Process for dyeing hair keratin fibres, comprising the steps of washing the hair keratin fibres with a particular composition, followed by the application to the hair keratin fibres of a particular dyeing composition

Abstract

The present invention relates to a method for dyeing hair keratin fibers, the method comprising: (a) washing the hair keratin fibers with a composition T, the composition T comprising at least one surfactant selected from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, and having an alkaline pH; and then (b) applying a dyeing composition C to the hair keratin fibers, the dyeing composition C comprising: - at least one (poly)carbodiimide compound of formula (II); - at least one polymer comprising at least one reactive group selected from carboxylic acids; and - at least one colorant selected from pigments, direct dyes and mixtures thereof.

Description

[0001] The present invention relates to a method for dyeing hair keratin fibers, the method comprising the steps of washing the hair keratin fibers with a composition comprising at least one anionic and / or amphoteric or zwitterionic surfactant and having an alkaline pH, and then applying a composition C for dyeing hair keratin fibers to the hair keratin fibers, the composition C comprising a (poly)carbodiimide compound, a polymer comprising at least one reactive group selected from carboxylic acids, and a colorant. Technical Field

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

[0003] There are basically three types of methods for dyeing hair keratin fibers: a) "Permanent" dyeing, which functions to provide a substantial alteration to the natural color, uses oxidative dyes that penetrate into the hair keratin fibers and form the color through an oxidative condensation process. b) Non-permanent, semi-permanent, or direct dyeing that does not use an oxidative condensation process and can withstand four or five shampoo washes; including dyeing keratin fibers with a coloring composition containing a direct dye. c) Temporary coloring, which causes a change in the natural color of the entire head of hair from one shampoo wash to the next, and is used to enhance or correct an already achieved tone. It can also be compared to a "makeup" process.

[0004] Another dyeing method involves the use of pigments. Specifically, applying pigments to the surface of keratin fibers typically allows for coloration visible on dark hair keratin fibers because the surface pigment masks the fiber's natural color. However, the coloration obtained through this method has disadvantages such as poor tolerance to shampoo washing and external agents like sebum, sweat, brushing, and / or friction. The resulting coloration may also be overly selective, meaning that the keratin fiber is sensitized to varying degrees between its tip and root, resulting in excessive color variation.

[0005] Therefore, there is still a need for a method for dyeing hair keratin fibers that has the advantages of obtaining a uniform color coating on the hair keratin fibers while forming a durable coating relative to shampoo washing and various stresses that the hair keratin fibers may experience (such as brushing and / or friction).

[0006] Therefore, the object of the present invention is to develop a method for dyeing hair keratin fibers, which has the advantages of obtaining a smooth and uniform colored coating on hair keratin fibers, while forming a coating that improves durability relative to shampoo washing and various stresses that hair keratin fibers may be subjected to (such as brushing and / or friction). Summary of the Invention

[0007] Therefore, one aspect of the present invention is a method for dyeing hair keratin fibers, the method comprising: (a) The step of washing hair keratin fibers with composition T, which comprises at least one surfactant selected from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, and has an alkaline pH; and then (b) Applying composition C for dyeing hair keratin fibers to hair keratin fibers, composition C comprising: - At least one (poly)carbodiimide compound selected from compounds of formula (II): (II), in: - X1 and X2 independently represent oxygen atom O, sulfur atom S or NH group; - R1 and R2 independently represent hydrocarbon-based groups optionally inserted with one or more heteroatoms; - n and z indicate integers from 1 to 20, where n+z ≥ 2 and w indicates integers from 1 to 3; - L1 independently represents C1-C 18 Divalent aliphatic hydrocarbons based on hydrocarbon groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocyclic alkyl or C6-C 14 aryl groups and their mixtures; - E independently represents a group selected from the following: -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; R3 and R4 independently represent divalent hydrocarbon-based groups optionally inserted with one or more heteroatoms; - R5 independently represents a covalent bond or optionally an inserted saturated divalent hydrocarbon-based group with one or more heteroatoms; - R6 independently represents a hydrogen atom or optionally a hydrocarbon-based group with one or more heteroatoms inserted; - At least one polymer containing at least one reactive group selected from carboxylic acids; and - At least one colorant selected from pigments, direct dyes and mixtures thereof.

[0008] By means of the method for dyeing hair keratin fibers according to the invention, a colored coating is obtained on the hair keratin fibers, which enables the obtaining of color visible on all types of hair keratin fibers and durable coloring relative to shampoo washing. This coating can withstand external stresses that hair keratin fibers may experience, such as blow-drying and sweating. The dyeing method according to the invention particularly enables the obtaining of a uniform coating.

[0009] the term" At least one / "It means one or more."

[0010] Unless otherwise indicated, the limits of the range of values ​​are included within that range, especially in expressions such as “between” and “ranging from… to…”.

[0011] This invention is not limited to the examples shown. Features of different examples can be combined in particular in variations not shown.

[0012] For the purposes of this invention and unless otherwise stated: -" alkyl "Indicates a straight-chain or branched saturated group containing, for example, 1 to 20 carbon atoms; -" aminoalkyl "Indicates an alkyl group as previously defined, wherein the alkyl group contains an NH2 group; -" Hydroxyalkyl "Indicates an alkyl group as previously defined, wherein the alkyl group contains an OH group; -" Alkylene "Indicates a straight-chain or branched divalent saturated C2-C4 hydrocarbon-based group, such as methylene, ethylene, or propylene;" -" cycloalkyl "or" Alicycloalkyl "Indicates a saturated monocyclic or polycyclic ring, preferably monocyclic, bicyclic or tricyclic, containing 1 to 3 rings, preferably 2 rings and containing 3 to 24 carbon atoms, particularly 3 to 20 carbon atoms, more particularly 3 to 13 carbon atoms, even more particularly 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, of a hydrocarbon-based group, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, particularly cyclopropyl, cyclopentyl or cyclohexyl. It should be understood that the cycloalkyl group may be substituted by one or more (C1-C4) alkyl groups such as methyl; preferably, the cycloalkyl group is isobornyl." -" Cycloalkylene "Indicates a divalent cycloalkyl group, wherein" cycloalkyl "As previously defined, it is preferably C3-C" 12 ; -" Aryl "Aromatic" is a monocyclic, bicyclic, or tricyclic, fused or non-fused, unsaturated, and aromatic hydrocarbon-based cyclic group comprising 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms; preferably, the aryl group comprises a ring having 6 carbon atoms, such as phenyl, naphthyl, anthracene, phenanthryl, and biphenyl; it should be understood that the aryl group may be substituted by one or more (C1-C4) alkyl groups such as methyl, preferably tolyl, xylyl, or methylnaphthyl; preferably, the aryl group represents phenyl. -" Aspartic "It is a divalent aryl group, in which " Aryl "As previously defined; preferably, arylene represents phenylene; -" Heterocyclic "The group indicates a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based group containing one or more heteroatoms, preferably from 1 to 5 atoms selected from O, S or N, including from 3 to 20 ring members, preferably between 5 and 10 ring members, such as imidazolyl, pyrrolel and furanyl." -" Heterocyclic alkyl " is a divalent heterocyclic group, in which " Heterocyclic "is as previously defined; -" Aryloxy "Indicates aryl-oxygen, wherein" Aryl "is as previously defined; -" Alkoxy "Indicates alkyl-oxygen, wherein" alkyl "is as previously defined; -" Acyloxy "Indicating the ester group RC(O)-O-, where R is an alkyl group as previously defined; -" Reactivity A functional group is a group that can form a covalent bond with another functional group, whether the same or different, through a chemical reaction.

[0013] Unless otherwise indicated, when a compound is mentioned in this patent application, it also includes, alone or as a mixture, its optical isomers, its geometric isomers, its tautomers or salts thereof.

[0014] The term "hair keratin fiber" refers to keratin hair fiber or hair. In other words, the expressions "hair keratin fiber," "keratin hair fiber," and "hair" are used interchangeably in the following sections of the instruction manual.

[0015] For the purposes of this invention, the term "hair keratin fibers" refers to the keratin fibers of the entire head of hair. This term does not correspond to body hair, eyebrows, or eyelashes.

[0016] Washing steps using composition T

[0017] As previously noted, the method according to the invention first includes step a) washing with composition T, which has an alkaline pH and contains at least one surfactant selected from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof.

[0018] Advantageously, the pH of the composition T is from 7.5 to 13, preferably from 8 to 12, more preferably from 8 to 10.

[0019] The pH of composition T can be adjusted to an alkaline pH in the presence of an alkaline pH adjuster.

[0020] Composition T can be in solid form, such as a shampoo in solid form. In this case, the pH useful in the present invention is the pH of the shampoo in contact with water, such as when applied to wet hair keratin fibers.

[0021] According to one specific embodiment, the composition T according to the invention comprises one or more alkali agents.

[0022] The alkaline agent can be selected from commonly used reagents, especially from alkali metal or alkaline earth metal hydroxides, ammonium hydroxide, organic amines, preferably alkanolamines, and mixtures thereof, preferably sodium hydroxide, potassium hydroxide, monoethanolamine, 2-amino-2-methyl-1-propanol and triethanolamine, preferably sodium hydroxide.

[0023] Composition T may contain water. Preferably, composition T contains water.

[0024] Advantageously, the water content (when present) is from 40% to 95% by weight relative to the total weight of composition T, preferably from 50% to 90% by weight, more preferably from 60% to 85% by weight, and even more preferably from 65% to 80% by weight.

[0025] Anionic and / or amphoteric or zwitterionic surfactants

[0026] According to the present invention, composition T comprises at least one surfactant selected from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof.

[0027] Advantageously, the total content of surfactant ranges from 1% to 50% by weight relative to the total weight of composition T, preferably from 5% to 40% by weight, more preferably from 10% to 30% by weight, even more preferably from 12% to 30% by weight, and even more preferably from 15% to 30% by weight.

[0028] Anionic surfactants

[0029] Anionic surfactants can be selected from sulfate, sulfonate, and / or carboxylic acid (or carboxylate) surfactants. Of course, mixtures of these surfactants can also be used.

[0030] It should be understood in this specification that: - Carboxylate anionic surfactants contain at least one carboxylic acid or carboxylate functional group (-COOH or -COO). - It may also optionally contain one or more sulfate and / or sulfonate functional groups; - Sulfonate anionic surfactants contain at least one sulfonate functional group (-SO3H or -SO3) - It may also optionally contain one or more sulfate functional groups, but not any carboxylate functional groups; and - Sulfate anionic surfactants contain at least one sulfate functional group, but do not contain any carboxylate or sulfonate functional groups.

[0031] Therefore, the carboxylate anionic surfactants that can be used contain at least one carboxylic acid or carboxylate functional group (-COOH or -COO). - ).

[0032] They can be selected from the following compounds: fatty acids, acylglycine salts, acyl lactates, acyl sarcosine salts, acyl glutamate salts; alkyl-D-galactoside uronic acid, alkyl ether carboxylic acid, alkyl (C6-C) 30 Aryl ether carboxylic acids, alkylamide ether carboxylic acids; and salts of these compounds; and mixtures thereof; wherein the alkyl and / or acyl groups of these compounds contain from 6 to 30 carbon atoms, particularly from 12 to 28, even more preferably from 14 to 24 or even from 16 to 22 carbon atoms; wherein the aryl group preferably indicates phenyl or benzyl; wherein these compounds may be polyoxyalkylene-substituted, particularly polyoxyethylene-substituted, and then preferably contain from 1 to 50 ethyleneoxy units, and even more preferably from 2 to 10 ethyleneoxy units.

[0033] C6-C polyglycosides-polycarboxylic acids can also be used. 24 Alkyl monoesters, such as polyglycoside-citric acid C6-C 24 Alkyl esters, polyglycosides-tartaric acid C6-C 24 Alkyl esters and polyglycosides-sulfosuccinic acid C6-C 24 Alkyl esters and their salts.

[0034] Preferably, the carboxylate anionic surfactant is selected, alone or in mixtures: - Fatty acids; - Acylglutamate, especially C6-C 24 Or even C 12-C 20 Acyl glutamate, such as stearoyl glutamate, and especially disodium stearoyl glutamate; - Acylsarcosine salts, especially C6-C 24 Or even C 12 -C 20 Acylsarcosine salts, such as palmitoylsarcosine salts, and especially palmitoylsarcosine sodium; - Acyl lactates, especially C 12 -C 28 Or even C 14 -C 24 Acyl lactates, such as benzyl lactate, and especially sodium benzyl lactate; - C6-C 24 And especially C 12 -C 20 Acylglycine salt; - (C6-C 24 )alkyl ether carboxylates and especially (C 12 -C 20 )alkyl ether carboxylates; - Polyoxyalkylene-modified (C6-C 24 Alkyl (amide) ether carboxylic acids, especially those containing 2 to 50 ethylene oxide groups; In particular, they are in the form of alkali metal or alkaline earth metal salts, ammonium salts or amino alkoxides.

