FR3157155A1 - Hair coloring process comprising a step of washing the hair with a composition at basic pH and comprising at least one anionic and/or amphoteric or zwitterionic surfactant - Google Patents

Abstract

Title: Hair coloring method comprising a step of washing the hair with a composition at a basic pH and comprising at least one anionic and/or amphoteric or zwitterionic surfactant, followed by applying to the hair a hair coloring composition comprising a particular (poly)carbodiimide compound, a specific polymer, and a coloring agent. The present invention relates to a hair coloring method comprising: (a) a step of washing the hair with a composition T comprising at least one surfactant selected from anionic surfactants, amphoteric or zwitterionic surfactants, and mixtures thereof, and having a basic pH; then (b) applying to the hair a coloring composition C comprising: - at least one (poly)carbodiimide compound of formula (II); - at least one polymer comprising at least one reactive group selected from carboxylic acids; and - at least one coloring agent selected from pigments, direct dyes, and mixtures thereof.

Description

A method of coloring hair comprising a step of washing the hair with a composition at basic pH and comprising at least one anionic and/or amphoteric or zwitterionic surfactant, followed by the application to the hair of a hair coloring composition comprising a particular (poly)carbodiimide compound, a specific polymer and a coloring agent.

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

In the field of coloring hair keratin fibers, it is already known to color hair keratin fibers using different techniques using direct dyes or pigments for non-permanent colorings or dye precursors for permanent colorings.

There are basically three types of hair coloring process:

(a) so-called permanent coloring, the function of which is to bring about a significant change in the natural color and which uses oxidation dyes which penetrate the hair fiber and form the dye by a process of oxidative condensation;

b) non-permanent, semi-permanent or direct coloring, which does not involve the oxidative condensation process and is resistant to 4 or 5 shampoos; consists of dyeing keratin fibers with dye compositions containing direct dyes;

c) temporary coloring which results in a change in the natural color of the hair that lasts from one shampoo to the next and which serves to enhance or correct a shade already obtained. It can also be likened to a “makeup” process.

Another coloring method is to use pigments. Indeed, the use of pigments on the surface of keratin fibers generally allows for visible coloring on dark hair since the surface pigment masks the natural color of the fiber. However, the colors obtained by this coloring method have the disadvantage of having low resistance to shampoos as well as external agents such as sebum, perspiration, brushing and/or friction. The colors obtained can also be too selective, that is to say that the color difference is too great along the same keratin fiber which is differently sensitized between its tip and its root.

There is therefore a need for a hair coloring process which has the advantage of obtaining a uniform colored coating on the hair, while forming a coating which is resistant to shampoos and various attacks that the hair may be subjected to, such as brushing and/or rubbing.

Thus, the aim of the present invention is to develop a hair coloring process which has the advantage of obtaining a homogeneous and smooth colored coating on the hair, while forming a coating improving the remanence. to shampoos and various aggressions that the hair can undergo such as brushing and/or friction.

The present invention therefore relates to a hair coloring process comprising:

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

(b) applying to the hair a hair coloring composition C comprising:

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

in which:

- X ₁ and X ₂ represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

- R ₁ and R ₂ independently represent a hydrocarbon radical optionally interrupted by one or more heteroatom(s);

- 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;

- L ₁ independently represents a divalent C ₁ -C ₁₈ aliphatic hydrocarbon radical, a C ₃ -C ₁₅ cycloalkylene radical, a C ₃ -C ₁₂ heterocycloalkylene group, or a C ₆ -C ₁₄ arylene group, and mixtures thereof;

- E independently represents a group chosen from:

-OR ₃ -O-; -SR ₄ -S-; -R ₅ -N(R ₆ )-R ₄ -N(R ₆ )-R ₅ -,

in which R ₃ and R ₄ independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s);

- R ₅ independently represents a covalent bond or a divalent saturated hydrocarbon radical, optionally interrupted by one or more heteroatom(s);

- R ₆ independently represents a hydrogen atom, or a hydrocarbon radical optionally interrupted by one or more heteroatom(s);

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

- at least one coloring agent chosen from pigments, direct dyes and their mixtures.

Thanks to the hair coloring process according to the invention, colored coatings are obtained on the hair, making it possible to obtain a visible color on all types of hair, and lasting after shampooing. Such a coating can be resistant to external aggressions that the hair may be subjected to, such as blow-drying and perspiration. The coloring process according to the invention makes it possible, in particular, to obtain a homogeneous coating.

