WO2025133309A1

WO2025133309A1 - Process for dyeing hair keratin fibres comprising a step of washing the hair keratin fibres with a specific composition, followed by the application to the hair keratin fibres of a particular dyeing composition

Info

Publication number: WO2025133309A1
Application number: PCT/EP2024/088196
Authority: WO
Inventors: Jean-Daniel Debain; Marie GRACIA; Chloe THIEULET; Fabien BROTHIER
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2023-12-21
Filing date: 2024-12-20
Publication date: 2025-06-26
Anticipated expiration: 2026-06-21
Also published as: FR3157155A1

Abstract

The present invention relates to a process for dyeing hair keratin fibres comprising: (a) a step of washing the hair keratin fibres with a composition T comprising at least one surfactant chosen from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, and having a basic pH; and then (b) the application to the hair keratin fibres of a dyeing composition C comprising: - at least one (poly)carbodiimide compound of formula (II); - at least one polymer comprising at least one reactive group chosen from carboxylic acids; and - at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

Description

DESCRIPTION

TITLE: Process for dyeing hair keratin fibres comprising a step of washing the hair keratin fibres with a specific composition, followed by the application to the hair keratin fibres of a particular dyeing composition

The present invention relates to a process for dyeing hair keratin fibres comprising a step of washing the hair keratin fibres with a composition comprising at least one anionic and/or amphoteric or zwitterionic surfactant and having a basic pH, and then the application to the hair keratin fibres of a composition C for dyeing hair keratin fibres comprising a (poly)carbodiimide compound, a polymer comprising at least one reactive group chosen from carboxylic acids, and a colouring agent.

Technical field

In the field of dyeing hair keratin fibres, it is already known practice to dye hair keratin fibres via various techniques using direct dyes or pigments for nonpermanent colouring, or dye precursors for permanent colouring.

There are essentially three types of process for dyeing hair keratin fibres: a) “permanent” dyeing, the function of which is to afford a substantial modification to the natural colour and which uses oxidation dyes which penetrate into the hair keratin fibre and form the dye via an oxidative condensation process; b) non-permanent, semi-permanent or direct dyeing, which does not use the oxidative condensation process and withstands four or five shampoo washes; it consists in colouring keratin fibres with colour compositions containing direct dyes; c) temporary dyeing, which gives rise to a modification of the natural colour of the head of hair that remains from one shampoo wash to the next, and which serves to enhance or correct a shade that has already been obtained. It may also be likened to a “makeup” process.

Another dyeing method consists in using pigments. Specifically, the use of pigments on the surface of keratin fibres generally makes it possible to obtain colourings that are visible on dark hair keratin fibres, since the surface pigment masks the natural colour of the fibre. However, the colourings obtained via this dyeing method have the drawback of having poor resistance to shampoo washing and also to external agents such as sebum, perspiration, brushing and/or rubbing. The colourings obtained can also be too selective, that is to say that the colouring difference is too great along a single keratin fibre which is sensitized to a different extent between its end and its root.

There is thus still a need for a process for dyeing hair keratin fibres which has the advantage of obtaining a uniform coloured coating on the hair keratin fibres, while at the same time forming a coating that is persistent with respect to shampoo washing and to the various stresses to which the hair keratin fibres may be subjected such as brushing and/or rubbing.

Thus, the aim of the present invention is to develop a process for dyeing hair keratin fibres which has the advantage of obtaining a smooth and uniform coloured coating on the hair keratin fibres, while at the same time forming a coating that improves persistence with respect to shampoo washing and to the various stresses to which the hair keratin fibres may be subjected, such as brushing and/or rubbing.

Disclosure of the invention

One subject of the present invention is thus a process for dyeing hair keratin fibres comprising:

(a) a step of washing the hair keratin fibres with a composition T comprising at least one surfactant chosen from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, and having a basic pH; and then

(b) the application to the hair keratin fibres of a composition C for dyeing hair keratin fibres comprising:

- at least one (poly)carbodiimide compound chosen from the compounds of formula (II) below:

in which:

- Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

- Ri and R2 independently represent a hydrocarbon-based radical optionally interrupted with one or more heteroatoms;

- n and z denote an integer ranging from 1 to 20, with n+z > 2 and w denotes an integer ranging from 1 to 3;

- Li independently represents a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof;

- E independently represents a group chosen from:

-O-R3-O-; -S-R4-S-; -R₅-N(R6)-R4-N(R₆)-R5-; in which R3 and R4 independently represent a divalent hydrocarbon-based radical optionally interrupted with one or more heteroatoms;

- Rs independently represents a covalent bond or a saturated divalent hydrocarbonbased radical, optionally interrupted with one or more heteroatoms;

- Re independently represents a hydrogen atom or a hydrocarbon-based radical, optionally interrupted with one or more heteroatoms;

- at least one polymer comprising at least one reactive group chosen from carboxylic acids; and

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

By virtue of the process for dyeing hair keratin fibres according to the invention, coloured coatings are obtained on the hair keratin fibres that make it possible to obtain a colouring that is visible on all types of hair keratin fibres and persistent with respect to shampoo washing. Such a coating may be resistant to the external stresses to which the hair keratin fibres may be subjected, such as blow-drying and perspiration. The dyeing process according to the invention makes it possible in particular to obtain a uniform coating.

The term “at least one" means one or more.

Unless otherwise indicated, the limits of a range of values are included in that range, notably in the expressions “between” and “ranging from ... to ..." .

The invention is not limited to the examples illustrated. The characteristics of the various examples may notably be combined within variants which are not illustrated.

For the purposes of the present invention and unless otherwise indicated: - an “alkyl” radical denotes a linear or branched saturated radical containing, for example, from 1 to 20 carbon atoms;

- an “aminoalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an NH2 group;

- a “hydroxyalkyl” radical denotes an alkyl radical as defined previously, said alkyl radical comprising an OH group;

- an “alkylene” radical denotes a linear or branched divalent saturated C2-C4 hydrocarbon-based group such as methylene, ethylene or propylene;

- a “ cycloalky T or “alicycloalkyl” radical denotes a saturated monocyclic, or polycyclic, preferably monocyclic, bicyclic or tricyclic, cyclic hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 24 carbon atoms, in particular comprising from 3 to 20 carbon atoms, more particularly from 3 to 13 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl; preferably, the cycloalkyl radical is then an isobomyl group;

- a “cycloalkylene” radical denotes a divalent cycloalkyl group with “cycloalkyF as defined previously, preferably of C3-C12;

- an “aryl” radical is a monocyclic, bicyclic or tricyclic, fused or non-fused, unsaturated and aromatic hydrocarbon-based cyclic radical, comprising from 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms; preferably, the aryl group comprises 1 ring of 6 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl, preferably tolyl, xylyl, or methylnaphthyl; preferably, the aryl group represents phenyl;

- an “arylene” radical is a divalent aryl radical with “aryl” as defined previously; preferably, arylene represents phenylene;

- a “heterocyclic” radical denotes a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based radical, comprising one or more heteroatoms, preferably from 1 to 5 atoms chosen from O, S orN, including from 3 to 20 ring members, preferably between 5 and 10 ring members, such as imidazolyl, pyrrolyl and furanyl; - a “helerocycloctlkylene" radical is a divalent heterocyclic group with “heterocyclic" as defined previously;

- an “aryloxy” radical denotes an aryl-oxy radical with “aryl” as defined previously;

- an “alkoxy” radical denotes an alkyl-oxy radical with “alkyl” as defined previously;

- an “acyloxy” radical denotes an ester radical R-C(O)-O- with R being an alkyl group as defined previously;

- a “reactive” group is a group that is capable of forming a covalent bond with another identical or different group, by chemical reaction.

Unless otherwise indicated, when compounds are mentioned in the present patent application, this also includes the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof or the salts thereof, alone or as a mixture.

The term “hair keratin fibres” means the keratin hair fibers or the hair. In other words, the expressions “hair keratin fibres”, “keratin hair fibers” and “hair” are equivalent in the continuation of the description.

For the purposes of the present invention, the term “hair keratin fibres” means hair keratin fibres of the head. This term does not correspond to bodily hairs, the eyebrows or the eyelashes.

Washing step with a composition T

As indicated previously, the process according to the invention first comprises a step a) of washing with a composition T having a basic pH and comprising at least one surfactant chosen from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof.

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

The pH of composition T may be adjusted to a basic pH through the presence of a basic pH adjustment agent.

Composition T may be in solid form, such as a shampoo in solid form. In this case, the pH that is useful in the present invention is the pH of the shampoo in contact with water, such as, for example, at the time of application to the wetted hair keratin fibres.

According to one particular embodiment, composition T according to the invention comprises one or more alkaline agents. The alkaline agents may be chosen from agents conventionally used, especially chosen from alkali metal or alkaline-earth metal hydroxides, ammonium hydroxides, organic amines, preferably alkanolamines, and mixtures thereof, preferably sodium hydroxide, potassium hydroxide, monoethanolamine, 2-amino-2- methyl-1 -propanol and triethanolamine, preferably sodium hydroxide.

Composition T may comprise water. Preferably, composition T comprises water.