[0035] The above-mentioned carboxylic acid surfactants can very specifically include fatty acid surfactants, especially C6-C. 30 Surfactants.

[0036] Fatty acids can include lauric acid, palmitic acid, myristic acid, stearic acid, oleic acid, and benzolic acid.

[0037] Fatty acids are preferably selected from palmitic acid, myristic acid, stearic acid and mixtures thereof.

[0038] Among the carboxylic acid surfactants mentioned above, sarcosine surfactants deserve special mention. In (C6-C... 30 Among acyl sarcosine salts, palmitoyl sarcosine salt, stearyl sarcosine salt, myristoyl sarcosine salt, lauroyl sarcosine salt, and cocoyl sarcosine salt can be mentioned in acidic or salted forms.

[0039] Anionic surfactants of the sarcosine salt type are advantageously selected from sodium lauroyl sarcosine, stearoyl sarcosine, myristoyl sarcosine, and mixtures thereof, and preferably from stearoyl sarcosine, myristoyl sarcosine, and mixtures thereof.

[0040] Among carboxylic acid surfactants, polyoxyalkylene-modified alkyl (amide) ether carboxylic acids and their salts may also be mentioned, especially those containing 2 to 50 alkylene oxides and particularly ethylene oxides, such as compounds marketed by Kao Corporation under the name Akypo.

[0041] Sulfonate anionic surfactants that can be used contain at least one sulfonate functional group (-SO3H or -SO3). - ).

[0042] They may be selected from the following compounds: alkyl sulfonates, alkylamide sulfonates, alkyl aryl sulfonates, α-olefin sulfonates, alkane sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, N-acyl taurates, acyl hydroxyethyl sulfonates, alkyl sulfosuccinates; and salts of these compounds; The alkyl groups of these compounds contain 6 to 30 carbon atoms, particularly 12 to 28, even more preferably 14 to 24 or even 16 to 22 carbon atoms; the aryl group preferably indicates a phenyl or benzyl group; These compounds can be polyoxyalkylene-, particularly polyoxyethylene-, and then preferably contain from 1 to 50 ethyleneoxy units, and even more preferably from 2 to 10 ethyleneoxy units.

[0043] Preferably, the sulfonate anionic surfactant is selected, alone or in mixtures: - C6-C 24 And especially C 12 -C 20 Alkyl sulfosuccinates, especially lauryl sulfosuccinates; - C6-C 24 And especially C 12 -C 20 Alkyl ether sulfosuccinate; - C6-C 24 And especially C 12 -C 20 N-acyl taurine; - (C6-C 24 Acylhydroxyethyl sulfonate, preferably (C 12 -C 18 Acyl hydroxyethyl sulfonate; In particular, they are in the form of alkali metal or alkaline earth metal salts, ammonium salts or amino alkoxides.

[0044] Preferably, the sulfonate-type anionic surfactant is selected from N-acyl taurates, and in particular N-acyl N-methyl taurates, acyl hydroxyethyl sulfonates, and their salts and mixtures thereof.

[0045] More preferably, the sulfonate type anionic surfactant is selected from acylhydroxyethyl sulfonates, as well as their salts and mixtures thereof.

[0046] When the anionic surfactant is in the form of a salt, the salt may be selected from alkali metal salts (such as sodium or potassium salts), ammonium salts, amine salts, and especially amino alkoxides and alkaline earth metal salts (such as magnesium salts).

[0047] Examples of amino alkoxides 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-prop-1,3-diol salts and tris(hydroxymethyl)aminomethane salts.

[0048] Alkali metal salts or alkaline earth metal salts are preferred, and sodium or magnesium salts are particularly preferred.

[0049] Preferably, the anionic surfactant is selected from: - C6-C 30 Especially C8-C 24 fatty acid; - C6-C 24 C is preferred 10 -C 22 Especially C 12 -C 20 Alkyl sulfates, - C6-C 24 C is preferred 10 -C 22 Especially C 12 -C 20 Alkyl ether sulfates, preferably containing from 1 to 20 ethylene oxide units, - C6-C 24 Especially C 12 -C 20 Alkyl sulfosuccinates, especially lauryl sulfosuccinates; - C6-C 24 Especially C 12 -C 20 Alkyl ether sulfosuccinate; - C6-C 24 Especially C 12 -C 20 N-acyl taurine; - (C6-C 24Acylhydroxyethyl sulfonate, preferably (C 12 -C 18 Acyl hydroxyethyl sulfonate; - C6-C 24 Especially C 12 -C 20 Acylsarcosine salts; especially palmitoylsarcosine, stearoylsarcosine and myristylsarcosine; - (C6-C 24 ) alkyl ether carboxylates, preferably (C 12 -C 20 )alkyl ether carboxylates; - Polyoxyalkylene-modified (C6-C 24 (alkylamido) ether carboxylic acids and their salts, especially those containing 2 to 50 alkylene groups, and more particularly ethylene groups; - C6-C 24 Especially C 12 -C 20 Acylglutamate; - C6-C 24 Especially C 12 -C 20 Acylglycine salt; - and its salts, especially its alkali metal or alkaline earth metal or zinc salts, ammonium salts or amino alcohols; - and its mixtures.

[0050] Preferably, the anionic surfactant in composition T is selected from sulfonate-type anionic surfactants, and more preferably from (C 10 -C 22 )alkyl sulfates, (C 10 -C 22 ) alkyl ether sulfates and mixtures thereof, more preferably selected from (C 10 -C 22 Sodium alkyl ether sulfate and its mixtures.

[0051] Amphoteric or zwitterionic surfactants

[0052] The composition T according to the invention may contain one or more amphoteric or zwitterionic surfactants.

[0053] In particular, the preferred non-silicone amphoteric or zwitterionic surfactant used in the composition T according to the invention can be, in particular, optionally quaternized derivatives of aliphatic secondary or tertiary amines, wherein the aliphatic group is a straight or branched chain containing 8 to 22 carbon atoms, and the amine derivative contains at least one anionic group, such as a carboxylate, sulfonate, sulfate, phosphate, or phosphonate group.

[0054] It is worth mentioning (C8-C) 20 )alkyl betaine, (C8-C 20 )alkyl sulfonyl betaine, (C8-C 20 )alkylamide (C1-C6)alkyl betaine, (C8-C 20 )alkylamide (C1-C6)alkylsulfonyl betaine, (C8-C 20 )alkylamide (C3-C8)alkyl betaine, (C8-C 20 Alkylamide (C6-C8) alkyl sulfonyl betaine and mixtures thereof.

[0055] These compounds were classified in the 5th edition of the CTFA dictionary in 1993 under the names disodium cocoamphodiacetate, disodium lauroylamphodiacetate, disodium decanoylamphodiacetate, disodium octanoylamphodiacetate, disodium cocoamphodiapropionate, disodium lauroylamphodiapropionate, disodium decanoylamphodiapropionate, disodium octanoylamphodiapropionate, lauroylamphodiapropionic acid, and cocoamphodiapropionic acid.

[0056] For example, one could mention Rhodia's product under the brand name Miranol. ® C2MConcentrate sells cocoamphodiacetate.

[0057] The compound that can be mentioned is classified in the CTFA dictionary under the name diethylaminopropylcocoyl asparagine sodium and is sold by Chimex under the name Chimexane HB.

[0058] These compounds can be used alone or as a mixture.

[0059] Among the amphoteric or zwitterionic surfactants mentioned above, (C8-C) is advantageously used. 20 Alkyl betaines, such as cocoyl betaine, (C8-C 20 Alkyl amide (C3-C8) alkyl betaines, such as cocamidopropyl betaine, (C8-C 20 )alkyl amphoteric acetate, (C8-C 20 ) alkyl amphoteric diacetates and mixtures thereof; and preferably (C8-C 20 )alkyl betaine, (C8-C 20 Alkylamide (C3-C8) alkyl betaine and mixtures thereof.

[0060] Advantageously, the amphoteric or zwitterionic surfactant in composition T is selected from (C8-C9) 20 )alkyl betaine, (C8-C 20)alkyl sulfonyl betaine, (C8-C 20 )alkylamide (C3-C8)alkyl betaine, (C8-C 20 alkylamide (C6-C8) alkyl sulfonyl betaine, and mixtures thereof, more preferably selected from (C8-C8) alkyl sulfonyl betaine. 20 )alkyl betaine, (C8-C 20 Alkylamide (C3-C8) alkyl betaines and mixtures thereof, more preferably selected from (C8-C8) alkyl betaines. 20 Alkylamide (C3-C8) alkyl betaine and mixtures thereof.

[0061] According to a preferred embodiment, composition T comprises a certain amount of a surfactant selected from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, in an amount of 1% to 50% by weight, preferably 5% to 40% by weight, and more preferably 10% to 30% by weight, relative to the total weight of composition T.

[0062] Preferably, the surfactant is selected from: - Especially C8 to C 26 And C is preferred. 10 To C 22 Alkyl sulfates; - Especially C8 to C 26 And C is preferred. 10 To C 22 Alkyl ether sulfates, preferably comprising 2 to 10 ethyleneoxy units; In particular, it exists in the form of alkali metal or alkaline earth metal salts, ammonium salts, or amino alkoxides. - (C8-C 20 )alkyl betaine, (C8-C 20 Alkylamide (C3-C8) alkyl betaines and mixtures thereof, preferably selected from (C8-C8) alkyl betaines. 20 )alkylamide (C3-C8) alkyl betaine and mixtures thereof; and its mixtures.

[0063] According to a preferred embodiment, the composition according to the invention comprises at least one anionic surfactant as defined above and at least one amphoteric or zwitterionic surfactant as defined above.

[0064] additive

[0065] Composition T used in the context of the staining method according to the invention may further contain any commonly used additives or auxiliaries.

[0066] Additives that may be used include reducing agents, thickeners, softeners, humectants, UV shielding agents, solubilizers, fragrances, vitamins, polymers, preservatives, fatty substances, and mixtures thereof.

[0067] (poly)carbodiimide compounds

[0068] As noted above, composition C used in the context of the method according to the invention comprises at least one (poly)carbodiimide compound of formula (II).

[0069] The composition may contain at least two different (poly)carbodiimide compounds, present as a mixture in the composition.

[0070] the term" (poly)carbodiimide compounds "This means a compound containing one or more carbodiimide groups, preferably at least two carbodiimide groups, more preferably at least three carbodiimide groups; in particular, the number of carbodiimide groups does not exceed 200, preferably 150, more preferably 100."

[0071] the term" carbodiimide group "This refers to the divalent straight-chain triatomic part of the general formula -(N=C=N)-.

[0072] Preferably, the (poly)carbodiimide compound is selected from compounds of formula (II): (II), in: - X1 and X2 independently represent oxygen atom O, sulfur atom S or NH group; - R1 and R2 independently represent hydrocarbon-based groups optionally inserted with one or more heteroatoms; - n and z indicate integers from 1 to 20, where n+z ≥ 2 and w indicates integers from 1 to 3; - L1 independently represents C1-C 18 Divalent aliphatic hydrocarbons based on hydrocarbon groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocyclic alkyl or C6-C 14 aryl groups and their mixtures; - E independently represents a group selected from the following: -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; R3 and R4 independently represent divalent hydrocarbon-based groups optionally inserted with one or more heteroatoms; - R5 independently represents a covalent bond or optionally an inserted saturated divalent hydrocarbon-based group with one or more heteroatoms; - R6 independently represents a hydrogen atom or optionally inserts a hydrocarbon-based group with one or more heteroatoms.

[0073] the term" Hydrocarbon-based groups "This means a saturated or unsaturated, straight-chain or branched group containing 1 to 300 carbon atoms, preferably 1 to 250 carbon atoms, and more preferably 1 to 200 carbon atoms. Preferably, the hydrocarbon-based group is a saturated straight-chain group."

[0074] Hydrocarbon-based groups can contain one or more cyclic groups.

[0075] Hydrocarbon-based groups may be inserted with one or more heteroatoms specifically selected from O, S, or N, and / or be replaced by one or more cations, anions, or zwitterions or cation groups such as ammonium, anion groups such as carboxylate, or zwitterions, and / or contain metal ions that may be introduced in the form of salts.