The expression " at least one " means one or more.

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

The invention is not limited to the examples illustrated. The characteristics of the different examples may in particular be combined within variants not illustrated.

For the purposes of the present invention and unless otherwise indicated,

- an “ alkyl ” radical designates a saturated linear or branched 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 NH ₂ group;

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

- an “ alkylene ” radical denotes a divalent saturated _C2 - _C4 hydrocarbon group, linear or branched, such as methylene, ethylene, or propylene;

- a “ cycloalkyl ” or “ alicycloalkyl ” radical denotes a mono- or polycyclic, preferably monocyclic, bicyclic or tricyclic, saturated cyclic hydrocarbon 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 by one or more (C ₁ -C ₄ )alkyl groups such as methyl, preferably the cycloalkyl radical is then an isobornyl group,

- a “ cycloalkylene ” radical denotes a divalent cycloalkyl group with “ cycloalkyl ” as defined previously, preferably C ₃ -C ₁₂ ;

- an “ aryl ” radical is an unsaturated and aromatic hydrocarbon cyclic radical, comprising from 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms, mono/bi/or tri/cyclic, fused or not, preferably the aryl group comprises 1 cycle with 6 carbon atoms such as phenyl, naphthlyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical may be substituted by one or more (C ₁ -C ₄ )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 above, preferably arylene represents phenylene;

- a “ heterocyclic ” radical denotes a mono- or polycyclic, saturated or unsaturated, non-aromatic or aromatic hydrocarbon radical, comprising one or more heteroatoms, preferably from 1 to 5 atoms chosen from O, S or N, comprising from 3 to 20 links, preferably between 5 and 10 links, such as imidazolyl, pyrrolyl and furanyl;

- a “ heterocycloalkylene ” radical is a divalent heterocyclic group with “ heterocyclic ” as defined above;

- 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 RC(O)-O- with R an alkyl group as defined previously;

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

Unless otherwise indicated, when compounds are mentioned in this application, their optical isomers, their geometric isomers, their tautomers, their salts, alone or in mixture, are also meant.

The term "keratin (hair) fibers" means hair. In other words, the expressions "keratin (hair) fibers" and "hair" are equivalent in the remainder of the description.

For the purposes of the present invention, the term "hair" means the hair of the head. This term does not correspond to body hair, eyebrows, or eyelashes.

Washing step with a T composition

As indicated previously, the process according to the invention firstly 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 their mixtures.

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

The pH of composition T can be adjusted to a basic pH thanks to the presence of a basic pH adjusting agent.

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

According to a particular embodiment, the compositions T according to the invention comprise one or more alkaline agents.

The alkaline agents may be chosen from conventionally used agents, in particular chosen from alkali 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, triethanolamine, preferably sodium hydroxide.

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

Advantageously, the water content, when present, ranges from 40 to 95% by weight, preferably from 50 to 90% by weight, more preferably from 60 to 85% by weight, even more preferably 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, the composition T comprises at least one surfactant chosen from anionic surfactants, amphoteric or zwitterionic surfactants and their mixtures.

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% relative to the total weight of the composition T.

Anionic surfactants

Anionic surfactants can be chosen from sulfate, sulfonate and/or carboxylic (or carboxylate) surfactants. A mixture of these surfactants can of course be used.

It is understood in this 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 anionic sulfonate surfactants comprise at least one sulfonate function (-SO ₃ H or -SO ₃ ^- ), and may optionally further comprise one or more sulfate functions, but do not comprise a carboxylate function; and

- anionic sulfate surfactants comprise at least one sulfate function but do not comprise a carboxylate or sulfonate function.

The anionic carboxylate surfactants that can be used therefore comprise at least one carboxylic or carboxylate function (-COOH or -COO ^- ).

They can be chosen from the following compounds: fatty acids, acylglycinates, acyllactylates, acylsarcosinates, acylglutamates; alkyl-D-galactoside-uronic acids, alkyl ether carboxylic acids, alkyl (C ₆ -C ₃₀ aryl) ether carboxylic acids, alkyl amidoether carboxylic acids; as well as the salts of these compounds; and their mixtures;
the alkyl and/or acyl groups of these compounds comprising from 6 to 30 carbon atoms, in particular from 12 to 28, even better from 14 to 24, or even from 16 to 22 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group;
these compounds may be polyoxyalkylenated, in particular polyoxyethylenated and then preferably comprising from 1 to 50 ethylene oxide units, better still from 2 to 10 ethylene oxide units.