Advantageously, the content of water, when present, is from 40% to 95% by weight, preferably from 50% to 90% by weight, more preferably from 60% to 85% by weight, more preferably still from 65% to 80% by weight, relative to the total weight of composition T.

Anionic and/or amphoteric or zwitterionic surfactants

According to the invention, composition T comprises at least one surfactant chosen from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof.

Advantageously, the total content of surfactant(s) ranges from 1% to 50% by weight, preferably from 5% to 40% by weight, more preferably from 10% to 30% by weight, even more preferably from 12% to 30% by weight, better still from 15% to 30% by weight relative to the total weight of composition T.

Anionic surfactants

The anionic surfactants may be chosen from sulfate, sulfonate and/or carboxylic (or carboxylate) surfactants. Of course, a mixture of these surfactants may be used.

It is understood in the present description that:

- the carboxylate anionic surfactants comprise at least one carboxylic or carboxylate function (-COOH or -COO') and may optionally also comprise one or more sulfate and/or sulfonate functions;

- the sulfonate anionic surfactants comprise at least one sulfonate function (-SO3H or -SO3 ) and may optionally also comprise one or more sulfate functions, but do not comprise any carboxylate functions; and

- the sulfate anionic surfactants comprise at least one sulfate function but do not comprise any carboxylate or sulfonate functions. The carboxylate anionic surfactants that may be used thus include at least one carboxylic or carboxylate function (-COOH or -COO').

They may be chosen from the following compounds: fatty acids, acyl glycinates, acyl lactylates, acyl sarcosinates, acyl glutamates; alkyl-D- galactosideuronic acids, alkyl ether carboxylic acids, alkyl(Ce-C3o aryl) ether carboxylic acids, alkylamido ether carboxylic acids; and also the salts of these compounds; and mixtures thereof; the alkyl and/or acyl groups of these compounds including from 6 to 30 carbon atoms, notably from 12 to 28, even better still from 14 to 24 or even from 16 to 22 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; it being possible for these compounds to be polyoxyalkylenated, particularly polyoxyethylenated, and then preferably including from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units.

Use may also be made of C6-C24 alkyl monoesters of polyglycosidepolycarboxylic acids such as C6-C24 alkyl polyglycoside-citrates, C6-C24 alkyl polyglycoside-tartrates and C6-C24 alkyl polyglycoside-sulfosuccinates, and salts thereof.

Preferentially, the carboxylate anionic surfactants are chosen, alone or as a mixture, from:

- fatty acids;

- acyl glutamates, notably C6-C24 or even C12-C20 acyl glutamates, such as stearoyl glutamates, and in particular disodium stearoyl glutamate;

- acyl sarcosinates, notably C6-C24 or even C12-C20 acyl sarcosinates, such as palmitoyl sarcosinates, and in particular sodium palmitoyl sarcosinate;

- acyl lactylates, notably C12-C28 or even C14-C24 acyl lactylates, such as behenoyl lactylates, and in particular sodium behenoyl lactylate;

- C6-C24 and notably C12-C20 acylglycinates;

- (Ce-C24)alkyl ether carboxylates, and notably (Ci2-C2o)alkyl ether carboxylates;

- polyoxyalkylenated (Ce-C24)alkyl(amido) ether carboxylic acids, in particular those including from 2 to 50 ethylene oxide groups; in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino alcohol salts.

The carboxylic surfactants above may very particularly include fatty acid surfactants, notably C6-C30 surfactants. The fatty acids may include lauric, palmitic, myristic, stearic, oleic and behenic acids.

The fatty acids are advantageously chosen from among palmitic acid, myristic acid, stearic acid and mixtures thereof.

Among the carboxylic surfactants above, mention may very particularly be made of sarcosinate surfactants. Among the (Ce-C3o)acyl sarcosinates, mention may be made of palmitoyl sarcosinates, stearoyl sarcosinates, myristoyl sarcosinates, lauroyl sarcosinates and cocoyl sarcosinates, in acid form or in salified form.

The anionic surfactant(s) of sarcosinate type are advantageously chosen from sodium lauroyl sarcosinate, stearoyl sarcosine, myristoyl sarcosine, and mixtures thereof, preferably from stearoyl sarcosine, myristoyl sarcosine, and mixtures thereof.

Among the carboxylic surfactants, mention may also be made of polyoxyalkylenated alkyl(amido) ether carboxylic acids and salts thereof, in particular those including from 2 to 50 alkylene oxide and in particular ethylene oxide groups, such as the compounds sold by the company Kao under the Akypo names.

The sulfonate anionic surfactants that may be used include at least one sulfonate function (-SO3H or -SO3 ).

They may be chosen from the following compounds: alkyl sulfonates, alkylamidesulfonates, alkylarylsulfonates, a-olefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, N-acyltaurates, acylisethionates, alkylsulfolaurates; and also the salts of these compounds; the alkyl groups of these compounds including from 6 to 30 carbon atoms, notably from 12 to 28, even better still from 14 to 24 or even from 16 to 22 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; it being possible for these compounds to be polyoxyalkylenated, particularly polyoxyethylenated, and then preferably including from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units.

Preferentially, the sulfonate anionic surfactants are chosen, alone or as a mixture, from:

- C6-C24 and notably C12-C20 alkyl sulfosuccinates, notably lauryl sulfosuccinates;

- C6-C24 and notably C12-C20 alkyl ether sulfosuccinates;

- C6-C24 and notably C12-C20 N-acyltaurates;

- (Ce-C24)acyl isethionates, preferably (Ci2-Cis)acyl isethionates; in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino alcohol salts.

Preferably, the anionic surfactant(s) of sulfonate type are chosen from N- acyltaurates, and in particular N-acyl N-methyltaurates, acylisethionates, and also salts thereof and mixtures thereof.

More preferentially, the anionic surfactant(s) of sulfonate type are chosen from acylisethionates, and also salts thereof and mixtures thereof.

When the anionic surfactant is in salt form, said salt may be chosen from alkali metal salts, such as the sodium or potassium salt, ammonium salts, amine salts and in particular amino alcohol salts, and alkaline-earth metal salts, such as magnesium salt.

Examples of amino alcohol salts that may be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2- methyl-1 -propanol salts, 2-amino-2-methyl-propane-l,3-diol salts and tri s(hydroxymethyl)aminom ethane salts.

Alkali metal or alkaline-earth metal salts and in particular sodium or magnesium salts are preferably used.

Preferentially, the anionic surfactant(s) are chosen from:

- C6-C30, notably C8-C24, fatty acids;

- C6-C24, preferably C10-C22, notably C12-C20 alkyl sulfates,

- C6-C24, preferably C10-C22, notably C12-C20 alkyl ether sulfates, preferably comprising from 1 to 20 ethylene oxide units,

- C6-C24, notably C12-C20 alkyl sulfosuccinates, notably lauryl sulfosuccinates;

- C6-C24, notably C12-C20 alkyl ether sulfosuccinates;

- C6-C24, notably C12-C20 N-acyltaurates_;

- (Ce-C24)acyl isethionates, preferably (Ci2-Cis)acyl isethionates;

- C6-C24, notably C12-C20 acyl sarcosinates; notably palmitoyl sarcosinates, stearoyl sarcosinates and myristoyl sarcosinates;

- (Ce-C24)alkyl ether carboxylates, preferably (Ci2-C2o)alkyl ether carboxylates;

- polyoxyalkylenated (Ce-C24)(alkylamido) ether carboxylic acids and their salts, in particular those including from 2 to 50 alkylene oxide, more particularly ethylene oxide, groups;

- C6-C24, notably C12-C20 acyl glutamates;

- C6-C24, notably C12-C20 acyl glycinates; -and also salts thereof, in particular their alkali metal or alkaline-earth metal or zinc, ammonium or amino alcohol salts;

- and mixtures thereof.

Preferably, the anionic surfactant(s) of composition T are chosen from anionic surfactants of sulfonate type, preferably from (Cio-C22)alkyl sulfates, (Cio-C22)alkyl ether sulfates and mixtures thereof, more preferably from sodium (Cio-C22)alkyl ether sulfates and mixtures thereof.

Amphoteric or zwitterionic surfactants

Composition T according to the present invention may comprise one or more amphoteric or zwitterionic surfactants.

In particular, the amphoteric or zwitterionic surfactant(s), which are preferably non-silicone, used in composition T according to the present invention may notably be derivatives of optionally quatemized aliphatic secondary or tertiary amines, in which the aliphatic group is a linear or branched chain including from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, such as for example a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.

Mention may in particular be made of (Cs-C2o)alkyl betaines, (Cs-C2o)alkyl sulfobetaines, (C8-C2o)alkylamido(Ci-C6)alkyl betaines, (C8-C2o)alkylamido(Ci- Ce)alkyl sulfobetaines, (C8-C2o)alkylamido(C3-C8)alkyl betaines, (Cs- C2o)alkylamido(C6-C8)alkyl sulfobetaines and mixtures thereof.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodi acetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol® C2M Concentrate.

Mention may be made of the compound classified in the CTFA dictionary under the name sodium di ethylaminopropyl cocoaspartamide and sold by the company Chimex under the name Chimexane HB.

These compounds may be used alone or as mixtures.