[0076] the term" heteroatoms "This refers to oxygen (O), sulfur (S), or nitrogen (N) atoms, as well as halogen atoms such as Cl, F, Br, and I. If the chain based on a hydrocarbon group contains heteroatoms, then the heteroatoms are preferably selected from oxygen (O), sulfur (S), or nitrogen (N) atoms."

[0077] Preferably, X1 and X2 independently represent oxygen atoms.

[0078] Preferably, R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols in which the hydroxyl groups have been removed, and mixtures thereof.

[0079] In a preferred embodiment, R1 and R2 are independently selected from the following groups (i) to (iv): (i) Compounds of formula (III): R7-OC(O)-C(R8)(H)- (III), Wherein R7 represents a C1-C3 alkyl group, and R8 represents a hydrogen atom or a C1-C3 alkyl group; preferably, R7 is a methyl group, and R8 is a hydrogen atom or a methyl group.

[0080] (ii) Compounds of formula (IV): R9-[O-CH2-C(H)(R 10 )] p - (IV), Where R9 represents a C1-C4 alkyl group, R 10 R represents a hydrogen atom or a C1-C4 alkyl group, and p indicates an integer from 1 to 3; preferably, R9 is methyl, ethyl, or butyl. 10 It is a hydrogen atom or a methyl group and p equals 1.

[0081] (iii) Compounds of the following formula (V): (R 11 )2N-CH2-C(H)(R 12 )- (V), Where R 11 It represents C1-C4 alkyl, and R 12 Represents a hydrogen atom or a C1-C4 alkyl group; preferably, R 11 It is methyl, ethyl, or butyl, and R 12 It is a hydrogen atom or a methyl group.

[0082] (iv) Compounds of formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI), Where R 13 Indicates C1-C4 alkyl or phenyl, R 14 Represents a hydrogen atom or a C1-C4 alkyl group, and q indicates an integer ranging from 4 to 30; preferably, R 13 It is methyl, ethyl, or butyl, and R 14 It is a hydrogen atom or a methyl group.

[0083] Preferably, R1 and R2 independently represent the compound of formula (VI), wherein R 13 R represents C1-C4 alkyl or phenyl, preferably C1-C4 alkyl, more preferably methyl. 14 It represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer from 4 to 30.

[0084] According to an alternative embodiment, R1 and R2 are different, and one of the groups R1 or R2 represents a compound of formula (IV) as described above, and the other of the groups R1 or R2 represents a compound of formula (VI) as described above.

[0085] Preferably, in formula (IV), R9 is methyl, ethyl, or butyl, and R 10 It is a hydrogen atom or a methyl group and p equals 1.

[0086] Preferably, in formula (VI), R 13 It is methyl, ethyl, or butyl, and R 14 It is a hydrogen atom or a methyl group and q indicates an integer from 4 to 30.

[0087] According to another alternative embodiment, R1 and R2 are the same and represent compounds of formula (VI), wherein R 13R represents C1-C4 alkyl or phenyl, preferably C1-C4 alkyl, more preferably methyl. 14 It represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer from 4 to 30.

[0088] Preferably, n indicates an integer ranging from 1 to 20, more preferably from 2 to 20.

[0089] Preferably, z indicates an integer ranging from 1 to 20, more preferably from 2 to 20.

[0090] Preferably, w equals 1.

[0091] Preferably, w equals 1, and n+z indicates an integer from 4 to 10.

[0092] Preferably, L1 is selected from C1-C 18 Divalent aliphatic hydrocarbon-based groups such as methylene, ethylene, and propylene, C3-C 15 Cycloalkylene compounds such as cyclopentylene, cycloheptylene, and cyclohexylene, C3-C 12 Heterocyclic alkyl groups such as imidazolyl, pyrrolidine, and furanyl, or C6-C 14 Aryl groups such as phenylene and mixtures thereof.

[0093] For example, L1 can be selected from groups derived from the following: toluene diisocyanate, hexamethylene diisocyanate, phenyl diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-1,3-dioctylcyclobutane, 4,4'-dicyclohexylmethane diisocyanate, tetramethylphenyl diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate and phenyl diisocyanate, and mixtures thereof.

[0094] Preferably, L1 is selected from C3-C 15 Cycloalkyl or C6-C 14 aryl compounds, and mixtures thereof, such as compounds of formula (VII): .

[0095] Preferably, L1 is 4,4-dicyclohexylenemethane corresponding to the following formula (VIII): (VIII)

[0096] According to another embodiment, when L1 is C6-C 14In the arylene form, L1 is not the m-tetramethylphenyldimethyl group represented by the following formula (IX): (IX).

[0097] As previously noted, E independently represents a group selected from: -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; R3 and R4 independently represent divalent hydrocarbon-based groups optionally inserted with one or more heteroatoms; - R5 independently represents a covalently bonded or optionally inserted saturated divalent hydrocarbon-based group with one or more heteroatoms; and - R6 independently represents a hydrogen atom or optionally inserts a hydrocarbon-based group with one or more heteroatoms.

[0098] Preferably, R3 and R4 are independently selected from C6-C atoms optionally intercalated with one or more heteroatoms. 14 arylene compounds such as phenylene, C3-C 12 Cycloalkylene compounds such as cyclopropylene and cyclobutylene, straight-chain or branched C1-C 18 Alkylenes such as methylene and ethylene, and mixtures thereof.

[0099] More preferably, R3 and R4 are independently selected from straight-chain or branched C1-C chains optionally intercalated with one or more heteroatoms. 18 Alkylenes, such as methylene, butylene, propylene, or ethylene.

[0100] Preferably, when R5 is not a covalent bond, R5 is selected from C6-C bonds optionally intercalated with one or more heteroatoms. 14 arylene compounds such as phenylene, C3-C 12 Cycloalkylene compounds such as cyclopropylene and cyclobutylene, straight-chain or branched C1-C 18 Alkylenes such as methylene and ethylene, and mixtures thereof.

[0101] Preferably, R6 is selected from C6-C, which may optionally have one or more heteroatoms inserted. 14 arylene compounds such as phenylene, C3-C 12 Cycloalkylene compounds such as cyclopropylene and cyclobutylene, straight-chain or branched C1-C 18 Alkylenes such as methylene and ethylene, and mixtures thereof.

[0102] Preferably, E represents the group -O-R3-O-, wherein R3 is selected from C6-C groups optionally intercalated with one or more heteroatoms. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18Alkylenes and mixtures thereof.

[0103] More preferably, E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C chain optionally intercalated with one or more heteroatoms. 18 Alkylenes, such as methylene, butylene, propylene, or ethylene.

[0104] According to a specific embodiment, the (poly)carbodiimide compound is a copolymer derived from α-methylstyrene isocyanate of the following formula (X): (X), Wherein R independently represents an alkyl group containing 1 to 24 carbon atoms, a cycloalkyl group containing 3 to 24 carbon atoms, or an aryl group containing 6 to 24 carbon atoms, and n indicates an integer ranging from 2 to 100.

[0105] In this embodiment, the term "alkyl" is as previously defined.

[0106] In this embodiment, the term "cycloalkyl" is as previously defined.

[0107] In this embodiment, n can indicate an integer ranging from 2 to 50, preferably from 3 to 30, and even more preferably from 5 to 10.

[0108] According to another specific embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI): (XI), 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.

[0109] “alkyl,” “cycloalkyl,” and “aryl” are as previously defined.

[0110] According to a preferred embodiment, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein: - X1 and X2 represent oxygen atoms independently; - R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols in which the hydroxyl groups have been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycols in which the hydroxyl groups have been removed, and more preferably compounds of formula (VI) previously described, wherein R 13 R represents C1-C4 alkyl or phenyl, preferably C1-C4 alkyl, more preferably methyl. 14 It represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30; - n and z (when they exist) indicate integers from 1 to 20, where n+z ≥ 2 and w equals 1; - L1 (when it exists) is selected from C1-C 18 Divalent aliphatic hydrocarbons based on hydrocarbon groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocyclic alkyl or C6-C 14 aryl groups and mixtures thereof, preferably C3-C 15 Cycloalkylene; - A (when it exists) is selected from C1-C 18 Divalent aliphatic hydrocarbons based on hydrocarbon groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocyclic alkyl or C6-C 14 aryl groups and mixtures thereof, preferably C3-C 15 Cycloalkylene; - E (when present) independently represents a group selected from the following: -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; R3 and R4 are independently selected from C6-C atoms that may optionally have one or more heteroatoms inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof; - When R5 is not covalent, R5 (when it is present) is selected from C6-C with one or more heteroatoms optionally inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof; and - R6 (when present) is selected from C6-C which may optionally have one or more heteroatoms inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof.

[0111] Preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein: - X1 and X2 represent oxygen atoms independently; - R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols in which the hydroxyl groups have been removed, and mixtures thereof; - n and z indicate integers from 1 to 20, where n+z ≥ 2 and w equals 1; - L1 is selected from C1-C 18 Divalent aliphatic hydrocarbons based on hydrocarbon groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocyclic alkyl or C6-C 14 aryl groups and their mixtures; - E independently represents a group selected from the following: -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; R3 and R4 are independently selected from C6-C atoms that may optionally have one or more heteroatoms inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof; - When R5 is not covalent, R5 is selected from C6-C with one or more heteroatoms optionally inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof; and - R6 is selected from C6-C which may optionally have one or more heteroatoms inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof.

[0112] More preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein: - X1 and X2 represent oxygen atoms independently; - R1 and R2 are independently monoalkyl ethers of (poly)alkylene glycols in which the hydroxyl groups have been removed; - n and z indicate integers from 1 to 20, where n+z ≥ 2 and w equals 1; - L1 is C3-C 15 Cycloalkylene; - E independently represents a group selected from the following: -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; R3 and R4 are independently selected from C6-C atoms that may optionally have one or more heteroatoms inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18Alkylenes and mixtures thereof; - When R5 is not covalent, R5 is selected from C6-C with one or more heteroatoms optionally inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof; and - R6 is selected from C6-C which may optionally have one or more heteroatoms inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof.

[0113] Even more preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein: - X1 and X2 represent oxygen atoms independently; - R1 and R2 independently represent compounds of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI), Where R 13 R represents C1-C4 alkyl or phenyl, preferably C1-C4 alkyl, more preferably methyl. 14 It represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30; - n and z indicate integers from 1 to 20, where n+z ranges from 4 to 10 and w equals 1; - L1 is C3-C 15 Cycloalkylene compounds, such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylmethane; and - E represents the group -O-R3-O-, where R3 is selected from C6-C groups optionally intercalated with one or more heteroatoms. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof.

[0114] Even more preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein: - X1 and X2 represent oxygen atoms independently; - R1 and R2 independently represent compounds of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q- (VI) Where R 13 R represents C1-C4 alkyl or phenyl, preferably C1-C4 alkyl, more preferably methyl. 14 It represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30; - n and z indicate integers from 1 to 20, where n+z ranges from 4 to 10 and w equals 1; - L1 is C3-C 15 Cycloalkylene compounds, such as cyclopentylene, cyclohepylene, cyclohexylene, and 4,4-dicyclohexylmethane, preferably 4,4-dicyclohexylmethane; and - E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C chain optionally intercalated with one or more heteroatoms. 18 Alkylenes, such as methylene, propylene, butylene, or ethylene.

[0115] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of the following formula (XII): (XII), Where L1 is 4,4-dicyclohexylmethane, n and z indicate integers from 1 to 20, where n+z ranges from 4 to 10, E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C optionally intercalated with one or more heteroatoms. 18 Alkylenes, such as methylene, propylene, butylene, or ethylene, and r and s indicate an integer range from 4 to 30.

[0116] Advantageously, the total content of the (poly)carbodiimide compound ranges from 0.01% to 20% by weight relative to the total weight of composition C, preferably from 0.1% to 15% by weight, more preferably from 0.2% to 10% by weight, even more preferably from 0.5% to 8% by weight, and even more preferably from 1% to 6% by weight.

[0117] Polymers containing at least one reactive group selected from carboxylic acids

[0118] Composition C used in the context of the method according to the invention comprises at least one polymer containing at least one reactive group selected from carboxylic acids, preferably at least one acrylic polymer.

[0119] Preferably, the polymer comprising at least one reactive group selected from carboxylic acids, preferably an acrylic polymer, is in the form of an aqueous dispersion of acrylic polymer particles.

[0120] Therefore, preferably, composition C comprises at least one acrylic polymer in the form of an aqueous dispersion of acrylic polymer particles.

[0121] A dispersion can be a simple dispersion in an aqueous medium of a cosmetic composition. Latex can be mentioned as a specific example of a dispersion.