Also useful are C ₆ -C ₂₄ alkyl monoesters of polyglycoside polycarboxylic acids such as C ₆ -C ₂₄ alkyl polyglycoside citrates, C ₆ -C ₂₄ alkyl polyglycoside tartrates and C ₆ -C ₂₄ alkyl polyglycoside sulfosuccinates, and their salts.

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

- fatty acids;

- acylglutamates, particularly _C6 - _C24 , or even _C12 - _C20 , such as stearoylglutamates, and in particular disodium stearoylglutamate;

- acylsarcosinates, particularly _C6 - _C24 , or even _C12 - _C20 , such as palmitoylsarcosinates, and in particular sodium palmitoylsarcosinate;

- acyllactylates, particularly C ₁₂ -C ₂₈ , or even C ₁₄ -C ₂₄ , such as behenoyllactylates, and in particular sodium behenoyllactylate;

- _C6 - _C24 acylglycinates, especially _C12 - _C20 ;
- alkyl(C ₆ -C ₂₄ )ethercarboxylates, and in particular alkyl(C ₁₂ -C ₂₀ )ethercarboxylates;

- polyoxyalkylenated alkyl(C ₆ -C ₂₄ ) (amido) ether carboxylic acids, in particular those containing from 2 to 50 ethylene oxide groups;

in particular in the form of salts of alkali or alkaline earth metals, ammonium, or amino alcohol.

Among the above carboxylic surfactants, mention may be made in particular of fatty acid type surfactants, in particular C ₆ -C ₃₀ .

Fatty acids include lauric, palmitic, myristic, stearic, oleic, and behenic acids.

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

Among the above carboxylic surfactants, sarcosinate-type surfactants may be particularly mentioned. Among the alkyl(C ₆ -C ₃₀ )sarcosinates, palmitoylsarcosinates, stearoylsarcosinates, myristoylsarcosinates, lauroylsarcosinates, and cocoylsarcosinates may be mentioned, 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 their salts, in particular those comprising from 2 to 50 alkylene oxide groups, in particular ethylene oxide, such as the compounds offered by the company KAO under the names AKYPO.

The anionic sulfonate surfactants that can be used contain at least one sulfonate function (-SO ₃ H or -SO ₃ ^- ).

They can be chosen from the following compounds: alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, alpha-olefin-sulfonates, paraffin-sulfonates, alkylsulfosuccinates, alkylethersulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, N-acyltaurates, acylisethionates; alkylsulfolaurates; as well as the salts of these compounds;

the alkyl groups of these compounds comprising from 6 to 30 carbon atoms, in particular from 12 to 28, even better from 14 to 24, or even from 16 to 22, carbon atoms; the aryl group preferably denoting a phenyl or benzyl group;

these compounds may be polyoxyalkylenated, in particular polyoxyethylenated and then preferably comprising from 1 to 50 ethylene oxide units, better still from 2 to 10 ethylene oxide units.

Preferably, the anionic sulfonate surfactants are chosen from, alone or in a mixture:

- _C6 - _C24 alkylsulfosuccinates, especially _C12 - _C20 alkylsulfosuccinates, especially laurylsulfosuccinates.

- _C6 - _C24 alkyl ethersulfosuccinates, in particular _C12 - _C20 ;

- _C6 - _C24 N-acyltaurates, in particular _C12 - _C20,

- (C ₆ -C ₂₄ )acylisethionates, preferably (C ₁₂ -C ₁₈ )acylisethionates,
in particular in the form of salts of alkali or alkaline earth metals, ammonium, or amino alcohol.

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

More preferably, the anionic surfactant(s) of sulfonate type are chosen from acylisethionates, as well as their salts and their mixtures.

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 the magnesium salt.

Examples of amino alcohol salts include mono-, di- and triethanolamine salts, mono-, di- or tri-isopropanolamine salts, 2-amino 2-methyl 1-propanol, 2-amino 2-methyl 1,3-propanediol and tris(hydroxymethyl)amino methane salts.

Preferably, salts of alkali or alkaline earth metals are used, and in particular sodium or magnesium salts.