Among the amphoteric or zwitterionic surfactants mentioned above, use is advantageously made of (C8-C2o)alkyl betaines, such as cocoyl betaine, (Cs- C2o)alkylamido(C3-C8)alkyl betaines, such as cocamidopropyl betaine, (Cs-C2o)alkyl amphoacetates, (Cs-C2o)alkyl amphodiacetates and mixtures thereof; and preferably (Cs-C2o)alkyl betaines, (C8-C2o)alkylamido(C3-C8)alkyl betaines, and mixtures thereof.

Advantageously, the amphoteric or zwitterionic surfactant(s) of the composition T are chosen from (C8-C2o)alkyl betaines, les (C8-C2o)alkyl sulfobetaines, (C8-C2o)alkylamido(C3-C8)alkyl betaines, (C8-C2o)alkylamido(C6-C8)alkyl sulfobetaines, and mixtures thereof, more preferably chosen from (C8-C2o)alkyl betaines, (C8-C2o)alkylamido(C3-C8)alkyl betaines and mixtures thereof, more preferably still from (C8-C2o)alkylamido(C3-C8)alkyl betaines and mixtures thereof.

According to one preferred embodiment, composition T comprises an amount of surfactant(s), chosen from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, of from 1% to 50% by weight, preferably from 5% to 40% by weight, more preferably from 10% to 30% by weight relative to the total weight of composition T.

Preferably, the surfactant(s) are chosen from:

- notably Cs to C26, and preferably C10 to C22, alkyl sulfates;

- notably Cs to C26, and preferably C10 to C22, alkyl ether sulfates, including preferably from 2 to 10 ethylene oxide units; in particular in the form of alkali metal or alkaline-earth metal, ammonium or amino alcohol salts,

- (C8-C2o)alkyl betaines, (C8-C2o)alkylamido(C3-C8)alkyl betaines and mixtures thereof, better still from (C8-C2o)alkylamido(C3-C8)alkyl betaines and mixtures thereof; and mixtures thereof.

According to one 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.

Additives

Composition T used in the context of the dyeing process according to the invention may further contain any commonly used additive or adjuvant.

The additives that may be used include reducing agents, thickeners, softeners, moisturizing agents, UV screening agents, solubilizers, fragrances, vitamins, polymers, preservatives, fatty substances and mixtures thereof. (Poly)carbodiimide compounds

Composition C used in the context of the process according to the invention comprises at least one (poly)carbodiimide compound of particular formula (II) as indicated above.

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

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

The term “carbodiimide group ” means a divalent linear triatomic fraction of general formula -(N=C=N)-.

Preferably, the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) below:

in which:

- n and z denote an integer ranging from 1 to 20, with n+z > 2 and w denotes an integer ranging from 1 to 3; - Li independently represents a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof;

- E independently represents a group chosen from:

- Re independently represents a hydrogen atom or a hydrocarbon-based radical, optionally interrupted with one or more heteroatoms.

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

The hydrocarbon-based radical may comprise one or more cyclic groups.

The hydrocarbon-based radical may be interrupted with one or more heteroatoms, in particular chosen from O, S or N and/or substituted with one or more cations, anions or zwitterions or cationic groups such as ammonium, anionic groups such as carboxylate, or zwitterionic groups, and/or comprising a metal ion which may be incorporated in the form of a salt.

The term "heleroalom(s)" means an oxygen O, sulfur S or nitrogen N atom, and also halogen atoms such as Cl, F, Br and I. If the heteroatom is included in the chain of the hydrocarbon-based radical, the heteroatom is preferably chosen from oxygen O, sulfur S or nitrogen N atoms.

Preferably, Xi and X2 independently represent an oxygen atom.

Preferably, Ri and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxy carboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, and mixtures thereof.

In a preferred embodiment, Ri and R2 are independently chosen from groups (i) to (iv) below:

(i) the compound of formula (III) below:

R₇-O-C(O)-C(R₈)(H)- (III), in which R7 represents a C1-C3 alkyl group and Rs represents a hydrogen atom or a Ci- C3 alkyl group; preferably, R7 is a methyl and Rs is a hydrogen atom or a methyl. (ii) the compound of formula (IV) below:

R9-[0-CH₂-C(H)(RIO)]_P- (IV), in which R9 represents a C1-C4 alkyl group, Rio represents a hydrogen atom or a C1-C4 alkyl group and p denotes an integer ranging from 1 to 3; preferably, R9 is a methyl, ethyl or butyl, Rio is a hydrogen atom or a methyl and p is equal to 1.

(iii) the compound of formula (V) below: (Rii)₂N-CH₂-C(H)(Ri2)- (V), in which Rn represents a C1-C4 alkyl group and RI₂ represents a hydrogen atom or a C1-C4 alkyl group; preferably, Rn is a methyl, ethyl or butyl and RI₂ is a hydrogen atom or a methyl.

(iv) the compound of formula (VI) below:

Ri3-[O-CH₂-C(H)(Ri₄)]_q- (VI), in which R13 represents a C1-C4 alkyl group or a phenyl, R14 represents a hydrogen atom or a C1-C4 alkyl group and q denotes an integer ranging from 4 to 30; preferably, R13 is a methyl, ethyl or butyl and R14 is a hydrogen atom or a methyl.

Preferably, Ri and R₂ independently represent a compound of formula (VI) in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.

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

Preferably, in formula (IV), R9 is a methyl, ethyl or butyl and Rio is a hydrogen atom or a methyl and p is equal to 1.

Preferably, in formula (VI), R13 is a methyl, ethyl or butyl and R14 is a hydrogen atom or a methyl and q denotes an integer ranging from 4 to 30.

According to another alternative embodiment, Ri and R₂ are identical and represent a compound of formula (VI) in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.

Preferably, n denotes an integer ranging from 1 to 20, more preferentially from 2 to 20.

Preferably, z denotes an integer ranging from 1 to 20, more preferentially from 2 to 20. Preferably, w is equal to 1.

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

Preferably, Li is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical such as methylene, ethylene and propylene, a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene and cyclohexylene, a C3-C12 heterocycloalkylene group such as imidazolene, pyrrolene and furanylene, or a Ce-Cu arylene group such as phenylene, and mixtures thereof.

For example, Li may be chosen from a radical derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4- trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-l,3-dioctylcyclobutane, 4,4’- dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-napththylene diisocyanate, 4,4’-diphenylmethane diisocyanate, 4, d’diphenyldimethylmethane diisocyanate and phenylene diisocyanate, and mixtures thereof.

Preferably, Li is chosen from a C3-C15 cycloalkylene radical or a Ce-Cu arylene group, and mixtures thereof, such as the compounds of formula (VII) below:

Preferably, Li is 4,4-dicyclohexylenemethane corresponding to formula (VIII) below:

(VIII).

According to another embodiment, when Li is a Ce-Cu arylene group, Li is not the m-tetramethylxylylene radical represented by formula (IX) below:

(IX).

As indicated previously, E independently represents a group chosen from: -O-R3-O-; -S-R4-S-; -R₅-N(R6)-R4-N(R₆)-R5-; in which R3 and R4 independently represent a divalent hydrocarbon-based radical optionally interrupted with one or more heteroatoms;

- Rs independently represents a covalent bond or a saturated divalent hydrocarbonbased radical, optionally interrupted with one or more heteroatoms; and

Preferably, R3 and R4 are independently chosen from a Ce-Cu arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Cis alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatoms, and mixtures thereof.

More preferentially, R3 and R4 are independently chosen from a linear or branched Ci-Cis alkylene radical such as methylene, butylene, propylene or ethylene, optionally interrupted with one or more heteroatoms.

Preferably, when R5 is not a covalent bond, R5 is chosen from a Ce-Cu arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Cis alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatoms, and mixtures thereof.

Preferably, Re is chosen from a Ce-Cu arylene radical such as phenylene, a C3-C12 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched Ci-Cis alkylene radical such as methylene and ethylene, optionally interrupted with one or more heteroatoms, and mixtures thereof. Preferably, E represents a group -O-R3-O- in which R3 is chosen from a Ce- C14 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

More preferentially, E represents a group -O-R3-O- in which R3 represents a linear or branched Ci-Cis alkylene radical such as methylene, butylene, propylene or ethylene, optionally interrupted with one or more heteroatoms.

According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from a-methyl styryl isocyanates of formula (X) below:

in which R independently represents an alkyl group containing from 1 to 24 carbon atoms, a cycloalkyl group containing from 3 to 24 carbon atoms or an aryl group containing from 6 to 24 carbon atoms, and n denotes an integer ranging from 2 to 100.

In this embodiment, the term “alkyl group” is as defined previously.

In this embodiment, the term “cycloalkyl group” is as defined previously.

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

According to another particular embodiment, the (poly)carbodiimide compound is a compound of formula (XI) below:

(XI), in which R independently represents an alkyl group containing from 1 to 24 carbon atoms, a cycloalkyl group containing from 3 to 24 carbon atoms or an aryl group containing from 6 to 24 carbon atoms. The “alkyl group”, the “cycloalkyl group” and the “aryl group” are as defined previously.