[0122] More preferably, the acrylic polymer is in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0123] For the purposes of this invention, the term " polymer "This refers to a compound that corresponds to one or more repeating units (which are derived from compounds called monomers). The unit or these units are repeated at least twice and preferably at least three times."

[0124] the term" Film-forming polymers "" refers to a polymer that can form a macroscopic continuous film, particularly on hair keratin fibers, either on its own or in the presence of an auxiliary film-forming agent, and preferably an adhesive film.

[0125] For the purposes of this invention, the term " acrylic polymers "This means a polymer synthesized from at least one monomer selected from (meth)acrylic acid and / or (meth)acrylate and / or (meth)acrylamide."

[0126] The units of the (meth)acrylic acid monomer derived from the polymer may optionally be in the form of salts, especially alkali metal salts, alkaline earth metal salts or ammonium salts, or organic alkali salts.

[0127] (meth)acrylates (also known as (meth)acrylates) are advantageously selected from alkyl (meth)acrylates, particularly (meth)acrylates C1 to C1. 30 Alkyl esters, preferably (meth)acrylic acid C1 to C1 20 Alkyl esters and even better (meth)acrylic acid C1 to C1 10 Alkyl esters; aryl esters of (meth)acrylate, especially C6 to C6 (meth)acrylate. 10 Aryl esters; and hydroxyalkyl esters of (meth)acrylate, especially C2 to C6 hydroxyalkyl esters of (meth)acrylate.

[0128] Among the alkyl esters of (meth)acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and cyclohexyl methacrylate may be mentioned.

[0129] Among (meth)acrylates, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate may be mentioned.

[0130] Among (meth)acrylate aryl esters, benzyl acrylate and phenyl acrylate can be mentioned.

[0131] Particularly preferred (meth)acrylates are alkyl, preferably C1 to C2. 30 More preferably C1 to C 20 Furthermore, it is even better from C1 to C 10 And even more specifically, C1 to C4 alkyl (meth)acrylates.

[0132] According to the present invention, the alkyl group of the ester may be fluorinated or even perfluorinated, that is, some or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms.

[0133] Examples of (meth)acrylamides that can be mentioned include (meth)acrylamides as well as N-alkyl (meth)acrylamides, particularly N-(C2 to C2)acrylamides. 12 Alkyl (methyl)acrylamide. Among the N-alkyl (methyl)acrylamides that may be mentioned are N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, and N-undecylacrylamide.

[0134] The acrylic polymers according to the invention can be homopolymers or copolymers, advantageously copolymers, and even better copolymers of (meth)acrylic acid and (meth)acrylates.

[0135] Preferably, the acrylic polymer according to the invention comprises one or more units derived from monomers: a) (meth)acrylic acid; and b) C1 to C 30 More preferably C1 to C 20 Furthermore, it is even better from C1 to C 10 And even more specifically, C1 to C4 alkyl (meth)acrylates.

[0136] Preferably, the aqueous dispersion of acrylic polymer particles does not contain any surfactants.

[0137] the term" surfactants "Refers to any reagent that can change the surface tension between two surfaces."

[0138] Among the acrylic polymers according to the invention, copolymers of (meth)acrylic acid and (meth)acrylate or (meth)acrylate, particularly copolymers of methacrylic acid and ethyl acrylate, may be mentioned, such as compounds sold by BASF under the trade name Luvimer MAE, or by Lubrizol under the trade name Fixate Superhold Polymer, or by Daito Kasei Kogyo under the trade name Daitosol 3000VP3, or by Daito Kasei Kogyo under the trade name Daitosol 3000 SLPN-PE1.

[0139] Acrylic polymers may optionally contain one or more additional monomers besides (meth)acrylic acid and / or (meth)acrylate and / or (meth)acrylamide monomers.

[0140] As another monomer, styrene monomers, particularly styrene and α-methylstyrene, will be mentioned, with styrene being preferred.

[0141] In particular, the acrylic polymer can be a styrene / (meth)acrylate copolymer, and especially selected from at least one styrene monomer and at least one (meth)acrylate C1 to C1. 20 Alkyl esters, preferably (meth)acrylic acid C1 to C1 10 Polymers of copolymers produced by the polymerization of alkyl ester monomers.

[0142] (Meth)acrylic acid C1 to C 10 The alkyl ester monomer can be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate.

[0143] As an acrylic polymer, styrene / (meth)acrylate copolymers can be mentioned, which are marketed by BASF under the name Joncryl 77, by Akzo Nobel under the name Yodosol GH41F, and by Interpolymer under the name Syntran 5760 CG.

[0144] Preferably, composition C comprises an aqueous dispersion of at least one acrylic polymer particle.

[0145] More preferably, composition C comprises an aqueous dispersion of at least one acrylic polymer particle containing one or more units derived from monomers: a) (meth)acrylic acid; and b) C1 to C 30 More preferably C1 to C 20 Furthermore, it is even better from C1 to C 10 And even more specifically, C1 to C4 alkyl (meth)acrylates.

[0146] Preferably, based on the weight of the dispersion, the aqueous dispersion of acrylic polymer particles has an acrylic polymer (or active material, or solid) content of 20% to 60% by weight, more preferably 22% to 55% by weight, and even more preferably 25% to 50% by weight.

[0147] Advantageously, the polymer containing at least one reactive group selected from carboxylic acids, preferably an acrylic polymer, is present in a total content ranging from 0.1% to 35% by weight relative to the total weight of composition C, preferably from 0.5% to 30% by weight, more preferably from 1% to 20% by weight, and even more preferably from 3% to 15% by weight.

[0148] According to specific embodiments, the total content of the aqueous dispersion of acrylic polymer particles is preferably from 0.1% to 35% by weight relative to the total weight of composition C, more preferably from 0.5% to 30% by weight, more preferably from 1% to 20% by weight, and even more preferably from 3% to 15% by weight.

[0149] Colorant

[0150] Composition C used in the context of the method according to the invention comprises at least one colorant selected from pigments, direct dyes and mixtures thereof.

[0151] Preferably, composition C used in the context of the method according to the invention comprises at least one pigment.

[0152] The term "pigment" refers to any pigment that imparts color to keratin materials. Their solubility in water at 25°C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

[0153] The pigments that can be used are particularly selected from organic and / or mineral pigments known in the art, especially those from Kirk-Othmer's... Encyclopedia of Chemical Technology Kirk Osmer Encyclopedia of Chemical Technology ] and Ullmann's Encyclopedia of Industrial Chemistry Ullman Encyclopedia of Industrial Chemistry Those described in [the text].

[0154] They can be natural, of natural origin, or non-natural.

[0155] These pigments can be in the form of pigment powder or paste. They can be coated or uncoated.

[0156] Pigments can be selected from mineral pigments, organic pigments, lakes, pigments with special effects such as mother-of-pearl or glitter, and mixtures thereof.

[0157] The pigment can be a mineral pigment. The term "mineral pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann's encyclopedia. Among the mineral pigments available in this invention, iron oxide, chromium oxide, manganese violet, ultramarine, chromium hydrate, iron blue, and titanium oxide may be mentioned.

[0158] Pigments can be organic pigments. The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann's Encyclopedia.

[0159] Organic pigments can be selected in particular from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complexes, isoindolineone, isoindoline, quinacridone, violetone, perylene, diketonepyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane, and quinoline phthalocyanine compounds.

[0160] Specifically, white or colored organic pigments may be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments with index numbers CI 42090, 69800, 69825, 74100, and 74160 in the Color Index; yellow pigments with index numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, and 47005 in the Color Index; green pigments with index numbers CI 61565, 61570, and 74260 in the Color Index; and pigments with index numbers CI 42090, 69800, 69825, 74100, and 74160 in the Color Index. Orange pigments numbered 11725, 45370, and 71105; red pigments numbered CI12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, and 75470 in the color index; and pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.

[0161] Other examples that may be mentioned include pigment pastes made from organic pigments, such as products marketed by Hoechst under the following names: - Cosmenyl Yellow 10G: Yellow pigment (CI 11710); - Cosmenyl Yellow G: Yellow 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: Purple 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).

[0162] The pigments according to the invention can also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments can in particular consist of particles comprising an inorganic core, at least one binder for attaching an organic pigment to the core, and at least one organic pigment that at least partially covers the core.

[0163] Organic pigments can also be lakes. The term "lake" refers to a dye adsorbed onto insoluble particles, thereby making the resulting component insoluble during use.

[0164] The inorganic substrates on which the dye is adsorbed are, for example, alumina, silicon dioxide, sodium calcium borosilicate, or aluminum calcium borosilicate.

[0165] Among these dyes, carmine acid may be mentioned. Dyes known by the following names may also be mentioned: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), and D&C Blue 1 (CI 42 090).

[0166] An example of a lake that may be mentioned is a product known by the following name: D&C Red 7 (CI 15 850:1).

[0167] Pigments can also be pigments with special effects. The term "pigments with special effects" refers to pigments that typically produce a non-uniform colored appearance (characterized by a certain chroma, vivacity, and brightness level) that varies with observation conditions (light, temperature, viewing angle, etc.). Therefore, they differ from colored pigments that provide standard, uniform opaque, translucent, or transparent hues.

[0168] There are several types of special effect pigments: those with low refractive index, such as fluorescent or photochromic pigments, and those with high refractive index, such as mother-of-pearl, interference pigments, or glitter sheets.

[0169] Examples of pigments with special effects that may be mentioned include pearlescent pigments, such as mica coated with titanium or bismuth oxychloride; colored pearlescent pigments, such as mica coated with titanium and iron oxides, mica coated with iron oxides, mica coated with titanium and especially with iron blue or chromium oxides, mica coated with titanium and organic pigments as previously defined, and also pearlescent pigments based on bismuth oxychloride. Pearlescent pigments that may be mentioned include Cellini (mica-TiO2-lake) marketed by BASF, Prestige (mica-TiO2) marketed by Eckart, Prestige Bronze (mica-Fe2O3) marketed by Eckart, and Colorona (mica-TiO2-Fe2O3) marketed by Merck.

[0170] Also noteworthy are the golden mother-of-pearls sold by BASF under the names Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite), and Monarch Gold 233X (Cloisonne); the bronze mother-of-pearls sold by Merck under the names Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona), and by BASF under the name Super Bronze (Cloisonne); the orange mother-of-pearls 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); and the mother-of-pearls sold by BASF under the names Nu-antique Copper 340XB (Cloisonne) and Brown. Brown mother-of-pearl sold under CL4509 (Chromalite); particularly copper-toned mother-of-pearl sold by BASF under the name Copper 340A (Timica); particularly red-toned mother-of-pearl sold by Merck under the name Sienna Fine (17386) (Colorona); particularly yellow-toned mother-of-pearl sold by BASF under the name Yellow (4502) (Chromalite); particularly red-toned mother-of-pearl sold by BASF under the name Sunstone G012 (Gemtone); particularly pink mother-of-pearl sold by BASF under the name Tan Opale G005 (Gemtone); particularly black mother-of-pearl sold by BASF under the name Nu-antique Bronze 240 AB (Timica); particularly blue mother-of-pearl sold by Merck under the name Matte Blue (17433) (Microna); particularly mother-of-pearl sold by Merck under the name Xirona Silver sells white mother-of-pearl with a silvery hue; and especially Merck sells gold-green, pink, and orange mother-of-pearl under the name Indian Summer (Xirona); and mixtures thereof.

[0171] As another example of mother-of-pearl, we can also mention particles comprising a borosilicate substrate coated with titanium oxide.

[0172] The particles containing glass substrates coated with titanium oxide are especially those sold by Toyal Corporation under the name Metashine MC1080RY.

[0173] Finally, examples of mother-of-pearl that can also be mentioned include polyethylene terephthalate glitter flakes, especially those marketed by Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (Silver Glitter Flakes). Multilayer pigments based on synthetic substrates, such as alumina, silica, sodium calcium borosilicate, aluminum calcium borosilicate, and aluminum, are also conceivable.

[0174] Pigments with special effects can also be selected from reflective particles, particularly those whose size, structure, especially the thickness of the layer to which they are made, as well as their physical and chemical properties and surface condition, allow them to reflect incident light. If appropriate, when applied to a carrier to be cosmetically applied, this reflection can have an intensity sufficient to produce visible highlights on the surface of the composition or mixture, i.e., points that make them appear shimmering and brighter in contrast to their environment.

[0175] Reflective particles can be selected so as not to significantly alter the coloring effect produced by the colorants bound to them, and more specifically, to optimize this effect in color reproduction. They can more specifically have yellow, pink, red, bronze, orange, brown, gold, and / or copper hues or tones.