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

- _C6 - _C30 fatty acids, particularly _C8 - _C24 ;

- C ₆ -C ₂₄ alkyl sulfates, preferably C ₁₀ -C _{22 alkyl} sulfates, in particular C ₁₂ -C _{20 alkyl sulfates} ;

- C ₆ -C ₂₄ alkyl ether sulfates, preferably C ₁₀ -C ₂₂ , in particular C ₁₂ -C ₂₀ ; preferably comprising from 1 to 20 ethylene oxide units;

- _C6 - _C24 alkylsulfosuccinates, in particular _C12 - _C20 , in particular laurylsulfosuccinates;

- _C6 - _C24 alkyl ethersulfosuccinates, in particular _C12 - _C20 ;

- _C6 - _C24 N-acyltaurates, especially _C12 - _C20;

- (C ₆ -C ₂₄ )acylisethionates, preferably (C ₁₂ -C ₁₈ )acylisethionates;

- _C6 - _C24 acylsarcosinates, in particular _C12 - _C20 ; in particular palmitoylsarcosinates, stearoylsarcosinates, myristoylsarcosinates;

- alkyl(C ₆ -C ₂₄ )ethercarboxylates, preferably alkyl(C ₁₂ -C ₂₀ )ethercarboxylates;

- polyoxyalkylenated alkyl(C ₆ -C ₂₄ ) (amido) ethercarboxylic acids and their salts, in particular those containing from 2 to 50 alkylene oxide groups, in particular ethylene;

- _C6 - _C24 acylglutamates, especially _C12 - _C20 ;

- _C6 - _C24 acylglycinates, especially _C12 - _C20 ;

- as well as their salts, in particular their alkali or alkaline-earth metal or zinc, ammonium or amino alcohol salts;

- and their mixtures.

Preferably, the anionic surfactant(s) of composition T are chosen from sulfate-type anionic surfactants, preferably from alkyl(C ₁₀ -C ₂₂ )sulfates, alkyl(C ₁₀ -C ₂₂ )ether sulfates and mixtures thereof, more preferably from sodium alkyl(C ₁₀ -C ₂₂ )ether sulfates and mixtures thereof.

Amphoteric or zwitterionic surfactants

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

In particular, the amphoteric or zwitterionic surfactant(s), preferably non-silicone, used in the composition T according to the present invention, may in particular be derivatives of secondary or tertiary aliphatic amines, optionally quaternized, in which the aliphatic group is a linear or branched chain comprising 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.

In particular, mention may be made of alkyl(C ₈ -C ₂₀ )betaines, alkyl(C ₈ -C ₂₀ )sulfobetaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₁ -C ₆ )betaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₁ -C ₆ )sulfobetaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₆ -C ₈ )sulfobetaines and mixtures thereof.

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

For example, we can cite cocoamphodiacetate marketed by the company RHODIA under the trade name MIRANOL ^® C2M concentrate.

We can cite the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and marketed by the company CHIMEX under the name CHIMEXANE HB.

These compounds can be used alone or in mixtures.

Among the amphoteric or zwitterionic surfactants mentioned above, advantageously used are alkyl(C ₈ -C ₂₀ )betaines, such as cocobetaine, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines, such as cocamidopropylbetaine, alkyl(C ₈ -C ₂₀ )amphoacetates, alkyl(C ₈ -C ₂₀ )amphodiacetates and mixtures thereof; and preferably alkyl(C ₈ -C ₂₀ )betaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines and mixtures thereof.

Advantageously, the amphoteric or zwitterionic surfactant(s) of composition T are chosen from alkyl(C ₈ -C ₂₀ )betaines, alkyl(C ₈ -C ₂₀ )sulfobetaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₆ -C ₈ )sulfobetaines, and mixtures thereof, more preferably chosen from alkyl(C ₈ -C ₂₀ )betaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines and mixtures thereof, even more preferably from alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines and mixtures thereof.

According to one embodiment, the composition T comprises an amount of surfactant(s) chosen from anionic surfactants, amphoteric or zwitterionic surfactants and their mixtures 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 the composition T.