According to a preferred embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

- Xi and X2 independently represent an oxygen atom;

- Ri and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, more preferentially the compound of formula (VI) as described previously in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q denotes an integer ranging from 4 to 30;

- n and z, when they are present, denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

- Li, when it is present, is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical;

- A, when it is present, is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical;

- E, when it is present, independently represents a group chosen from:

-O-R3-O-; -S-R4-S-; -R₅-N(R6)-R4-N(R₆)-R5-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;

- when R5 is not a covalent bond, R5, when it is present, is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof; and

- Re, when it is present, is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

Preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

- Xi and X2 independently represent an oxygen atom; - Ri and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, and mixtures thereof;

- n and z denote an integer ranging from 1 to 20, with n+z > 2 and w is equal to 1;

- Li is chosen from a Ci-Cis divalent aliphatic hydrocarbon-based radical, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a Ce-Cu arylene group, and mixtures thereof;

- E independently represents a group chosen from:

- when R5 is not a covalent bond, R5 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof; and

- Re is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

More preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

- Xi and X2 independently represent an oxygen atom;

- Ri and R2 are, independently, monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed;

- Li is a C3-C15 cycloalkylene radical;

- E independently represents a group chosen from:

-O-R3-O-; -S-R4-S-; -R₅-N(R6)-R4-N(R6)-RS-; in which R3 and R4 are independently chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof;

- when Rs is not a covalent bond, Rs is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof; and - Re is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

Even more preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:

- Xi and X2 independently represent an oxygen atom;

- Ri and R2 independently represent the compound of formula (VI) below:

Ri3-[O-CH₂-C(H)(Ri₄)]_q- (VI), in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;

- n and z denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10 and w is equal to 1;

- Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4, 4-di cyclohexylenemethane; and

- E represents a group -O-R3-O- in which R3 is chosen from a Ce-Cu arylene radical, a C3-C12 cycloalkylene radical, a linear or branched Ci-Cis alkylene radical, optionally interrupted with one or more heteroatoms, and mixtures thereof.

- Xi and X2 independently represent an oxygen atom;

- Ri and R2 independently represent the compound of formula (VI) below: Ri3-[O-CH₂-C(H)(Ri₄)]_q- (VI) in which R13 represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferentially a methyl, R14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;

- Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylenemethane, preferably 4,4- dicyclohexylenemethane; and

- E represents a group -O-R3-O- in which R3 represents a linear or branched Ci-Cis alkylene radical such as methylene, propylene, butylene or ethylene, optionally interrupted with one or more heteroatoms. According to a preferred embodiment, the (poly)carbodiimide compound is a compound of formula (XII) below:

in which LI is 4,4-dicyclohexylenemethane, n and z denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10, E represents a group -O-R3-O- in which R3 represents a linear or branched Ci-Cis alkylene radical such as methylene, propylene, butylene or ethylene, optionally interrupted with one or more heteroatoms, and r and s denote an integer ranging from 4 to 30.

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

Polymer comprising at least one reactive group chosen from carboxylic acids

Composition C used in the context of the process according to the invention comprises at least one polymer comprising at least one reactive group chosen from carboxylic acids, preferably at least one acrylic polymer. Preferably, the polymer(s) comprising at least one reactive group chosen from carboxylic acids, preferably acrylic polymers, are in the form of aqueous dispersions of particles of acrylic polymer(s).

Thus, preferably, composition C comprises at least one acrylic polymer in the form of aqueous dispersions of particles of acrylic polymers.

The dispersion(s) may be simple dispersions in the aqueous medium of the cosmetic composition. As a particular case of dispersions, mention may be made of latices.

More preferentially, the acrylic polymer(s) are in the form of aqueous dispersions of film-forming acrylic polymer particles.

For the purposes of the invention, the term "polymer" means a compound corresponding to the repetition of one or more units (these units being derived from compounds known as monomers). This or these unit(s) are repeated at least twice and preferably at least three times.

The term ‘film-forming polymer" refers to a polymer that is capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, notably on hair keratin fibres, and preferably a cohesive film.

For the purposes of the present invention, the term “acrylic polymer" means a polymer synthesized from at least one monomer chosen from (meth)acrylic acid and/or (meth)acrylic acid ester and/or (meth)acrylic acid amide.

The unit(s) derived from the (meth)acrylic acid monomers of the polymer may optionally be in the form of salt(s), notably of alkali metal, alkaline-earth metal or ammonium salt(s), or organic base salt(s).

The (meth)acrylic acid esters (also known as (meth)acrylates) are advantageously chosen from alkyl (meth)acrylates, in particular Ci to C30, preferably Ci to C20 and better still Ci to C10 alkyl (meth)acrylates, aryl (meth)acrylates, in particular Ce to C10 aryl (meth)acrylates, and hydroxyalkyl (meth)acrylates, in particular C2 to Ce hydroxyalkyl (meth)acrylates.

Among the alkyl (meth)acrylates that may be mentioned are methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, lauryl (meth)acrylate and cyclohexyl (meth)acrylate.

Among the hydroxyalkyl (meth)acrylates that may be mentioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2- hydroxypropyl methacrylate. Among the aryl (meth)acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.

The (meth)acrylic acid esters that are particularly preferred are alkyl, preferably Ci to C30, more preferentially Ci to C20, better still Ci to C10, and even more particularly Ci to C4, alkyl (meth)acrylates.

According to the present invention, the alkyl group of the esters may be fluorinated, or even perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are replaced with fluorine atoms.

As (meth)acrylic acid amides, examples that may be mentioned include (meth)acrylamides and also N-alkyl(meth)acrylamides, in particular N-(C2 to C12 alkyl)(meth)acrylamides. Among the N-alkyl(meth)acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and N- undecylacrylamide.

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

Preferably, the acrylic polymer(s) according to the invention comprise one or more units derived from the following monomers: a) (meth)acrylic acid; and b) Ci to C30, more preferentially Ci to C20, better still Ci to C10, and even more particularly Ci to C4, alkyl (meth)acrylate.

Preferably, the aqueous dispersion of acrylic polymer particles does not comprise any surfactant.

The term ''siirfactarit" refers to any agent that is capable of modifying the surface tension between two surfaces.

Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and of methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and of ethyl acrylate such as the compound sold under the trade name Luvimer MAE by the company BASF, or the compound Polyacrylate- 2 Crosspolymer sold under the trade name Fixate Superhold Polymer by the company Lubrizol, or the compound Acrylate Copolymer sold under the trade name Daitosol 3000VP3 by the company Daito Kasei Kogyo, or the compound Acrylate Polymer sold under the trade name Daitosol 3000 SLPN-PE1 by the company Daito Kasei Kogyo. The acrylic polymer may optionally comprise one or more additional monomers, other than the (meth)acrylic acid and/or (meth)acrylic acid ester and/or (meth)acrylic acid amide monomers.

As additional monomer, mention will be made, for example, of styrene monomers, in particular styrene and a-m ethyl styrene, and preferably styrene.

In particular, the acrylic polymer may be a styrene/(meth)acrylate copolymer and notably a polymer chosen from copolymers resulting from the polymerization of at least one styrene monomer and at least one Ci to C20, preferably Ci to C10, alkyl (meth)acrylate monomer.

The Ci to C10 alkyl (meth)acrylate monomer may be chosen from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate.

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

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

More preferentially, composition C comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more units derived from the following monomers: a) (meth)acrylic acid; and b) Ci to C30, more preferentially Ci to C20, better still Ci to C10, and even more particularly Ci to C4, alkyl (meth)acrylate.

Preferably, the aqueous dispersion of acrylic polymer particles has an acrylic polymer (or active material, or solids) content, on the basis of the weight of the dispersion, of from 20% to 60% by weight, more preferentially from 22% to 55% by weight and better still from 25% to 50% by weight.

Advantageously, the polymer(s) comprising at least one reactive group chosen from carboxylic acids, preferably acrylic polymers, are 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.

According to a particular embodiment, the total content of the aqueous dispersion(s) of acrylic polymer particle(s) preferably ranges 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.

Colouring agent

Composition C used in the context of the process according to the invention comprises at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.

Preferably, composition C used in the context of the process according to the invention comprises at least one pigment.

The term “pigment” refers to any pigment that gives colour to keratin materials. Their solubility in water at 25°C and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

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

They may be natural, of natural origin, or non-natural.

These pigments may be in pigment powder or paste form. They may be coated or uncoated.

The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof.

The pigment may be a mineral pigment. The term “mineral pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

The pigment may be an organic pigment. The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’s Encyclopedia in the chapter on organic pigments.

The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

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

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

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

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

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

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

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

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

- Cosmenyl Blue A2R: Blue 15.1 pigment (CI 74160);

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

- Cosmenyl Black R: Black 7 pigment (CI 77266).

The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may notably be composed of particles including an inorganic core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core.

The organic pigment may also be a lake. The term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use. The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.

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

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

The pigment may also be a pigment with special effects. The term “pigments with special effects” means pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from coloured pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.

Several types of special-effect pigments exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.