[0176] These particles can take different forms and can be in particular flake or spherical form, especially spherical form.

[0177] Regardless of their form, reflective particles may or may not have a multilayer structure, and in the case of a multilayer structure, they may have, for example, at least one layer of reflective material of uniform thickness.

[0178] When reflective particles do not have a multilayer structure, they can be composed of, for example, metal oxides, especially synthetically obtained titanium or iron oxides.

[0179] When reflective particles have a multilayer structure, they may include, for example, natural or synthetic substrates, particularly synthetic substrates at least partially coated with at least one layer of reflective material, especially at least one metal or metallic material. The substrate may be made of one or more organic and / or mineral materials.

[0180] More specifically, it can be selected from glass, ceramics, graphite, metal oxides, alumina, silicon dioxide, silicates (especially aluminosilicates and borosilicates), and synthetic mica, and mixtures thereof; this list is not limiting.

[0181] Reflective materials may include a metal layer or a layer of metallic material.

[0182] Reflective particles are particularly described in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0183] Furthermore, as an example of reflective particles comprising mineral substrates coated with a metal layer, particles comprising borosilicate substrates coated with silver can also be mentioned.

[0184] The flake-shaped glass substrate particles with a silver coating are sold by Toyo Corporation under the name MicroglassMetashine REFSX 2025 PS. The glass substrate particles coated with a nickel / chromium / molybdenum alloy are sold by the same company under the names Crystal Star GF 550 and GF 2525.

[0185] 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 used. The substrate is coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxide, and mixtures thereof.

[0186] Examples that may be mentioned include aluminum powder, bronze powder, or copper powder coated with SiO2, which is sold by ECAR under the name Visionaire.

[0187] Interference pigments that are not attached to the substrate can also be mentioned, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter sheets (Geometric Pigments or Spectraf / x from Spectratek). Special effects pigments also include fluorescent pigments (whether these fluoresce in sunlight or produce ultraviolet fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments, and quantum dots, such as those sold by QuantumDots Corporation.

[0188] The various pigments that can be used in this invention enable a wide range of colors to be obtained, as well as specific optical effects, such as metallic or interference effects.

[0189] The pigments used in the compositions according to the invention are generally between 10 nm and 200 µm, preferably between 20 nm and 80 µm, and more preferably between 30 nm and 50 µm.

[0190] Pigments can be dispersed in the composition using dispersants.

[0191] Dispersants are used to protect dispersed particles from agglomeration or flocculation. The dispersant can be a surfactant, oligomer, polymer, or mixture thereof carrying one or more functional groups that have a strong affinity for the surface of the particles to be dispersed. In particular, they can become physically or chemically attached to the surface of the pigment. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid and esters of C8 to C20 fatty acids, as well as esters of polyols such as glycerol or diglycerol, are used, for example, poly(12-hydroxystearic acid) stearates with a molecular weight of about 750 g / mol, such as products sold by Avecia under the name Solsperse 21 000, polyglycerol-2-dihydroxystearate (CTFA name) sold by Henkel under the index number Dehymyls PGPH, or polyhydroxystearic acids such as products sold by Uniqema under the index number Arlacel P100, and mixtures thereof.

[0192] As other dispersants that can be used in the compositions of the present invention, references may be made to quaternary ammonium derivatives of condensed fatty acids, such as Solsperse 17 000 sold by Avecia, and polydimethylsiloxane / oxypropylene mixtures, such as those sold by Dow Corning under index numbers DC2-5185 and DC2-5225 C.

[0193] The pigments used in the composition can be surface-treated with organic reagents.

[0194] Therefore, in the context of this invention, pre-treated pigments are pigments that have undergone, in whole or in part, chemical, electronic, electrochemical, mechanochemical, or mechanical surface treatment with an organic reagent, and are then dispersed in the composition according to the invention, such organic reagent as those described in particular. Cosmetics and Toiletries [change Cosmetics and toiletriesFebruary 1990, Volume 105, pages 53-64. These organic reagents may be selected, for example, from waxes, such as carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and their derivatives; anionic surfactants; lecithin; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, such as aluminum stearate or aluminum laurate; metal alkoxides; polyethylene; (meth)acrylic acid polymers, such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, such as silicones, especially polydimethylsiloxane; organofluorine compounds, such as perfluoroalkyl ethers; fluorosilicone compounds.

[0195] Surface-treated pigments that can be used in the composition may have been treated with mixtures of these compounds and / or may have undergone several surface treatments.

[0196] The surface-treated pigments used in the context of this invention can be prepared according to surface treatment techniques well known to those skilled in the art, or can be commercially available as is.

[0197] Preferably, the surface-treated pigment is coated with an organic layer.

[0198] Organic reagents for treating pigments can adhere to pigments through solvent evaporation, chemical reactions between surface agent molecules, or the formation of covalent bonds between the surface agent and the pigment.

[0199] Surface treatment can therefore be performed, for example, by a chemical reaction between a surface agent and the pigment surface, and the formation of covalent bonds between the surface agent and the pigment or filler. This method is particularly described in patent US 4,578,266.

[0200] Organic reagents that are covalently bonded to pigments are preferred.

[0201] The reagent used for surface treatment may account for 0.1% to 50% by weight of the total weight of the surface-treated pigment, preferably 0.5% to 30% by weight of the total weight of the surface-treated pigment, and even more preferably 1% to 20% by weight of the total weight of the surface-treated pigment.

[0202] Preferably, the surface treatment agent for the pigment is selected from the following treatment agents: - PEG-silicone treatment agents, such as AQ surface treatment agents sold by LCW; - Polymethylsiloxane treatment agents, such as SI surface treatment agents sold by LCW; - Polydimethylsiloxane treatment agents, such as Covasil 3.05 surface treatment agent sold by LCW; - Polydimethylsiloxane / trimethylsiloxane treatment agents, such as Covasil 4.05 surface treatment agent sold by LCW; - Magnesium myristate treatment agents, such as MM surface treatment agents sold by LCW; - Aluminum dimyristate treatment agents, such as MI surface treatment agents sold by Miyoshi Corporation; - Perfluoropolymethyl isopropyl ether treatment agents, such as FHC surface treatment agents sold by LCW; - Sebacic acid isostearyl ester treatment agent, such as HS surface treatment agent sold by Miyoshi Chemical Co., Ltd.; - Perfluoroalkyl phosphate treatment agents, such as PF surface treatment agents sold by Daito Corporation; - Acrylic ester / polydimethylsiloxane copolymer and perfluoroalkyl phosphate treatment agents, such as FSA surface treatment agents sold by Daito Corporation; - Polymethylhydrosiloxane / perfluoroalkyl phosphate treatment agents, such as FS01 surface treatment agent sold by Daito Corporation; - Acrylic copolymer / polydimethylsiloxane treatment agents, such as ASC surface treatment agent sold by Daito Corporation; - Triisostearate titanate isopropyl ester treatment agent, such as ITT surface treatment agent sold by Daito Corporation; - Acrylic copolymer treatment agents, such as APD surface treatment agents sold by Daito Corporation; - Perfluoroalkyl phosphate / triisostearate titanate isopropyl ester treatment agents, such as PF +ITT surface treatment agents sold by Daito Corporation.

[0203] According to a specific embodiment of the invention, the dispersant is present together with organic or mineral pigments in the form of submicron-sized particles.

[0204] The term "submicron-sized" or "submicron" refers to a pigment whose particle size has been micronized by a micronization method and has an average particle size of less than a micrometer (µm), particularly between 0.1 and 0.9 µm and preferably between 0.2 and 0.6 µm.

[0205] According to one embodiment, the dispersant and pigment are present in an amount (dispersant: pigment) according to a weight ratio between 1:4 and 4:1, particularly between 1.5:3.5 and 3.5:1, or even better between 1.75:3 and 3:1.

[0206] Therefore, dispersants can have a silicone backbone, such as silicone polyether and amino silicone type dispersants. Among suitable dispersants, the following can be mentioned: -Amino silicones, i.e., silicones containing one or more amino groups, such as those sold under the following names and index numbers: BYK LPX 21879 from BYK Chemical Company, and GP-4, GP-6, GP-344, GP-851, GP-965, GP-967, and GP-988-1 sold by Genesee Polymers. - Silicone acrylates, such as Tego® RC 902, Tego® RC 922, Tego® RC 1041 and Tego® RC 1043 sold by Evonik. - Carboxyl-containing polydimethylsiloxane (PDMS) silicones such as Shin-Etsu's X-22162 and X-22370, epoxy silicones such as Genecast Polymers' GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682 and GP-695, or Evonik's Tego® RC 1401, Tego® RC 1403 and Tego® RC 1412.

[0207] According to a specific embodiment, the dispersant is of the aminosilicone type and is cationic.

[0208] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments, or organic pigments.

[0209] In one variant of the invention, the pigment is an organic pigment, preferably an organic pigment surface-treated with an organic reagent selected from silicone compounds. In another variant of the invention, the pigment is a mineral pigment.

[0210] Preferably, the pigment is selected from iron oxide, especially red, brown, or black iron oxide. As an example of iron oxide, one may mention iron oxide sold by Sun Chemical under the name SunPuro® Red Iron Oxide.

[0211] Direct dyes

[0212] Composition C used in the context of the method according to the invention may contain one or more direct dyes.

[0213] The term "direct dyes" refers to natural and / or synthetic dyes, excluding oxidative dyes. These are dyes that are superficially spread onto fibers. They can be ionic, such as cationic or anionic, or nonionic.

[0214] Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methimide dyes, such as cyanine, hemicyanine and styryl dyes; carbonyl dyes; azazine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, either alone or in mixtures.

[0215] Direct dyes can be selected from anionic direct dyes. The anionic direct dyes of this invention are dyes commonly referred to as "acidic" direct dyes due to their affinity for basic substances. The term "anionic direct dye" means any direct dye that includes at least one CO2R or SO3R substituent in its structure, where R indicates a hydrogen atom or a cation derived from a metal or amine, or an ammonium ion. Anionic dyes can be selected from direct nitro acid dyes, azo acid dyes, azazine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigo dyes, and natural acid dyes.

[0216] Examples of acid dyes include: 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, and Food Red 13. Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Purple 7, Acid Purple 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; Acid Red 111, Acid Red 134, Acid Yellow 38.

[0217] Examples of pyrazolinone anionic azo dyes include: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and Acid Yellow 17.

[0218] Examples of anthraquinone dyes 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 Acid Black 48.

[0219] Examples of nitro dyes include: Acid Brown 13 and Acid Orange 3; examples of dyes of formula (XXII') include: Acid Yellow 1,2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidinyl-5-nitrobenzenesulfonic acid, 2-(4'-N,N-(2”-hydroxyethyl)amino-2'-nitro)aniline ethanesulfonic acid, sodium salts of 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; and EXT D&C Yellow 7.

[0220] Examples of triarylmethane dyes include: Acid Blue 1; Acid Blue 3; Acid Blue 7 and Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50.

[0221] Examples of zeolite dyes include: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; and Acid Violet 9.

[0222] As an example of an indole dye, Acid Blue 74 can be mentioned.

[0223] Examples of quinoline dyes that can be mentioned include: Acid Yellow 2, Acid Yellow 3, and Acid Yellow 5.

[0224] Among the natural direct dyes that can be used according to the present invention are henna quinone, juglone, alizarin, erythropomorphic acid, carmine acid, carmine ketone acid, red gallol, protocatechaldehyde, indigo, indigo red, curcumin, apigenin, celeryin, and lichen red. Extracts or decoctions containing these natural dyes, and especially henna-based poultices or extracts, may also be used.

[0225] The colorant may be present in a total amount ranging from 0.001% to 20% by weight relative to the total weight of composition C, and preferably from 0.005% to 15% by weight; preferably, the colorant is selected from pigments.

[0226] The pigment may preferably be present in a total amount ranging from 0.05% to 20% by weight relative to the total weight of composition C, more preferably from 0.1% to 15% by weight, and more preferably from 0.5% to 10% by weight.

[0227] The direct dye may be present in a total amount ranging from 0.001% to 10% by weight relative to the total weight of composition C, and preferably from 0.005% to 5% by weight.

[0228] Non-carboxylic acid anionic thickeners

[0229] Composition C used in the context of the method according to the invention may also contain at least one noncarboxylic acid anionic thickener.

[0230] For the purposes of this invention, the term "non-carboxylic acid reagent" means that it does not contain any carboxylic acid functional group (-COOH) or carboxylate functional group (-COO). - ) reagents.