Preferably, the surfactant(s) are chosen from:

- alkyl sulfates, in particular C ₈ to C ₂₆ , and preferably C ₁₀ to C ₂₂ ;

- alkyl ether sulfates, in particular C ₈ to C ₂₆ , and preferably C ₁₀ to C ₂₂ , preferably comprising from 2 to 10 ethylene oxide units;

• les alkyl(C₈-C₂₀)bétaïnes, les alkyl(C₈-C₂₀)amidoalkyl(C₃-C₈)bétaïnes et leurs mélanges, mieux parmi les alkyl(C₈-C₂₀)amidoalkyl(C₃-C₈)bétaïnes et leurs mélanges ;

in particular in the form of alkali or alkaline-earth metal salts, ammonium salts, or amino alcohol salts,

• alkyl(C ₈ -C ₂₀ )betaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines and mixtures thereof, better among alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines and mixtures thereof;

and their mixtures.

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

Additives

The composition T used in the coloring process according to the invention may also contain any adjuvant or additive usually used.

Among the additives that may be used, we can cite reducing agents, thickening agents, softeners, moisturizing agents, UV filters, solubilizers, perfumes, vitamins, polymers, preservatives, fatty substances and their mixtures.

(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 distinct (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 preferably at least three carbodiimide groups; in particular, the number of carbodiimide groups does not exceed 200, preferably 150, more preferably 100.

The term " carbodiimide group " means a divalent linear triatomic moiety of general formula - (N=C=N) -.

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

in which:

- X ₁ and X ₂ represent, independently, an oxygen atom O, a sulfur atom S or an NH group;

- R ₁ and R ₂ independently represent a hydrocarbon radical optionally interrupted by one or more heteroatom(s);

- 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;

- L ₁ independently represents a divalent C ₁ -C ₁₈ aliphatic hydrocarbon radical, a C ₃ -C ₁₅ cycloalkylene radical, a C ₃ -C ₁₂ heterocycloalkylene group, or a C ₆ -C ₁₄ arylene group, and mixtures thereof;

- E independently represents a group chosen from:

- -OR ₃ -O-; -SR ₄ -S-; -R ₅ -N(R ₆ )-R ₄ -N(R ₆ )-R ₅ -,

in which R ₃ and R ₄ independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s);

- R ₅ independently represents a covalent bond or a divalent saturated hydrocarbon radical, optionally interrupted by one or more heteroatom(s);

- R ₆ independently represents a hydrogen atom, or a hydrocarbon radical optionally interrupted by one or more heteroatom(s).

The term “ hydrocarbon radical ” means a saturated or unsaturated, linear or branched radical having from 1 to 300 carbon atoms, preferably from 1 to 250 carbon atoms, more preferably from 1 to 200 carbon atoms. Preferably, the hydrocarbon radical is a linear and saturated radical.

The hydrocarbon radical may comprise one or more cyclic groups.

The hydrocarbon radical may be interrupted by one or more heteroatom(s), in particular chosen from O, S or N and/or substituted by one or more cation(s), anion(s), or zwitterion(s) or cationic group(s) such as ammonium, anionic group(s) such as carboxylate, or zwitterionic group(s), and/or comprising a metal ion which may be incorporated in the form of a salt.

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

Preferably, X ₁ and X ₂ independently represent an oxygen atom.

Preferably, R ₁ and R ₂ are independently selected from dialkylamino alcohols, hydroxycarboxylic acid alkyl esters and (poly)alkylene glycol monoalkyl ethers, in which a hydroxy group has been removed, and mixtures thereof.

According to a preferred embodiment, R ₁ and R ₂ are independently chosen from the following groups (i) to (iv):

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

R ₇ -OC(O)-C(R ₈ )(H)- (III),

wherein R ₇ represents a C ₁ -C ₃ alkyl group, and R ₈ represents a hydrogen atom or a C ₁ -C ₃ alkyl group, preferably R ₇ is methyl and R ₈ is a hydrogen atom or methyl.

(ii) the compound of formula (IV) following:

R ₉ -[O-CH ₂ -C(H)(R ₁₀ )] _p - (IV),

wherein R ₉ represents a C ₁ -C ₄ alkyl group, R ₁₀ represents a hydrogen atom or a C ₁ -C ₄ alkyl group and p denotes an integer ranging from 1 to 3; preferably, R ₉ is methyl, ethyl or butyl and R ₁₀ is a hydrogen atom or methyl and p is 1.

(iii) the compound of formula (V) following:

(R ₁₁ ) ₂ N-CH ₂ -C(H)(R ₁₂ )- (V),

wherein R ₁₁ represents a C ₁ -C ₄ alkyl group and R ₁₂ represents a hydrogen atom or a C ₁ -C ₄ alkyl group; preferably R ₁₁ is methyl, ethyl or butyl and R ₁₂ is a hydrogen atom or methyl.