Examples of pigments with special effects that may be mentioned include nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and notably with ferric blue or with chromium oxide, mica covered with titanium and with an organic pigment as defined previously, and also nacreous pigments based on bismuth oxychloride. Nacreous pigments that may be mentioned include the nacres Cellini sold by BASF (mica-TiCh-lake), Prestige sold by Eckart (mica-TiCE), Prestige Bronze sold by Eckart (mica-Fe2O3) and Colorona sold by Merck (mica-TiO2-Fe2O3).

Mention may also be made of the gold-coloured nacres sold notably by the company BASF under the name Brilliant Gold 212G(Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); the bronze nacres sold notably by the company Merck under the name Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super Bronze (Cloisonne); the orange nacres sold notably by the company BASF under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion Orange (Colorona) and Matte Orange (17449) (Microna); the brown nacres sold notably by the company BASF under the name Nu-antique Copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper tint sold notably by the company BASF under the name Copper 340A (Timica); the nacres with a red tint sold notably by the company Merck under the name Sienna Fine (17386) (Colorona); the nacres with a yellow tint sold notably by the company BASF under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold notably by the company BASF under the name Sunstone GO 12 (Gemtone); the pink nacres sold notably by the company BASF under the name Tan Opale G005 (Gemtone); the black nacres with a gold tint sold notably by the company BASF under the name Nu-antique Bronze 240 AB (Timica), the blue nacres sold notably by the company Merck under the name Matte Blue (17433) (Microna), the white nacres with a silvery tint sold notably by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold notably by the company Merck under the name Indian Summer (Xirona), and mixtures thereof.

Still as examples of nacres, mention may also be made of particles including a borosilicate substrate coated with titanium oxide.

Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.

Finally, examples of nacres that may also be mentioned include polyethylene terephthalate glitter flakes, notably those sold by the company Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver glitter flakes). It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.

The pigments with special effects may also be chosen from reflective particles, i.e. notably from particles whose size, structure, notably the thickness of the layer(s) of which they are made and their physical and chemical nature, and surface state, allow them to reflect incident light. This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. more luminous points that contrast with their environment making them appear to sparkle. The reflective particles may be selected so as not to significantly alter the colouring effect generated by the colouring agents with which they are combined, and more particularly so as to optimize this effect in terms of colour rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or tint.

These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form.

The reflective particles, whatever their form, may or may not have a multilayer structure and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, notably of a reflective material.

When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, notably titanium or iron oxides obtained synthetically.

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

More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, notably aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.

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

Reflective particles are notably described in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

Again as an example of reflective particles including a mineral substrate coated with a layer of metal, mention may also be made of particles including a silver- coated borosilicate substrate.

Particles with a silver-coated glass substrate, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by the company Toyal. Particles with a glass substrate coated with a nickel/chromium/molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.

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

Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiCh sold under the name Visionaire by the company Eckart.

Mention may also be made of interference pigments which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek). Special-effect pigments also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.

The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects.

The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 pm, preferably between 20 nm and 80 pm and more preferentially between 30 nm and 50 pm.

The pigments may be dispersed in the composition by means of a dispersant.

The dispersant serves to protect the dispersed particles against agglomeration or flocculation thereof. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxy stearic acid in particular and of C8 to C20 fatty acid and of polyols such as glycerol or diglycerol are used, such as poly( 12-hydroxy stearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or else polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof.

As other dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C.

The pigments used in the composition may be surface-treated with an organic agent.

Thus, the pigments surface-treated beforehand that are useful in the context of the invention are pigments which have been completely or partially subjected to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those described notably in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, notably polydimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.

The surface-treated pigments that are useful in the composition may also have been treated with a mixture of these compounds and/or may have undergone several surface treatments.

The surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.

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

The organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.

The surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in patent US 4 578 266.

An organic agent covalently bonded to the pigments will preferably be used.

The agent for the surface treatment may represent from 0.1% to 50% by weight relative to the total weight of the surface-treated pigment, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of the surface-treated pigment.

Preferably, the surface treatments of the pigments are chosen from the following treatments:

- a PEG-silicone treatment, for instance the AQ surface treatment sold by LCW;

- a methicone treatment, for instance the SI surface treatment sold by LCW;

- a dimethicone treatment, for instance the Covasil 3.05 surface treatment sold by LCW;

- a dimethicone/trimethyl siloxysilicate treatment, for instance the Covasil 4.05 surface treatment sold by LCW;

- a magnesium myristate treatment, for instance the MM surface treatment sold by LCW;

- an aluminium dimyristate treatment, for instance the MI surface treatment sold by Miyoshi;

- a perfluoropolymethyl isopropyl ether treatment, for instance the FHC surface treatment sold by LCW;

- an isostearyl sebacate treatment, for instance the HS surface treatment sold by Miyoshi;

- a perfluoroalkyl phosphate treatment, for instance the PF surface treatment sold by Daito;

- an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment, for instance the FSA surface treatment sold by Daito;

- a polymethylhydrogenosiloxane/perfluoroalkyl phosphate treatment, for instance the FS01 surface treatment sold by Daito;

- an acrylate copolymer/dimethicone treatment, for instance the ASC surface treatment sold by Daito;

- an isopropyl titanium triisostearate treatment, for instance the ITT surface treatment sold by Daito; - an acrylate copolymer treatment, for instance the APD surface treatment sold by Daito;

- a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, for instance the PF + ITT surface treatment sold by Daito.

According to a particular embodiment of the invention, the dispersant is present with organic or mineral pigments in submicron-sized particulate form.

The term “submicron-sized” or “submicronic” refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometre (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm.

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

The dispersant(s) may therefore have a silicone backbone, such as silicone polyether and dispersants of amino silicone type. Among the suitable dispersants that may be mentioned are:

- amino silicones, i.e. silicones comprising one or more amine groups such as those sold under the names and references: BYK LPX 21879 by BYK, 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,

- polydimethylsiloxane (PDMS) silicones bearing carboxyl groups such as X-22162 and X-22370 by Shin-Etsu, epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695 by Genesee Polymers, or Tego® RC 1401, Tego® RC 1403, Tego® RC 1412 by Evonik.

According to a particular embodiment, the dispersant(s) are of amino-silicone type and are cationic.

Preferably, the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments.

In one variant of the invention, the pigment(s) are organic pigments, preferentially organic pigments surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment(s) are mineral pigments. Preferably, the pigment(s) are chosen from iron oxides, notably red, brown or black iron oxides. As an example of an iron oxide, mention may be made of the iron oxide sold by the company Sun Chemical under the name SunPuro® Red Iron Oxide.

Direct dye

Composition C used in the context of the process according to the invention may comprise one or more direct dyes.

The term “direct dye” means natural and/or synthetic dyes, other than oxidation dyes. These are dyes which will spread superficially over the fibre. They may be ionic, for example cationic or anionic, or nonionic.

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

The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances. The term “anionic direct dye” means any direct dye including in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes.

As examples of acid dyes, mention may be made of: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or Sunset Yellow; Acid Red 111, Acid Red 134, Acid Yellow 38.

As examples of pyrazolone anionic azo dyes, mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, Acid Yellow 17. As examples of anthraquinone dyes, mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2; Acid Black 48.

As examples of nitro dyes, mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XXII’), mention may be made of: Acid Yellow 1, the sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid, 2-piperidino-5- nitrobenzenesulfonic acid, 2-(4’-N, N-(2” -hydroxy ethyl)amino-2’- nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7.

As examples of triarylmethane dyes, mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50.

As examples of xanthene dyes, mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9.

As examples of indole dyes, mention may be made of: Acid Blue 74.

As examples of quinoline dyes, mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions containing these natural dyes and particularly henna-based poultices or extracts.

The colouring agent(s) may be present in a total amount ranging from 0.001% to 20% by weight and preferably from 0.005% to 15% by weight relative to the total weight of composition C; preferably, the colouring agents are chosen from pigments.

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

The direct dye(s) may be present in a total amount ranging from 0.001% to 10% by weight and preferably from 0.005% to 5% by weight relative to the total weight of composition C. Non-carboxylic anionic thickener

Composition C used in the context of the process according to the invention may also comprise at least one non-carboxylic anionic thickener.

For the purposes of the present invention, the term “non-carboxylic agent” means an agent which does not comprise any carboxylic acid functions (-COOH) or carboxylate functions (-COO ).

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

Preferably, the non-carboxylic anionic thickener(s) are chosen from non- carboxylic anionic polymers, more preferentially from anionic polymers bearing (a) sulfonic group(s).

For the purposes of the invention, the term “anionic polymer” means a polymer comprising one or more anionic or anionizable groups, and not comprising any cationic or cationizable groups.

Advantageously, the non-carboxylic anionic thickener(s) are chosen from anionic polymers including at least one ethylenically unsaturated monomer bearing a sulfonic group, in free form or partially or totally neutralized form.

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

These polymers may be associative or non-associative, preferably non- associative.

It is recalled that “associative polymers” are polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

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

The term “hydrophobic group” means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.

Preferentially, the hydrocarbon-based group originates from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.

The ethylenically unsaturated monomers bearing a sulfonic group are notably chosen from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci- C22)alkylsulfonic acids, N-(Ci-C22)alkyl(meth)acrylamido(Ci-C22)alkylsulfonic acids such as undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.