[0231] For the purposes of this invention, the term "thickener" means a compound that, at room temperature (25°C), at atmospheric pressure, and within 1 second... -1 At a shear rate, the viscosity of a composition in which the compound is introduced to a concentration of 0.05% by weight relative to the total weight of the composition increases by at least 20 cps, preferably at least 50 cps (viscosity can be measured using a cone / plate viscometer, Haake R600 rheometer, etc.).

[0232] Preferably, the noncarboxylic acid anionic thickener is selected from noncarboxylic acid anionic polymers, and more preferably from anionic polymers carrying sulfonic acid groups.

[0233] For the purposes of this invention, the term "anionic polymer" means a polymer that contains one or more anionic or anionizable groups and does not contain any cationic or cationizable groups.

[0234] Advantageously, the noncarboxylic acid anionic thickener is selected from anionic polymers containing at least one olefinic unsaturated monomer carrying a sulfonic acid group, which is in free form or in a partially or completely neutralized form.

[0235] These polymers can be cross-linked or non-cross-linked. They are preferably cross-linked.

[0236] These polymers can be associative or non-associative, but are preferably non-associative.

[0237] It should be understood that "associative polymers" are polymers that can reversibly associate with each other or with other molecules in an aqueous medium.

[0238] Their chemical structures are particularly characterized by containing at least one hydrophilic region and at least one hydrophobic region.

[0239] The term "hydrophobic group" refers to a group or polymer having a saturated or unsaturated, straight or branched hydrocarbon-based chain containing at least 8 carbon atoms, preferably 10 to 30 carbon atoms, particularly 12 to 30 carbon atoms, and more preferably 18 to 30 carbon atoms.

[0240] Preferably, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group can be derived from fatty alcohols such as stearyl alcohol, dodecyl alcohol, or decanol. It can also indicate a hydrocarbon-based polymer, such as polybutadiene.

[0241] The olefinic unsaturated monomers carrying sulfonic acid groups are particularly selected from vinyl sulfonic acid, styrene sulfonic acid, and (meth)acrylamide (C1-C2) groups. 22 )alkyl sulfonic acid, N-(C1-C 22 )alkyl (meth)acrylamide group (C1-C 22 Alkyl sulfonic acids such as undecylacrylamidomethanesulfonic acid and their partially or completely neutralized forms.

[0242] More preferably, (meth)acrylamide (C1-C) will be used. 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-methacrylamido-dodecyl sulfonic acid, or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and their partially or completely neutralized forms.

[0243] More specifically, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) is used, as well as its partially or completely neutralized forms.

[0244] In the context of 2-acrylamido-2-methylpropanesulfonic acid copolymers, reference may be made to crosslinked copolymers in which 2-acrylamido-2-methylpropanesulfonic acid and acrylamide are partially or completely neutralized; in particular, reference may be made to the products described in Example 1 of EP 503 853, and further reference may be made to these polymers in the literature described therein.

[0245] Also mentioned are copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts with hydroxyethyl acrylate, such as the compound sold by SEPPIC under the name Sepinov EMT 10 (INCI name: hydroxyethyl acrylate / sodium acryloyl dimethyl taurate copolymer).

[0246] Associative AMPS polymers can be selected, in particular, from those obtained by interaction with C6-C. 22Statistically associated AMPS polymers modified by reaction of monoalkylamines or dialkylamines, and those as described in patent application WO 00 / 31154 (which form part of the content of this specification). These polymers may also contain other olefinically unsaturated hydrophilic monomers selected from, for example, (meth)acrylic acid derivatives, such as esters obtained from them with monohydric alcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, or mixtures of these compounds.

[0247] Preferred polymers in this family are selected from associative copolymers of AMPS and at least one olefinically bonded unsaturated hydrophobic monomer.

[0248] Preferably, the non-carboxylic acid anionic thickener is selected from sodium 2-acrylamido-2-methylpropanesulfonate / hydroxyethyl acrylate copolymer (INCI name: hydroxyethyl acrylate / acryloyl dimethyl taurate copolymer) sold by Seppic Company.

[0249] Advantageously, the total content of the noncarboxylic acid anionic thickener ranges from 0.01% to 20% by weight relative to the total weight of composition C, preferably from 0.1% to 10% by weight, more preferably from 0.1% to 5% by weight, and even more preferably from 0.1% to 3% by weight.

[0250] Associative polymers

[0251] Composition C used in the context of the method according to the invention may also contain at least one associative polymer that is different from acrylic polymers and different from noncarboxylic acid anionic thickeners as previously defined.

[0252] As mentioned above, "associative polymers" are polymers that can reversibly associate with each other or with other molecules in an aqueous medium.

[0253] Their chemical structures are particularly characterized by containing at least one hydrophilic region and at least one hydrophobic region.

[0254] the term" hydrophobic groups "This means a group or polymer having a saturated or unsaturated, straight or branched hydrocarbon-based chain containing at least 10 carbon atoms, preferably 10 to 30 carbon atoms, particularly 12 to 30 carbon atoms, and more preferably 18 to 30 carbon atoms."

[0255] Associative polymers can have nonionic, anionic, cationic, or amphoteric properties.

[0256] Preferably, the associative polymer is selected from anionic associative polymers.

[0257] In anionic associative polymers, copolymers in which the monomers of the copolymer contain α,β-mono-olefinic unsaturated carboxylic acids and esters of α,β-mono-olefinic unsaturated carboxylic acids and oxyalkylene-modified fatty alcohols can be mentioned.

[0258] Preferably, these compounds also comprise esters of α,β-mono-olefinic unsaturated carboxylic acids and C1-C4 alcohols as monomers.

[0259] Examples of this type of compound that can be mentioned are Aculyn 22®, marketed by Röhm & Haas, which is a terpolymer of methacrylate / ethyl acrylate / oxyalkylene-modified stearyl methacrylate; and Aculyn 88, also marketed by Röhm & Haas.

[0260] Advantageously, the associative polymers, which are different from acrylic polymers and different from the previously described noncarboxylic acid anionic thickeners, are selected from copolymers whose monomers include esters of α,β-mono-olefinic unsaturated carboxylic acids and α,β-mono-olefinic unsaturated carboxylic acids and oxyalkylene-derived fatty alcohols.

[0261] Advantageously, the total content of the associative polymer, which is different from acrylic polymers and different from the previously described non-carboxylic acid anionic thickeners, ranges from 0.05% to 15% by weight relative to the total weight of composition C, preferably from 0.05% to 10% by weight, more preferably from 0.1% to 5% by weight, and even more preferably from 0.1% to 1% by weight.

[0262] solvent

[0263] Composition C used in the context of the method according to the invention may be aqueous. The water content may range from 1% to 90% by weight relative to the total weight of composition C, preferably from 10% to 80% by weight, and more preferably from 20% to 75% by weight.

[0264] Composition C may also contain one or more organic solvents.

[0265] Examples of organic solvents that may be mentioned include C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, pentanediol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; and aromatic alcohols (especially aromatic monohydric alcohols, such as benzyl alcohol or phenoxyethanol), and mixtures thereof.

[0266] The organic solvent may be present in a total amount between 0.01% and 60% by weight, preferably between 0.05% and 50% by weight, and more preferably between 0.1% and 45% by weight, and including the extreme values, relative to the total weight of composition C.

[0267] additive

[0268] Composition C used in the context of the method according to the invention may contain any commonly used adjuvants or additives.

[0269] Among the additives that may be included in the composition are reducing agents, softeners, defoamers, humectants, UV shielding agents, colloidal solvents, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than those previously described, preservatives, silicones, oils, waxes other than silicones in wax form, and mixtures thereof.

[0270] Composition C used in the context of the method according to the invention can be in particular in the form of suspension, dispersion, gel, emulsion, especially oil-in-water (O / W) or water-in-oil (W / O) emulsion, or multiple emulsion (W / O / W or polyol / O / W or O / W / O), cream, mousse, stick, vesicle dispersion, especially vesicle dispersion of ionic or nonionic lipids, or two-phase or multiphase lotion.

[0271] Those skilled in the art can, based on their general knowledge, first consider the properties of the components used, especially their solubility in the carrier, and secondly the intended application of the composition, to select a suitable presentation form and its preparation method.

[0272] plan

[0273] Composition T as defined above can be applied to wet or dry hair keratin fibers, as well as any type of gold or dark, natural or dyed, permanently wavy, bleached or loose hair keratin fibers.

[0274] Preferably, rinsing, wringing and / or drying steps are performed after applying composition T as previously defined.

[0275] More preferably, a rinsing step is performed after the application of composition T as previously defined.

[0276] Composition T can be applied at room temperature (between 15°C and 25°C).

[0277] After applying composition T and allowing it to foam, you may wait between 1 minute and 30 minutes, preferably up to 15 minutes, or even 10 minutes, before rinsing off composition T.

[0278] According to this embodiment, after washing and then rinsing and optionally wringing and / or drying the hair keratin fibers, one can wait between 1 minute and 12 hours, particularly between 1 minute and 10 hours, more particularly between 1 minute and 7 hours, and more preferably between 1 minute and 6 hours, before applying composition C to the hair keratin fibers.

[0279] Preferably, the retention time on the hair keratin fibers is between 1 minute and 5 hours, preferably between 1 minute and 1 hour, after washing and rinsing with composition T and before applying composition C.

[0280] Composition C described above can be used on wet or dry hair keratin fibers, as well as on all types of gold or dark, natural or dyed, permanently wavy, bleached or loose hair keratin fibers.

[0281] Preferably, the steps of washing, rinsing, wringing and / or drying are performed after applying composition C to hair keratin fibers.

[0282] More preferably, the drying step is performed after the composition C is applied to the hair keratin fibers.

[0283] Composition C can be applied to hair keratin fibers by any conventional means, particularly using a comb, fine brush, coarse brush, sponge, or fingers.

[0284] The application of composition C to hair keratin fibers is typically carried out at room temperature (15°C to 25°C).

[0285] After applying composition C to hair keratin fibers, a waiting period of 1 minute to 6 hours, particularly 1 minute to 2 hours, more particularly 1 minute to 1 hour, and more preferably 1 minute to 30 minutes may be allowed before steps such as washing, rinsing, wringing and / or drying.

[0286] After applying composition C, the hair keratin fibers can be air-dried or, for example, dried at a temperature greater than or equal to 30°C.

[0287] Therefore, the method according to the invention may include the step of applying heat to hair keratin fibers using a heating tool.

[0288] This heat application step can be performed using a cover, hair dryer, straightener or curling iron, Climazon cover, etc.

[0289] Preferably, the heat application step is performed using a hair dryer.

[0290] When the method of the present invention uses the step of applying heat to hair keratin fibers, the step of applying heat to hair keratin fibers is performed after applying composition C to hair keratin fibers.

[0291] During the step of applying heat to the hair keratin fibers, mechanical action can be applied to the hair strands, such as combing, brushing, or running fingers through them.

[0292] When applying heat to the hair keratin fibers using a hood or hair dryer, the temperature is preferably between 30°C and 110°C, and more preferably between 50°C and 90°C.

[0293] When the step of applying heat to the hair keratin fibers is performed using a straightener, the temperature is preferably between 110°C and 220°C, and more preferably between 140°C and 200°C.

[0294] In certain variations, the method of the present invention involves the step of applying heat using a cover, hair dryer or Climazon cover, preferably a hair dryer (c1) and the step of applying heat using a straightener or curling iron, preferably a straightener (c2).

[0295] Step (c1) can be performed before step (c2).

[0296] During step (c1), also known as the drying step, the hair keratin fibers can be dried, for example, at a temperature greater than or equal to 30°C. According to a specific embodiment, this temperature is greater than 40°C. According to a specific embodiment, this temperature is greater than 45°C and less than 110°C.

[0297] Preferably, if drying hair keratin fibers, they are dried using an airflow in addition to heating. This airflow during drying allows for improved separation of the coated hair strands.

[0298] During the drying process, mechanical action can be applied to the hair strands, such as combing, brushing, or running your fingers through them.

[0299] During step (c2), the straightener or curling iron, preferably the straightener, can be used at a temperature ranging from 110°C to 220°C, preferably between 140°C and 200°C.

[0300] After the heating step, a styling step can be performed, for example, using a straightener; the temperature for the hair styling step can be between 110°C and 220°C, preferably between 140°C and 200°C.

