand is then placed on a watch glass and left for 1 minute.

[0399] The keratin hair fiber strand is then rinsed with water (15 times) while passing it between the fingers, after which the keratin hair fiber strand is squeezed between two fingers before the next shampoo wash.

[0400] After several shampoo washes the keratin hair fibre strands are combed and dried with a hair dryer.

[0401] result The color durability of the tresses was evaluated in the CIE L*a*b* system using a Minolta CM3610A spectrophotometer (D65 illuminant, 10° angle, including specular reflection component).

[0402] In this L*a*b* system, L* represents the intensity of the color, a* indicates the green / red axis, and b* indicates the blue / yellow axis.

[0403] The durability of the color is evaluated by the color difference ΔE between measurements taken before the dyed hair tress is subjected to the shampoo wash test and after five subsequent shampoo washes according to the protocol described above.

[0404] The ΔE value is calculated according to the following formula:

number

[0405] In this formula, L*, a*, and b* represent values ​​measured after dyeing keratin hair fibers and washing with shampoo, and L0*, a0*, and b0* represent values ​​measured after dyeing keratin hair fibers and before washing with shampoo.

[0406] [Table 5]

[0407] A lock of keratinous hair fibres treated with the process P2 according to the invention and washed five times with shampoo has a significantly lower colour difference ΔE than a lock of keratinous hair fibres treated with the comparative process P1.

[0408] Thus, the pigmented coatings obtained by the process according to the invention exhibit improved resistance to shampoo washing.

Claims

1. 1. A method for dyeing keratinous hair fibers, comprising: a) applying to keratin hair fibers at least one composition T comprising at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant and less than 1% by weight of silicone relative to the total weight of composition T; then b) at least one (poly)carbodiimide compound, applying to the keratinous hair fibres at least one composition C containing at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; 1. A method for dyeing keratinous hair fibers, comprising: The (poly)carbodiimide compound is a compound of the following formula (II): 【Chemistry 1】 (In the formula, -X １ and X ２ independently represent an oxygen atom O, a sulfur atom S, or an NH group; -R １ and R ２ independently represent a hydrocarbon-based group optionally interrupted by one or more heteroatoms; n and z represent integers ranging from 1 to 20, with n+z≧2, and w represents an integer ranging from 1 to 3; - L １ are independently divalent C １ ~C １８ Aliphatic hydrocarbon group, C ３ ~C １５ Cycloalkylene group, C ３ ~C １２ Heterocycloalkylene group or C ６ ~C １４ represents arylene groups and mixtures thereof, E is independently -O-R ３ -O-;-S-R ４ -S-;-R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - represents a group selected from ３ and R ４ independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; -R ５ independently represent a covalent bond or a divalent saturated hydrocarbon-based group optionally interrupted by one or more heteroatoms; -R ６ independently represent a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms. A method selected from the following.

2. 2. The method of claim 1, wherein the anionic surfactant is selected from sulfate-type anionic surfactants.

3. 3. The method according to claim 1 or 2, characterized in that the anionic surfactants are present in a total amount ranging from 1% to 50% by weight, preferably from 5% to 40% by weight, more preferentially from 10% to 30% by weight and even more preferentially from 12% to 20% by weight relative to the total weight of composition T.

4. The amphoteric or zwitterionic surfactant is ８ ~C ２０ ) alkyl betaine, (C ８ ~C ２０ ) alkyl sulfobetaine, (C ８ ~C ２０ ) alkylamide (C ３ ~C ８ ) alkyl betaine, (C ８ ~C ２０ ) alkylamide (C ６ ~C ８ ) alkyl sulfobetaines, and mixtures thereof, more preferentially selected from (C ８ ~C ２０ ) alkyl betaine, (C ８ ~C ２０ ) alkylamide (C ３ ~C ８ ) alkylbetaines, and mixtures thereof, and even more preferentially (C ８ ~C ２０ ) alkylamide (C ３ ~C ８ 4. The method according to claim 1, wherein the alkyl group is selected from the group consisting of alkyl betaines and mixtures thereof.

5. 5. Method according to any one of claims 1 to 4, characterized in that the amphoteric or zwitterionic surfactants are present in a total amount ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferentially from 0.75% to 15% by weight, even more preferentially from 1% to 10% by weight and even better still from 1.2% to 5% by weight relative to the total weight of composition T.

6. 6. The method according to claim 1, wherein composition T is silicone-free.

7. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ independently represent an oxygen atom, -R １ and R ２ are independently selected from dialkylamino alcohols from which the hydroxyl groups have been removed, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols, and mixtures thereof; n and z represent integers ranging from 1 to 20, with n+z≧2 and w equal to 1; - L1 is a divalent C １ ~C １８ Aliphatic hydrocarbon group, C ３ ~C １５ Cycloalkylene group, C ３ ~C １２ Heterocycloalkylene group or C ６ ~C １４ arylene groups and mixtures thereof; - E independently -O-R ３ -O-;-S-R ４ -S-;-R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - wherein R and R independently represent a group selected from C optionally interrupted by one or more heteroatoms. ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups, and mixtures thereof; -R ５ is not a covalent bond, R ５ is a C optionally interrupted by one or more heteroatoms ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups, and mixtures thereof; -R ６ C optionally interrupted by one or more heteroatoms ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ 7. The method according to claim 1, wherein the alkylene group is selected from the group consisting of alkylene groups, alkylene groups, and mixtures thereof.

8. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ each independently represents an oxygen atom, -R １ and R ２ are independently monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl groups have been removed, n and z represent integers ranging from 1 to 20, with n+z≧2 and w equal to 1; - L １ But C ３ ~C １５ is a cycloalkylene group, - E independently -O-R ３ -O-;-S-R ４ -S-;-R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - In these formulas, R represents a group selected from ３ and R ４ are independently C optionally interrupted by one or more heteroatoms ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups, and mixtures thereof; -R ５ is not a covalent bond, R ５ is a C optionally interrupted by one or more heteroatoms ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ alkylene groups, and mixtures thereof; -R ６ C optionally interrupted by one or more heteroatoms ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ 8. The method according to claim 1, wherein the alkylene group is selected from the group consisting of alkylene groups, alkylene groups, and mixtures thereof.

9. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ each independently represents an oxygen atom, -R １ and R ２ are independently represented by the following formula (VI): R １３ -[O-H ２ -C(H)(R １４ )] ｑ - (VI) represents a compound of R １３ But C １ ~C ４ alkyl group or phenyl, preferably C １ ~C ４ represents an alkyl group, more preferably methyl, R １４ is a hydrogen atom or C １ ~C ４ represents an alkyl group, preferably a hydrogen atom; q represents an integer ranging from 4 to 30; n and z represent integers ranging from 1 to 20, n+z ranging from 4 to 10, and w is equal to 1; - L １ However, C cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane ３ ~C １５ is a cycloalkylene group, - E is -O-R ３ represents an —O— group, and R ３ is a C optionally interrupted by one or more heteroatoms ６ ~C １４ Arylene group, C ３ ~C １２ Cycloalkylene group, linear or branched C １ ~C １８ 9. The method according to any one of claims 1 to 8, characterized in that it is selected from alkylene groups, and mixtures thereof.

10. The (poly)carbodiimide compound is selected from the compounds of formula (II) above, wherein: -X １ and X ２ each independently represents an oxygen atom, -R １ and R ２ are independently represented by the following formula (VI): R １３ -[O-H ２ -C(H)(R １４ )] ｑ - (VI) R １３ is C １ ~C ４ alkyl group or phenyl, preferably C １ ~C ４ represents an alkyl group, more preferably methyl, R １４ is a hydrogen atom or C １ ~C ４ represents an alkyl group, preferably a hydrogen atom; q represents an integer ranging from 4 to 30; n and z represent integers ranging from 1 to 20, n+z ranging from 4 to 10, and w is equal to 1; - L １ However, C cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane ３ ~C １５ a cycloalkylene group, preferably 4,4-dicyclohexylenemethane; - E is -O-R ３ represents an —O— group, and R ３ is a straight or branched C alkyl group such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms; １ ~C １８ 10. The method according to any one of claims 1 to 9, characterized in that it represents an alkylene group.

11. The (poly)carbodiimide compound is a compound of the formula (XII): 【Chemistry 2】 (In the formula, L １ is 4,4-dicyclohexylenemethane, n and z represent integers ranging from 1 to 20, n+z is in the range of 4 to 10, and E is -O-R ３ represents an —O— group, and R ３ is a straight or branched C alkyl group such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms. １ ~C １８ 11. The method according to claim 1, wherein r and s represent an alkylene group and r and s represent integers ranging from 4 to 30.

12. 12. The method according to any one of claims 1 to 11, characterized in that the total amount of (poly)carbodiimide compounds ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferentially from 0.2% to 10% by weight, even more preferentially from 0.5% to 8% by weight and better still from 1% to 6% by weight relative to the total weight of composition C.

13. 13. The method according to any one of claims 1 to 12, characterized in that the total amount of colorants chosen from pigments, direct dyes and mixtures thereof ranges from 0.001% to 20% by weight, preferably from 0.005% to 15% by weight, relative to the total weight of composition C.

14. step b) comprises extemporaneously mixing at least two compositions A and B at the time of use to obtain composition C, and applying composition C to keratinous fibers, composition A comprises at least one (poly)carbodiimide compound according to any one of claims 1 and 7 to 11, 14. The method according to any one of claims 1 to 13, characterized in that composition A and / or composition B comprise at least one colorant selected from the pigments, direct dyes and mixtures thereof according to claim 1.

15. 15. The method according to any one of claims 1 to 14, characterized in that composition C or composition B comprises at least one compound containing at least one carboxyl functional group, preferably chosen from silicone compounds, polyurethanes, acrylic polymers, and mixtures thereof, containing at least one carboxyl group.

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