More preferentially, use will be made of (meth)acrylamido(Ci- C22)alkylsulfonic acids, for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2- acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3- heptanesulfonic acid, and also the partially or completely neutralized forms thereof.

Use will more particularly be made of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially or totally neutralized forms thereof.

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

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

The associative AMPS polymers may notably be chosen from statistical associative AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine, and such as those described in patent application WO 00/31154 (forming an integral part of the content of the description). These polymers may also contain other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acid derivatives, such as esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, or mixtures of these compounds.

The preferred polymers of this family are chosen from associative copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer. Preferably, the non-carboxylic anionic thickener(s) are chosen from sodium 2-acrylamido-2-methylpropanesulfonate/hydroxy ethyl acrylate copolymer, sold by the company SEPPIC (INCI name hydroxy ethyl aery late/ sodium acryloyldimethyl taurate copolymer).

Advantageously, the total content of the non-carboxylic anionic thickener(s) ranges from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, more preferably from 0.1% to 5% by weight, even more preferably from 0.1% to 3% by weight relative to the total weight of composition C.

Associative polymers

Composition C used in the context of the process according to the invention may also comprise at least one associative polymer different from the acrylic polymer and different from the non-carboxylic anionic thickener as defined previously.

As recalled above, “associative polymers” are polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

The term “hydrophobic group'" means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.

The associative polymers may be of nonionic, anionic, cationic or amphoteric nature.

Preferably, the associative polymer(s) are chosen from anionic associative polymers.

Among the associative polymers of anionic type, mention may be made of copolymers comprising, among their monomers, an a,P-monoethylenically unsaturated carboxylic acid and an ester of an a,P-monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.

Preferentially, these compounds also comprise, as monomer, an ester of an a,P-monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.

An example of a compound of this type that may be mentioned is Aculyn 22® sold by the company Rohm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer; and also Aculyn 88, also sold by the company Rohm & Haas. Advantageously, the associative polymer(s), different from the acrylic polymers and different from the non-carboxylic anionic thickeners described previously, are chosen from copolymers including among their monomers an a,P- monoethylenically unsaturated carboxylic acid and an ester of an a,P- monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.

Advantageously, the total content of the associative polymer(s), different from the acrylic polymers and different from the non-carboxylic anionic thickener(s) described previously, ranges from 0.05% to 15% by weight, preferably from 0.05% to 10% by weight, more preferably from 0.1% to 5% by weight, even more preferably from 0.1% to 1% by weight relative to the total weight of composition C.

Solvents

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

Composition C may also comprise one or more organic solvents.

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

The organic solvents may be present in a total content of between 0.01% and 60% by weight, preferably between 0.05% and 50% by weight and more preferablyinclusively between 0.1% and 45% by weight relative to the total weight of composition C.

Additives

Composition C used in the context of the process according to the invention may contain any adjuvant or additive usually used.

Among the additives that may be contained in the composition, mention may be made of reducing agents, softeners, antifoams, moisturizers, UV-screening agents, peptizers, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers described previously, preserving agents, silicones, oils, waxes different from the silicones in the form of a wax, and mixtures thereof.

Composition C used in the context of the process according to the invention may notably be in the form of a suspension, a dispersion, a gel, an emulsion, notably an oil-in-water (O/W) or water-in-oil (W/O) emulsion, or a multiple emulsion (W/O/W or polyol/O/W or O/W7O), in the form of a cream, a mousse, a stick, a dispersion of vesicles, notably of ionic or nonionic lipids, or a two-phase or multi-phase lotion.

A person skilled in the art may select the appropriate presentation form, and also the method for preparing it, on the basis of his general knowledge, taking into account firstly the nature of the constituents used, notably their solubility in the support, and secondly the intended application of the composition.

Protocol

Composition T as defined above may be applied to wet or dry hair keratin fibres, and also to any type of fair or dark, natural or dyed, permanent-waved, bleached or relaxed hair keratin fibres.

Preferably, a rinsing, wringing and/or drying step is performed after the application of composition T as defined previously.

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

Composition T may be applied at room temperature (between 15 and 25°C).

After application of composition T and foaming of the composition, it is possible to wait for between 1 minute and 30 minutes, preferably up to 15 minutes, or even 10 minutes, before rinsing of the composition T.

According to this embodiment, after washing and then rinsing, and optionally wringing and/or drying of the hair keratin fibres, it is possible to wait for between 1 minute and 12 hours, in particular between 1 minute and 10 hours, more particularly between 1 minute and 7 hours, more preferably between 1 minute and 6 hours, before applying composition C to the hair keratin fibres.

Preferably, the leave-on time after washing with composition T and rinsing and before the application of composition C is between 1 minute and 5 hours, preferably between 1 minute and 1 hour, on the hair keratin fibres.

The composition C described above may be employed on wet or dry hair keratin fibres, and also on all types of fair or dark, natural or dyed, permanent- waved, bleached or relaxed hair keratin fibres. Preferably, a step of washing, rinsing, wringing and/or drying is performed after the application of composition C to the hair keratin fibres.

More preferably, a step of drying is performed after the application of composition C to the hair keratin fibres.

The application of composition C to the hair keratin fibres may be performed via any conventional means, in particular using a comb, a fine brush, a coarse brush, a sponge or with the fingers.

The application of composition C to the hair keratin fibres is generally performed at room temperature (between 15 and 25°C).

After application of composition C to the hair keratin fibres, it is possible to wait for between 1 minute and 6 hours, in particular between 1 minute and 2 hours, more particularly between 1 minute and 1 hour, more preferentially between 1 minute and 30 minutes, before, for example, a washing, rinsing, wringing step and/or drying step.

After application of composition C, the hair keratin fibres can be left to dry or dried, for example at a temperature of greater than or equal to 30°C.

The process according to the invention may thus comprise a step of applying heat to the hair keratin fibres using a heating tool.

The heat application step may be performed using a hood, a hairdryer, a straightening or curling iron, a Climazon hood, etc.

Preferably, the heat application step is performed using a hairdryer.

When the process of the invention employs a step of applying heat to the hair keratin fibres, the step of applying heat to the hair keratin fibres takes place after the application of composition C to the hair keratin fibres.

During the step of applying heat to the hair keratin fibres, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through.

When the step of applying heat to the hair keratin fibres is performed using a hood or hairdryer, the temperature is preferably between 30 and 110°C, preferentially between 50 and 90°C.

When the step of applying heat to the hair keratin fibres is performed using a straightening iron, the temperature is preferably between 110 and 220°C, preferably between 140 and 200°C.

In a particular variant, the process of the invention involves a step (cl) of applying heat using a hood, a hairdryer or a Climazon hood, preferably a hairdryer, and a step (c2) of applying heat using a straightening or curling iron, preferably a straightening iron.

Step (cl) may be performed before step (c2).

During step (cl), also known as the drying step, the hair keratin fibres may be dried, for example at a temperature of greater than or equal to 30°C. According to a particular embodiment, this temperature is greater than 40°C. According to a particular embodiment, this temperature is greater than 45°C and less than 110°C.

Preferably, if the hair keratin fibres are dried, they are dried, in addition to using a supply of heat, with a flow of air. This flow of air during drying makes it possible to improve the strand separation of the coating.

During the drying, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through.

During step (c2), the passage of the straightening or curling iron, preferably the straightening iron, may be performed at a temperature ranging from 110°C to 220°C, preferably between 140°C and 200°C.

After the heating step, a hair-shaping step may be performed with, for example, a straightening iron; the temperature for the hair-shaping step may be between 110°C and 220°C, preferably between 140°C and 200°C.

According to one embodiment, the invention is a process for dyeing hair keratin fibres comprising the following steps: i) the application to the hair keratin fibres of a composition T comprising at least one surfactant chosen from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, and having a basic pH, as defined previously; ii) optionally a leave-on time of said composition T on the hair keratin fibres of from 1 minute to 1 hour, preferably from 1 minute to 30 minutes; iii) optionally a step of rinsing, wringing and/or drying said hair keratin fibres, preferably rinsing; and then iv) the application to the hair keratin fibres of at least one composition C comprising:

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

- at least one polymer comprising at least one reactive group chosen from carboxylic acids, as defined previously; and

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof as described previously; and then v) optionally a leave-on time of said composition C on the hair keratin fibres of from 1 minute to 30 minutes, preferably from 1 to 20 minutes; and then vi) optionally a step of washing, rinsing, wringing and/or drying said hair keratin fibres.

Advantageously, the step of applying composition C to the hair keratin fibres is repeated several times.

According to a preferred embodiment, step b) of the process according to the invention in extemporaneously mixing, at the time of use, at least two compositions A and B to obtain a composition C and in applying composition C to the hair keratin fibres, with:

- composition A comprising at least one (poly)carbodiimide compound as defined previously, composition A and/or composition B comprising at least one polymer comprising at least one reactive group chosen from carboxylic acids, preferably at least one acrylic polymer, as defined previously, and at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, as defined previously.

Advantageously, composition B comprises at least one polymer comprising at least one reactive group chosen from carboxylic acids, preferably an acrylic polymer, as defined previously.

Preferably, composition B comprises at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, as described previously.