[0301] According to one embodiment, the present invention is a method for dyeing hair keratin fibers, the method comprising the following steps: i) Applying a previously defined composition T to hair keratin fibers, the composition T comprising at least one surfactant selected from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, and having an alkaline pH; ii) Optionally, the composition T may be left on hair keratin fibers for a period of 1 minute to 1 hour, preferably 1 minute to 30 minutes; iii) Optionally, rinse, wring out, and / or dry the hair keratin fibers, preferably rinsing; and then... iv) Applying at least one composition C to hair keratin fibers, said dyeing composition C comprising: - At least one (poly)carbodiimide compound as previously described; - At least one polymer as previously defined, comprising at least one reactive group selected from carboxylic acids; and - At least one coloring agent selected from pigments, direct dyes, and mixtures thereof as previously described; and then v) Optionally, the composition C is left on hair keratin fibers for a period of 1 to 30 minutes, preferably 1 to 20 minutes; and then... vi) Optionally, the steps of washing, rinsing, wringing and / or drying the hair keratin fibers.

[0302] Advantageously, the step of applying composition C to hair keratin fibers is repeated several times.

[0303] According to a preferred embodiment, step b) of the method according to the invention includes instantaneously mixing at least two compositions A and B upon use to obtain composition C and applying composition C to hair keratin fibers, wherein: Composition A comprises at least one (poly)carbodiimide compound as previously defined. Composition A and / or composition B comprise at least one polymer containing at least one reactive group selected from carboxylic acids, preferably at least one acrylic polymer as previously defined, and at least one colorant selected from pigments, direct dyes and mixtures thereof as previously defined.

[0304] Advantageously, composition B comprises at least one polymer containing at least one reactive group selected from carboxylic acids, preferably an acrylic polymer as previously defined.

[0305] Preferably, composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof as previously described.

[0306] According to a preferred embodiment, step b) of the method according to the invention includes instantaneously mixing at least two compositions A and B upon use to obtain composition C and applying composition C to hair keratin fibers, wherein: Composition A comprises at least one (poly)carbodiimide compound as previously defined.

[0307] Composition B comprises at least one acrylic polymer as previously defined and at least one colorant selected from pigments, direct dyes and mixtures thereof as previously defined.

[0308] Preferably, composition A does not contain at least one colorant selected from pigments, direct dyes and mixtures thereof as previously described.

[0309] According to this embodiment, compositions A and B are preferably mixed less than 15 minutes before application to hair keratin fibers, more preferably less than 10 minutes before application, and even more preferably less than 5 minutes before application.

[0310] The weight ratio of composition A to composition B preferably ranges from 0.1 to 10, more preferably from 0.2 to 5, and even more preferably from 0.5 to 2, or even from 0.6 to 1.5. In a specific embodiment, the weight ratio of composition A to composition B is equal to 1.

[0311] The total content of the (poly)carbodiimide compound is preferably from 0.01% to 40% by weight relative to the total weight of composition A, more preferably from 0.1% to 30% by weight, even more preferably from 0.5% to 20% by weight, and even more preferably from 1% to 12% by weight.

[0312] The total content of the acrylic polymer is preferably from 0.2% to 60% by weight relative to the total weight of composition B, more preferably from 1% to 40% by weight, even more preferably from 1% to 30% by weight, and even more preferably from 2% to 20% by weight.

[0313] According to a preferred embodiment, the present invention is a method for dyeing hair keratin fibers, the method comprising the following steps: i) Applying a previously defined composition T to hair keratin fibers, the composition T comprising water, at least one surfactant selected from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, and having an alkaline pH; ii) Optionally, the composition T may be left on hair keratin fibers for a period of 1 minute to 30 minutes, preferably 1 minute to 10 minutes; iii) The steps of rinsing, optionally wringing and / or drying the hair keratin fibers; and then iv) Applying at least one composition C to hair keratin fibers, said dyeing composition C comprising: - At least one (poly)carbodiimide compound as previously described; - At least one acrylic polymer as previously defined; and - At least one coloring agent selected from pigments, direct dyes, and mixtures thereof as previously described; and then v) Optionally, the composition C is left on hair keratin fibers for a period of 1 to 30 minutes, preferably 1 to 20 minutes; and then... vi) Optionally, the steps of washing, rinsing, wringing and / or drying the hair keratin fibers.

[0314] Multi-compartment device (reagent kit)

[0315] The present invention also relates to an apparatus for dyeing hair keratin fibers, comprising a plurality of compartments accommodating the following: - The first compartment contains composition T as previously defined. - A second compartment containing composition A as previously defined, which contains at least one (poly)carbodiimide compound; - A third compartment contains composition B as previously defined, which contains at least one pigment as previously defined, and at least one polymer containing at least one reactive group selected from carboxylic acids.

[0316] The invention will now be described in more detail by way of examples, which do not in any way limit the scope of the invention. However, these examples enable the display of specific features, variations, and preferred embodiments of the invention.

[0317] Example

[0318] The (poly)carbodiimide of the present invention is a commercially available product or reagent that can be synthesized according to chemical reactions also known to those skilled in the art, via synthetic methods known to them. For example, references can be made to books. Sciences of Synthesis - Houben - Weyl Methods of Molecular Transformations[ Synthetic Science [-Houben-Weyl Molecular Transformation Methods], 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D-70469 Stuttgart, or US Patent 4,284,730 or Canadian Patent Application CA2,509,861.

[0319] More specifically, the method for preparing the (poly)carbodiimide of the present invention involves a diisocyanate reagent (1) in the first step: O=C=N-L1-N=C=O (1), In formula (1), L1, as previously defined, reacts in the presence of a carboimidation catalyst (2) (such as those described in US 4,284,730, especially phosphorus-based catalysts particularly selected from cyclophosphine oxides and cyclophosphine sulfoxides, diaza- and oxaza-phosphacyclopentanes), preferably in an inert atmosphere (nitrogen or argon), and particularly in a polar solvent (preferably an aprotic solvent such as THF, glycol dimethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, or DMF), at a temperature between room temperature and the reflux temperature of the solvent, preferably at about 140°C; to obtain the carbodiimide diisocyanate compound (3): O = C = N - L1 - (N = C = N - L1) n -N=C=O (3), In equation (3), L1 and n are as previously defined. Benzoyl halides, such as benzoyl chloride, can be added to deactivate the catalyst.

[0320] To obtain a “symmetric” (poly)carbodiimide, during the second step of the preparation method, compound (3) is reacted with 1 molar equivalent (1 equivalent) of nucleophile R1-X1-H, and then with 0.5 equivalent of reagent HEH, wherein R1, X1, and E are as previously defined, to obtain the “symmetric” compound (4) according to the invention: [R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)]2-E (4), In equation (4), R1, X1, L1, n, and E are as previously defined. According to a variant of compound (4) obtained from (3), 0.5 equivalents of reagent HEH can be added first, and then 1 equivalent of reagent R1-X1-H can be added.

[0321] To obtain the “asymmetric” (poly)carbodiimide, during the second step of the preparation method, compound (3) is reacted with 1 molar equivalent (1 equivalent) of the nucleophile R1-X1-H, and then with 1 equivalent of the reagent HEH, wherein R1, X1, and E are as previously defined, to obtain compound (5): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-EH (5), In equation (5), R1, X1, L1, n and E are as previously defined.

[0322] According to the variant of compound (5) obtained from (3), 1 equivalent of reagent R1-X1-H can be added first, and then 0.5 equivalent of reagent HEH can be added.

[0323] During the third step, compound (5) is reacted with 1 equivalent of compound (6).

[0324] R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O (6), said compound (6) is prepared in advance from compound (3'): O = C = N - L1 - (N = C = N - L1) z -N=C=O (3'), In equation (3'), L1 and z, as previously defined, react with a 1 equivalent of the nucleophile R2-X2-H, wherein L1, R2, X2, and z, as previously defined, 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 equation (7), R1, X1, L1, R2, X2, n, z and E are as previously defined.

[0325] One molar equivalent of the compound can be made to have O=C=N-L1-(N=C=N-L1). z -N=C=O (3') reacts with 1 / w molar equivalent of HEH, and then with 1 equivalent of the nucleophile R2-X2-H to give compound (8): H-[EC(O)-NH-L1-(N=C=N-L1) z ] w -NH-C(O)-X2-R2 (8), In equation (8), L1, R2, X2, z and E are as previously defined, and w is an integer between 1 and 3; more preferably, w = 1.

[0326] Then this final compound (8) can react 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 nucleophile 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 -NH C(O)-X2-R2 (9), In equation (9), L1, R1, X1, R2, X2, n, z, w and E are as previously defined.

[0327] (Poly)carbodiimide compounds, as well as all reaction intermediates and reagents, can be purified by conventional methods known to those skilled in the art, such as extraction with water and water-immiscible organic solvents, precipitation, centrifugation, filtration and / or chromatography.

[0328] Example 1: A method for synthesizing (poly)carbodiimide compounds

[0329] 50 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphacyclopentadiene 1-oxide were placed in a 500 mL three-necked round-bottom flask equipped with a thermometer, stirrer and reflux tube under stirring.

[0330] The reaction medium was heated at 140°C for 4 hours under nitrogen atmosphere, and the results were obtained by infrared spectroscopy at 2200 and 2300 cm⁻¹. -1 The reaction was monitored by the absorption of isocyanate functional groups between the molecules, and then cooled to 120°C.

[0331] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol was introduced into the reaction medium under stirring. The temperature was maintained at 120°C until the isocyanate functional groups had completely disappeared. The results were obtained by infrared spectroscopy at 2200-2300 cm⁻¹. -1 Monitor, and then cool to room temperature.

[0332] After cooling to room temperature, the reaction medium was poured dropwise into a 500 mL glass beaker containing 85 g of distilled water under vigorous stirring to obtain the desired product in the form of a translucent yellow liquid.

[0333] Example 2

[0334] Compositions T1 and T2 as described in Table 1 below were prepared: unless otherwise mentioned, amounts are expressed as g / 100 g of active material.

[0335] [Table 1]

[0336] The pH of compositions T1 and T2 was measured using a Mettler Toledo Seven Go pH meter.

[0337] Compositions A and B as described in Tables 2 and 3 below were prepared: unless otherwise mentioned, amounts are expressed as g of the original starting material / 100 g.

[0338] [Table 2]

[0339] (1) Synthesize according to the synthesis method described in Example 1 (containing 40% active material in water). (2) Sold by Sepinov Company under the name Sepinov EMT10 (containing 90% active material).

[0340] [Table 3]

[0341] (3) An acrylic polymer sold by Daito Kasei Corporation under the trade name Daitosol 3000SLPN-PE1 (an aqueous dispersion containing 30% active material). (4) Marketed by Dow Corning under the name Dow Corning HMW 2220 nonionic emulsion (divinyl polydimethylsiloxane / polydimethylsiloxane block copolymer in an aqueous emulsion) (containing 60% active material). (5) An associative polymer marketed by Rohm and Haas under the trade name Aculyn 22® (a terpolymer of oxyalkylene-containing methacrylate / ethyl acrylate / stearyl methacrylate containing 30% active material).

[0342] Composition A is then mixed with composition B at a mass ratio of 50 / 50 to obtain composition C.

[0343] plan

[0344] Two different methods were used.

[0345] According to methods 1 and 2, composition T1 or T2 is first applied to sensitized hair keratin fiber strands (hereinafter referred to as SA20). Each of these compositions is applied to the hair keratin fiber strands at a ratio of 0.8 g composition / gram of hair strands. The hair keratin fiber strands are then rinsed.

[0346] Composition C is then applied to hair strands previously treated with Composition T1 or Composition T2 at a ratio of 0.8 g composition / gram of hair strand. The hair keratin fibers are then combed and dried with a hair dryer.

[0347] The method of using composition T1 and then composition C is a comparative method because composition T1 does not have an alkaline pH. It is hereinafter referred to as method P1. The method of using composition T2 and then composition C is a method according to the present invention. It is hereinafter referred to as method P2.

[0348] The methods used are summarized in Table 4 below: [Table 4]

[0349] The hair keratin fiber strands treated via methods P1 to P2 were then subjected to a test consisting of several repeated shampoo washes in order to evaluate the tolerance (durability) of the obtained color to shampoo washes according to the shampoo washing protocol described below.

[0350] Shampoo washing instructions

[0351] Comb through the dyed hair keratin fibers, wet with water at 35°C, and then pass the hair between your fingers five times, holding for five seconds each time. Then squeeze the hair keratin fibers dry between two fingers.

[0352] Apply standard shampoo (Garnier Ultra Doux) evenly to the dyed hair strands at a ratio of 0.4 g standard shampoo / gram of hair strand, and gently massage the hair keratin fibers along the length from root to tip (6 passes) for 15 seconds.

[0353] Then place the hair keratin fiber strands on a petri dish and let them stand for 1 minute.