According to a preferred embodiment, step b) of the process according to the invention consists in extemporaneously mixing, at the time of use, at least two compositions A and B to obtain a composition C and in applying composition C to the hair keratin fibres, with:

- composition A comprising at least one (poly)carbodiimide compound as defined previously,

- composition B comprising at least one acrylic polymer as defined previously, and at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, as defined previously.

Preferably, composition A does not comprise at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, as described previously.

According to this embodiment, compositions A and B are mixed preferably less than 15 minutes before application to the hair keratin fibres, more preferentially less than 10 minutes before application, better still less than 5 minutes before application.

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

The total content of the (poly)carbodiimide compound(s) preferably ranges from 0.01% to 40% by weight, more preferably from 0.1% to 30% by weight, even more preferably from 0.5% to 20% by weight, better still from 1% to 12% by weight relative to the total weight of composition A.

The total content of the acrylic polymer(s) preferably ranges from 0.2% to 60% by weight, more preferably from 1% to 40% by weight, even more preferably from 1% to 30% by weight, better still from 2% to 20% by weight relative to the total weight of composition B.

According to a preferred embodiment, the invention is a process for dyeing hair keratin fibres comprising the following steps: i) the application to the hair keratin fibres of a composition T, as defined previously, comprising water, at least one surfactant chosen from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, and having a basic pH; ii) optionally a leave-on time of said composition T on the hair keratin fibres of from 1 minute to 30 minutes, preferably from 1 minute to 10 minutes; iii) a step of rinsing, optionally of wringing and/or drying said hair keratin fibres; and then iv) the application to the hair keratin fibres of at least one composition C comprising:

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

- at least one acrylic polymer as defined previously; and

- at least one colouring agent chosen from pigments, direct dyes and mixtures thereof, as described previously; and then v) optionally a leave-on time of said composition C on the hair keratin fibres of from 1 minute to 30 minutes, preferably from 1 to 20 minutes; and then vi) optionally a step of washing, rinsing, wringing and/or drying said hair keratin fibres.

Multi-compartment device (kit)

The present invention also relates to a device for dyeing hair keratin fibres, comprising several compartments containing:

- a first compartment comprising composition T as defined previously,

- a second compartment comprising composition A comprising at least one (poly)carbodiimide compound as defined previously; - a third compartment comprising composition B comprising at least one pigment as defined previously, and at least one polymer comprising at least one reactive group chosen from carboxylic acids, as defined previously.

The present invention will now be described more specifically by means of examples, which do not in any way limit the scope of the invention. However, the examples make it possible to support specific features, variants and preferred embodiments of the invention.

EXAMPLES

The (poly)carbodiimide(s) of the invention are accessible via synthetic methods known to those skilled in the art starting from commercial products or reagents that can be synthesized according to chemical reactions that are also known to those skilled in the art. Mention may be made, for example, of the book Sciences of Synthesis - Houben - Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D-70469 Stuttgart, or the American patent US 4 284 730 or the Canadian patent application CA 2 509 861.

More particularly, the process for preparing the (poly)carbodiimides of the invention involves, in a first step, a diisocyanate reagent (1):

O=C=N-Li-N=C=O (1), in which formula (1) Li is as defined previously, which reacts in the presence of a carboimidation catalyst (2) such as those described in US 4 284 730, notably phosphorus-based catalysts particularly chosen from phospholene oxides and phospholene sulfoxides, diaza- and oxaza-phospholanes, preferably under an inert atmosphere (nitrogen or argon), and in particular in a polar solvent which is preferably aprotic such as THF, glyme, diglyme, 1,4-di oxane or DMF, at a temperature between room temperature and the reflux temperature of the solvent, preferably at about 140°C; to give the carbodiimide diisocyanate compound (3):

O=C=N-Li-(N=C=N-Li)_n-N=C=O (3), in which formula (3) Li and n are as defined previously. Benzoyl halogen such as benzoyl chloride may be added to deactivate the catalyst.

To obtain “symmetrical” (poly)carbodiimides, during the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq.) of nucleophilic reagent Ri-Xi-H and then 0.5 eq. of reagent H-E-H with Ri, Xi and E as defined previously, to give the “symmetrical” compound (4) according to the invention:

[Ri-Xi-C(O)-NH-Li-(N=C=N-Li)_n-NH-C(O)]₂-E (4), in which formula (4) Ri, Xi, Li, n and E are as defined previously. According to one variant to obtain compound (4) from (3), it is possible first to add 0.5 eq. of reagent H-E-H and then 1 eq. of reagent Ri-Xi-H.

To obtain “dissymmetrical” (poly)carbodiimides, during the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq.) of nucleophilic reagent Ri-Xi-H and then 1 eq. of reagent H-E-H with Ri, Xi and E as defined previously, to give compound (5):

Ri-Xi-C(O)-NH-Li-(N=C=N-Li)_n-NH-C(O)-E-H (5), in which formula (5) Ri, Xi, Li, n and E are as defined previously.

According to one variant to obtain compound (5) from (3), it is possible first to add 1 eq. of reagent Ri-Xi-H and then 0.5 eq. of reagent H-E-H.

During a third step, compound (5) reacts with 1 eq. of compound (6)

R₂-X2-C(O)-NH-LI-(N=C=N-LI)_Z-N=C=O (6), said compound (6) is prepared beforehand from compound (3’):

O=C=N-Li-(N=C=N-Li)_z-N=C=O (3’), in which formula (3’) Li and z are as defined previously, which reacts with 1 eq. of nucleophilic reagent R₂-X₂-H with Li, R₂, X₂ and z as defined previously, to give the dissymmetrical compound (7):

Ri-Xi-C(O)-NH-Li-(N=C=N-Li)n-NH-C(O)-E-C(O)-NH-Li-(N=C=N-Li)_z-NH- C(O)-X₂-R₂ (7), in which formula (7) Ri, Xi, Li, R₂, X₂, n, z and E are as defined previously.

It is also possible to react 1 molar equivalent of compound O=C=N-Li- (N=C=N-Li)_z-N=C=O (3’) with 1/w molar equivalent of H-E-H, followed by 1 eq. of nucleophilic reagent R₂-X₂-H to give compound (8):

H-[E-C(O)-NH-LI-(N=C=N-LI)Z]W-NH-C(O)-X₂-R₂ (8), in which formula (8) Li, R₂, X₂, z and E are as defined previously, and w is an integer between 1 and 3; more preferentially, w = 1.

This last compound (8) can then react with 1 eq. of compound (4’):

Ri-Xi-C(O)-NH-Li-(N=C=N-Li)n-N=C=O (4’), (said compound (4’) being able to be synthesized by reaction of 0.5 eq. of nucleophilic reagent Ri-Xi-H with 1 equivalent of compound (3)), to give the (poly)carbodiimide (9) of the invention: Ri-Xi-C(O)-NH-Li-(N=C=N-Li)_n-NH-C(O)-[E-C(O)-NH-Li-(N=C=N- Li)_z]_w-NH C(O)-X₂-R₂ (9), in which formula (9) Li, Ri, Xi, R₂, X₂, n, z, w and E are as defined previously.

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

Example 1: Process for synthesizing the (poly)carbodiimide compound

50 g of 4,4’ -di cyclohexylmethane diisocyanate and 0.5 g of 4, 5 -dihydro-3 - methyl- 1 -phenyl- IH-phosphole 1 -oxide were placed with stirring in a 500 mL threenecked round-bottomed flask equipped with a thermometer, a stirrer and a reflux tube.

The reaction medium was heated at 140°C under nitrogen for 4 hours, the reaction being monitored by infrared spectroscopy by means of the absorption of the isocyanate functions between 2200 and 2300 cm'¹, and then cooled to 120°C.

A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4- butanediol are introduced with stirring into the reaction medium. The temperature of 120°C is maintained until the isocyanate functions have totally disappeared, monitored by infrared spectroscopy at 2200-2300 cm'¹, and is then cooled to room temperature.

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

Example 2

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

[Table 1]

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

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

[Table 2]

(1) synthesized according to the synthetic process described in Example 1 (containing 40% active material in water),

(2) sold by the company SEPPIC under the name Sepinov EMTIO (containing 90% active material).

[Table 3]

(3) acrylic polymer sold by the company Daito Kasei Kogyo under the trade name Daitosol 3000SLPN-PE1 (aqueous dispersion containing 30% active material),

(4) sold by the company Dow Corning under the name Dow Coming HMW 2220 Nonionic Emulsion (divinyldimethicone/dimethicone block copolymer in aqueous emulsion) (containing 60% active material),

(5) associative polymer sold by the company Rohm & Haas under the trade name Aculyn 22® (oxyalkylenated methacrylic acid/ethyl acrylate/stearyl methacrylate terpolymer containing 30% active material).

Composition A was then mixed with composition B in a 50/50 mass ratio to obtain a composition C.

Protocol

Two different processes were employed.

According to processes 1 and 2, the compositions T1 or T2, respectively, were first applied to sensitized locks of hair keratin fibres referred to hereinafter as SA20. Each of these compositions was applied to locks of hair keratin fibres, at a rate of 0.8 g of composition per gram of lock. The locks of hair keratin fibres were then rinsed.

Composition C was then applied to the locks which had been previously treated with composition T1 or composition T2, at a rate of 0.8 g of composition per gram of lock. The locks of hair keratin fibres were subsequently combed out and dried with a hairdryer.

The process employing composition T1 and then composition C is a comparative process, since composition T1 does not have a basic pH. It is referred to hereinafter as process Pl . The process employing composition T2 and then composition C is a process according to the invention. Hereinafter it is referred to as process P2.

The processes applied are collated in Table 4 below: [Table 4]

The locks of hair keratin fibres treated via processes Pl to P2 were then subjected to a test consisting of several repeated shampoo washes in order to evaluate the resistance (persistence) of the colouring obtained with respect to shampoo washing, according to the shampoo washing protocol described below.

Shampoo washing protocol

The locks of dyed hair keratin fibres are combed, moistened with water at 35°C and then passed between the fingers five times for 5 seconds. The locks of hair keratin fibres are then squeezed dry between two fingers.

A standard shampoo (Garnier Ultra Doux) is applied uniformly to the dyed locks, in a proportion of 0.4g of standard shampoo per gram of locks, the locks of hair keratin fibres being massaged gently along the length (6 passes) for 15 seconds, from the root to the end.

The locks of hair keratin fibres are then placed on a watch glass and left to stand for 1 minute.

Next, the locks of hair keratin fibres are rinsed with water while passing the locks between the fingers (15 passes). The locks of hair keratin fibres are then squeezed dry between two fingers before the next shampoo wash.

Once the tests of several shampoo washes have been performed, the locks of hair keratin fibres are combed and dried with a hairdryer.

Results

The persistence of the colour of the locks was evaluated in the CIE L*a*b* system, using a Minolta CM3600A Spectrophotometer colorimeter (illuminant D65, angle 10°, specular component included).

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

The persistence of the colouring is evaluated by the colour difference AE between the dyed locks before shampoo washing, then after having undergone five shampoo washes according to the protocol described above. The lower the AE value, the more persistent the colour with respect to shampoo washing.

The AE value is calculated according to the following equation:

In this equation, L*, a* and b* represent the values measured after dyeing the hair keratin fibres and after performing shampoo washes, and Lo*, ao* and bo* represent the values measured after dyeing the hair keratin fibres but before shampoo washing.

The results are collated in Table 5 below.

[Table 5]

The locks of hair keratin fibres treated by means of the process according to the invention and washed with five shampoo washes have a significantly lower AE value than that of the locks of hair keratin fibres treated by means of the comparative process.

Thus, the coloured coating that is obtained by means of the process according to the invention shows improved resistance to shampoo washing.

Example 3

Tests were carried out using shampoos having different pH values according to the protocol above on locks of natural hair keratin fibres (BN) and on bleached locks (SA80).

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

These results show that the process of the invention enables an improvement in the persistence of the color on the hair keratin fibres. This improvement is obtained on natural hair keratin fibres, and it is substantially superior on damaged hair keratin fibres.

Example 4

Compositions T2, A and B as described above in example 2 were used.

In addition, composition D as described in Table 7 below was prepared: the amounts are expressed as g of starting material as obtained/100 g, unless otherwise mentioned (am below means active matter).

[Table 7]

(6) sold by the company Stahl under the name PERMUTEX® XR-13-554.

Composition A was then mixed with composition B in a 50/50 mass ratio to obtain a composition C. Composition D was then mixed with composition B in a 50/50 mass ratio to obtain a composition E. Protocol

Two different processes were employed.

One of the two processes is the process P2 as described above.

According to process 3, the composition T2 was first applied to sensitized locks of hair keratin fibres referred to hereinafter as SA20. This composition was applied to locks of hair keratin fibres, at a rate of 0.8 g of composition per gram of lock. The locks of hair keratin fibres were then rinsed.

Composition E was then applied to the locks at a rate of 0.8 g of composition per gram of lock. The locks of hair keratin fibres were subsequently combed out and dried with a hairdryer.

The process employing composition T2 and then composition E is a comparative process, since composition E does not comprise a (poly)carbodiimide compound chosen from the compounds of formula (II). It is referred to hereinafter as process P3.

The processes applied are collated in Table 8 below:

[Table 8]

The locks of hair keratin fibres treated via processes P2 and P3 were then subjected to a test consisting of several repeated shampoo washes in order to evaluate the resistance (persistence) of the colouring obtained with respect to shampoo washing, according to the shampoo washing protocol described above in example 2.

Results

The persistence of the colour of the locks was evaluated in the CIE L*a*b* system, as described above in example 2.

The persistence of the colouring is evaluated by the colour difference AE as also described above.

The results are collated in Table 9 below. [Table 9]

The locks of hair keratin fibres treated by means of the process according to the invention and washed with three shampoo washes have a significantly lower AE value than that of the locks of hair keratin fibres treated by means of the comparative process.

Thus, the coloured coating that is obtained by means of the process according to the invention shows improved resistance to shampoo washing

Claims

1. Process for dyeing hair keratin fibres comprising:

(II), in which:

- E independently represents a group chosen from:

2. Process 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. Process according to Claim 1 or 2, characterized in that composition T comprises at least one alkaline agent, preferably chosen from alkali metal or alkaline- earth metal hydroxides, ammonium hydroxides, alkanolamines and mixtures thereof, preferably sodium hydroxide.

4. Process according to any one of the preceding claims, characterized in that the anionic surfactant(s) of composition T are chosen from anionic surfactants of sulfate type, preferably from (Cio-C22)alkyl sulfates, (Cio-C22)alkyl ether sulfates and mixtures thereof, preferably from sodium (Cio-C22)alkyl ether sulfates and mixtures thereof.

5. Process according to any one of the preceding claims, characterized in that the amphoteric or zwitterionic surfactant(s) of composition T are chosen from (Cs- C2o)alkyl betaines, (Cs-C2o)alkyl sulfobetaines, (C8-C2o)alkylamido(C3-C8)alkyl betaines, (C8-C2o)alkylamido(C6-C8)alkyl sulfobetaines and mixtures thereof, more preferably chosen from alkyl(C8-C2o) betaines, (C8-C2o)alkylamido(C3-C8)alkyl betaines and mixtures thereof, more preferably still from (C8-C2o)alkylamido(C3- C8)alkyl betaines and mixtures thereof.

6. Process according to any one of Claims 1 to 5, wherein composition T comprises an amount of surfactant(s), chosen from anionic surfactants, amphoteric or zwitterionic surfactants and mixtures thereof, ranging from 1% to 50% by weight, preferably from 5% to 40% by weight, more preferably from 10% to 30% by weight relative to the total weight of composition T.

7. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) in which:

- Xi and X2 independently represent an oxygen atom;

- Ri and R2 are independently chosen from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed, and mixtures thereof;

- E independently represents a group chosen from:

8. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) in which:

- Xi and X2 independently represent an oxygen atom;

- Li is a C3-C15 cycloalkylene radical; - E independently represents a group chosen from:

9. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) in which:

- Xi and X2 independently represent an oxygen atom;

- Ri and R2 independently represent the compound of formula (VI) below:

10. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (II) in which:

- Xi and X2 independently represent an oxygen atom;

- Ri and R2 independently represent the compound of formula (VI) below:

- E represents a group -O-R3-O- in which R3 represents a linear or branched Ci-Cis alkylene radical such as methylene, propylene, butylene or ethylene, optionally interrupted with one or more heteroatoms.

11. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) are chosen from the compounds of formula (XII) below:

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

13. Process according to any one of the preceding claims, characterized in that the polymer(s) comprising at least one reactive group chosen from carboxylic acids is an acrylic polymer, preferably an acrylic polymer comprising one or more units derived from the following monomers: a) (meth)acrylic acid; and b) Ci to C30, more preferentially Ci to C20, better still Ci to C10, and even more particularly Ci to C4, alkyl (meth)acrylate.

14. Process according to any one of the preceding claims, characterized in that the polymer(s) comprising at least one reactive group chosen from carboxylic acids, preferably acrylic polymers, are 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. Process according to any one of the preceding claims, characterized in that the total content of colouring agent(s) ranges from 0.001% to 20% by weight and preferably from 0.005% to 15% by weight relative to the total weight of composition C; preferably the colouring agent(s) are chosen from pigments.

16. Process according to any one of the preceding claims, characterized in that step (b) consists in extemporaneously mixing, at the time of use, at least two compositions A and B to obtain a composition C and in applying composition C to the hair keratin fibres, with: - composition A comprising at least one (poly)carbodiimide compound as defined in any one of Claims 1 and 7 to 11;

- composition B comprising at least one polymer comprising at least one reactive group chosen from carboxylic acids, as defined in Claim 1 or 13, and at least one colouring agent as defined in Claim 1.

17. Device for dyeing hair keratin fibres, comprising several compartments containing:

- a first compartment comprising composition T as defined in any one of Claims 1 to 6;

- a second compartment comprising composition A comprising a (poly)carbodiimide compound as defined in any one of Claims 1 and 7 to 11;

- a third compartment comprising composition B comprising at least one pigment as defined in Claim 1, and at least one polymer comprising at least one reactive group chosen from carboxylic acids, as defined in Claim 1 or 13.