[0354] Next, rinse the hair strands with water while passing them between your fingers through the keratin fibers (15 times). Then squeeze the keratin fibers dry between two fingers before proceeding with the next shampoo wash.

[0355] After several shampoo washes, the hair keratin fibers were combed and dried with a hairdryer.

[0356] result

[0357] In CIE L a b The system uses a Minolta CM3600A spectrophotometer colorimeter (light source D65, angle 10°, including specular reflection component) to evaluate the color durability of hair strands.

[0358] In the L a b In the system, L Indicates the intensity of color, a Indicates the green / red axis and b Indicates the blue / yellow axis.

[0359] The durability of the color was evaluated by the color difference ΔE between dyed hair strands before shampoo washing and after five shampoo washes, according to the scheme described above. The lower the ΔE value, the longer the color lasts relative to shampoo washing.

[0360] Calculate the value of ΔE according to the following equation:

[0361] In this equation, L a and b This indicates the value measured after dyeing the hair keratin fibers and after shampooing, and L0 a0 and b0 This indicates the value measured after the hair keratin fibers have been dyed but before shampooing.

[0362] The results are summarized in Table 5 below.

[0363] [Table 5]

[0364] Hair keratin fibers treated according to the method of the present invention and washed with five shampoos have a significantly lower ΔE value than hair keratin fibers treated by a comparative method.

[0365] Therefore, the colored coating obtained by means of the method according to the invention exhibits improved tolerance to shampoo washing.

[0366] Example 3

[0367] Based on the above protocol, shampoos with different pH values ​​were used to test natural hair keratin fiber strands (BN) and bleached hair strands (SA80).

[0368] The results are reported in Table 6 below.

[0369] [Table 6]

[0370] These results demonstrate that the method of the present invention enables improved color durability on hair keratin fibers. This improvement is achieved on natural hair keratin fibers, and it is significantly superior on damaged hair keratin fibers.

[0371] Example 4

[0372] Use the compositions T2, A, and B as described above in Example 2.

[0373] In addition, composition D as described in Table 7 below was prepared: unless otherwise mentioned, the amount is expressed as g of starting material obtained as is / 100 g (am means active substance).

[0374] [Table 7]

[0375] (6) Sold by Stahl under the name PERMUTEX® XR-13-554.

[0376] Composition A is then mixed with composition B at a 50 / 50 mass ratio to obtain composition C. Composition D is then mixed with composition B at a 50 / 50 mass ratio to obtain composition E.

[0377] plan

[0378] Two different methods were used.

[0379] One of these two methods is method P2, as described above.

[0380] According to method 3, composition T2 is first applied to sensitized hair keratin fiber strands (hereinafter referred to as SA20). This composition is applied to the hair keratin fiber strands at a ratio of 0.8 g composition / gram of hair strand. The hair keratin fiber strands are then rinsed.

[0381] Composition E is then applied to the hair strands at a ratio of 0.8 g composition / gram of hair strand. The hair keratin fibers are then combed and dried with a hair dryer.

[0382] The method of using composition T2 and then composition E is a comparative method because composition E does not contain a (poly)carbodiimide compound selected from compounds having formula (II). It is referred to below as method P3.

[0383] The methods used are summarized in Table 8 below: [Table 8]

[0384] The hair keratin fiber strands treated by methods P2 and P3 were then subjected to a test consisting of several repeated shampoo washes in order to evaluate the tolerance (durability) of the obtained color to shampoo washes according to the shampoo washing protocol described above in Example 2.

[0385] result

[0386] As described above in Example 2, in CIE L a b The system evaluates the durability of hairline color.

[0387] The durability of the color is also evaluated by the color difference ΔE, as mentioned above.

[0388] The results are summarized in Table 9 below.

[0389] [Table 9]

[0390] Hair keratin fibers treated according to the method of the present invention and washed with shampoo three times have a significantly lower ΔE value than hair keratin fibers treated by the comparative method.

[0391] Therefore, the colored coating obtained by means of the method according to the invention exhibits improved tolerance to shampoo washing.

Claims

1. A method for dyeing hair keratin fibers, the method comprising: (a) The step of washing the hair keratin fibers with composition T, said composition T comprising at least one surfactant selected from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, and having an alkaline pH; and then (b) Applying composition C for dyeing hair keratin fibers to the hair keratin fibers, said composition C comprising: - At least one (poly)carbodiimide compound selected from compounds of formula (II): (II), in: - X1 and X2 independently represent oxygen atom O, sulfur atom S or NH group; - R1 and R2 independently represent hydrocarbon-based groups optionally inserted with one or more heteroatoms; - n and z indicate integers from 1 to 20, where n+z ≥ 2 and w indicates integers from 1 to 3; - L1 independently represents C1-C 18 Divalent aliphatic hydrocarbons based on hydrocarbon groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocyclic alkyl or C6-C 14 aryl groups and their mixtures; - E independently represents a group selected from the following: -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; R3 and R4 independently represent divalent hydrocarbon-based groups optionally inserted with one or more heteroatoms; - R5 independently represents a covalent bond or optionally an inserted saturated divalent hydrocarbon-based group with one or more heteroatoms; - R6 independently represents a hydrogen atom or optionally a hydrocarbon-based group with one or more heteroatoms inserted; - At least one polymer containing at least one reactive group selected from carboxylic acids; and - At least one colorant selected from pigments, direct dyes and mixtures thereof.

2. The method according to claim 1, characterized in that, Composition T has a pH ranging from 7.5 to 13, more preferably from 8 to 10.

3. The method according to claim 1 or 2, characterized in that, Composition T comprises at least one alkali agent, which is preferably selected from alkali metal or alkaline earth metal hydroxides, ammonium hydroxide, alkanolamines and mixtures thereof, and preferably sodium hydroxide.

4. The method according to any one of the preceding claims, characterized in that, The anionic surfactant in composition T is selected from sulfate-type anionic surfactants, preferably from (C 10 -C 22 )alkyl sulfates, (C 10 -C 22 ) alkyl ether sulfates and mixtures thereof, preferably selected from (C 10 -C 22 Sodium alkyl ether sulfate and its mixtures.

5. The method according to any one of the preceding claims, characterized in that, The amphoteric or zwitterionic surfactant in composition T is selected from (C8-C9) 20 )alkyl betaine, (C8-C 20 )alkyl sulfonyl betaine, (C8-C 20 )alkylamide (C3-C8)alkyl betaine, (C8-C 20 alkylamide (C6-C8) alkyl sulfonyl betaine and mixtures thereof, more preferably selected from (C8-C8) alkyl sulfonyl betaine. 20 )alkyl betaine, (C8-C 20 Alkylamide (C3-C8) alkyl betaines and mixtures thereof, more preferably selected from (C8-C8) alkyl betaines. 20 Alkylamide (C3-C8) alkyl betaine and mixtures thereof.

6. The method according to any one of claims 1 to 5, wherein, Composition T contains a certain amount of surfactant selected from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, the amount ranging from 1% to 50% by weight, preferably from 5% to 40% by weight, and more preferably from 10% to 30% by weight relative to the total weight of composition T.

7. The method according to any one of the preceding claims, characterized in that, The (poly)carbodiimide compound is selected from compounds of formula (II), wherein: - X1 and X2 represent oxygen atoms independently; - R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols in which the hydroxyl groups have been removed, and mixtures thereof; - n and z indicate integers from 1 to 20, where n+z ≥ 2 and w equals 1; - L1 is selected from C1-C 18 Divalent aliphatic hydrocarbons based on hydrocarbon groups, C3-C 15 Cycloalkylene, C3-C 12 Heterocyclic alkyl or C6-C 14 aryl groups and their mixtures; - E independently represents a group selected from the following: -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; R3 and R4 are independently selected from C6-C atoms that may optionally have one or more heteroatoms inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof; - When R5 is not covalent, R5 is selected from C6-C with one or more heteroatoms optionally inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof; and - R6 is selected from C6-C which may optionally have one or more heteroatoms inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof.

8. The method according to any one of the preceding claims, characterized in that, The (poly)carbodiimide compound is selected from compounds of formula (II), wherein: - X1 and X2 represent oxygen atoms independently; - R1 and R2 are independently monoalkyl ethers of (poly)alkylene glycols in which the hydroxyl groups have been removed; - n and z indicate integers from 1 to 20, where n+z ≥ 2 and w equals 1; - L1 is C3-C 15 Cycloalkylene; - E independently represents a group selected from the following: -O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5-; R3 and R4 are independently selected from C6-C atoms that may optionally have one or more heteroatoms inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof; - When R5 is not covalent, R5 is selected from C6-C with one or more heteroatoms optionally inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof; and - R6 is selected from C6-C which may optionally have one or more heteroatoms inserted. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof.

9. The method according to any one of the preceding claims, characterized in that, The (poly)carbodiimide compound is selected from compounds of formula (II), wherein: - X1 and X2 represent oxygen atoms independently; - R1 and R2 independently represent compounds of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q -(WE), Where R 13 R represents C1-C4 alkyl or phenyl, preferably C1-C4 alkyl, more preferably methyl. 14 It represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30; - n and z indicate integers from 1 to 20, where n+z ranges from 4 to 10 and w equals 1; - L1 is C3-C 15 Cycloalkylene compounds, such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylmethane; and - E represents the group -O-R3-O-, where R3 is selected from C6-C groups optionally intercalated with one or more heteroatoms. 14 Aromatic, C3-C 12 Cycloalkylene, straight-chain or branched C1-C 18 Alkylenes and mixtures thereof.

10. The method according to any one of the preceding claims, characterized in that, The (poly)carbodiimide compound is selected from compounds of formula (II), wherein: - X1 and X2 represent oxygen atoms independently; - R1 and R2 independently represent compounds of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q -(WE), Where R 13 R represents C1-C4 alkyl or phenyl, preferably C1-C4 alkyl, more preferably methyl. 14 It represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30; - n and z indicate integers from 1 to 20, where n+z ranges from 4 to 10 and w equals 1; - L1 is C3-C 15 Cycloalkylene compounds, such as cyclopentylene, cyclohepylene, cyclohexylene, and 4,4-dicyclohexylmethane, preferably 4,4-dicyclohexylmethane; and - E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C chain optionally intercalated with one or more heteroatoms. 18 Alkylenes, such as methylene, propylene, butylene, or ethylene.

11. The method according to any one of the preceding claims, characterized in that, The (poly)carbodiimide compound is selected from compounds of formula (XII): (XII), Where L1 is 4,4-dicyclohexylmethane, n and z indicate integers from 1 to 20, where n+z ranges from 4 to 10, E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C optionally intercalated with one or more heteroatoms. 18 Alkylenes, such as methylene, propylene, butylene, or ethylene, and r and s indicate an integer range from 4 to 30.

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

13. The method according to any one of the preceding claims, characterized in that, The polymer containing at least one reactive group selected from carboxylic acids is an acrylic polymer, preferably an acrylic polymer containing one or more units derived from monomers such as: a) (meth)acrylic acid; and b) C1 to C 30 More preferably C1 to C 20 Furthermore, it is even better from C1 to C 10 And even more specifically, C1 to C4 alkyl (meth)acrylates.

14. The method according to any one of the preceding claims, characterized in that, The polymer containing at least one reactive group selected from carboxylic acids, preferably an acrylic polymer, is present in a total content ranging from 0.1% to 35% by weight, preferably from 0.5% to 30% by weight, more preferably from 1% to 20% by weight, and even more preferably from 3% to 15% by weight relative to the total weight of composition C.

15. The method according to any one of the preceding claims, characterized in that, The total content of the colorant ranges from 0.001% to 20% by weight relative to the total weight of composition C, and preferably from 0.005% to 15% by weight; preferably, the colorant is selected from pigments.

16. The method according to any one of the preceding claims, characterized in that, Step (b) includes instantaneously mixing at least two compositions A and B upon use to obtain composition C and includes applying composition C to the hair keratin fibers, wherein: - Composition A comprises at least one (poly)carbodiimide compound as defined in any one of claims 1 to 11; Composition B comprises at least one polymer containing at least one reactive group selected from carboxylic acids as defined in claim 1 or 13, and at least one colorant as defined in claim 1.

17. An apparatus for dyeing hair keratin fibers, the apparatus comprising a plurality of compartments housing the following: - A first compartment comprising composition T as defined in any one of claims 1 to 6; - A second compartment containing composition A, said composition A comprising a (poly)carbodiimide compound as defined in any one of claims 1 to 11; - A third compartment containing composition B, which contains at least one pigment as defined in claim 1, and at least one polymer as defined in claim 1 or 13 containing at least one reactive group selected from carboxylic acids.

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