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

R ₁₃ -[O-CH ₂ -C(H)(R ₁₄ )] _q - (VI),

wherein R ₁₃ represents a C ₁ -C ₄ alkyl group or a phenyl, R ₁₄ represents a hydrogen atom or a C ₁ -C ₄ alkyl group and q denotes an integer ranging from 4 to 30; preferably R ₁₃ is a methyl, ethyl or butyl and R ₁₄ is a hydrogen atom or a methyl.

Preferably, R ₁ and R ₂ independently represent a compound of formula (VI) in which R ₁₃ represents a C ₁ -C ₄ alkyl group or a phenyl, preferably a C ₁ -C ₄ alkyl group, more preferably a methyl, R ₁₄ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.

According to an alternative embodiment, R ₁ and R ₂ are different and one of the radicals R ₁ or R ₂ represents a compound of formula (IV) as described above and the other radical R ₁ or R ₂ represents a compound of formula (VI) as described above.

Preferably, in formula (IV), R ₉ is methyl, ethyl or butyl and R ₁₀ is hydrogen or methyl and p is 1.

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

According to another alternative embodiment, R ₁ and R ₂ are identical and represent a compound of formula (VI) in which R ₁₃ represents a C ₁ -C ₄ alkyl group or a phenyl, preferably a C ₁ -C ₄ alkyl group, more preferably a methyl, R ₁₄ represents a hydrogen atom or a C ₁ -C ₄ 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 preferably from 2 to 20.

Preferably, z denotes an integer ranging from 1 to 20, more preferably 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, L ₁ is chosen from a divalent C ₁ -C ₁₈ aliphatic hydrocarbon radical such as methylene, ethylene, and propylene, a C ₃ -C ₁₅ cycloalkylene radical such as cyclopentylene, cycloheptylene, and cyclohexylene, a C ₃ -C ₁₂ heterocycloalkylene group such as imidazolene, pyrrolene and furanylene, or a C ₆ -C ₁₄ arylene group such as phenylene, and mixtures thereof.

For example, L ₁ may be selected 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-isocyanateoctyl)-1,3-dioctylcyclobutane, 4,4'-dicylclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate and phenylene diisocyanate and mixtures thereof.

Preferably, L ₁ is chosen from a C ₃ -C ₁₅ cycloalkylene radical, or a C ₆ -C ₁₄ arylene group and mixtures thereof, such as the compounds of formula (VII) below:
.

Preferably, L1 is 4,4-dicyclohexylene methane corresponding to the following formula (VIII):
(VIII).

According to another embodiment, when L1 is a _C6 - _C14 arylene group, _L1 is not the m-tetramethylxylylene radical represented by the following formula (IX):
(IX).

As previously indicated, E independently represents a group chosen from:

- -OR ₃ -O-; -SR ₄ -S-; -R ₅ -N(R ₆ )-R ₄ -N(R ₆ )-R ₅ -;

in which R ₃ and R ₄ independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s);

- R ₅ independently represents a covalent bond or a divalent saturated hydrocarbon radical, optionally interrupted by one or more heteroatom(s); and

- R ₆ independently represents a hydrogen atom, or a hydrocarbon radical optionally interrupted by one or more heteroatom(s).

Preferably, R ₃ and R ₄ are independently chosen from a C ₆ -C ₁₄ arylene radical such as phenylene, a C ₃ -C ₁₂ cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C ₁ -C ₁₈ alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatom(s) and mixtures thereof.

More preferably, R ₃ and R ₄ are independently chosen from a linear or branched C ₁ -C ₁₈ alkylene radical such as methylene, butylene, propylene, ethylene, optionally interrupted by one or more heteroatom(s).

Preferably, when R ₅ is not a covalent bond, R ₅ is chosen from a C ₆ -C ₁₄ arylene radical such as phenylene, a C ₃ -C ₁₂ cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C ₁ -C ₁₈ alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

Preferably, R ₆ is chosen from a C ₆ -C ₁₄ arylene radical such as phenylene, a C ₃ -C ₁₂ cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C ₁ -C ₁₈ alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

Preferably, E represents a group -OR ₃ -O- in which R ₃ is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

More preferably, E represents a group - -OR ₃ -O- in which R ₃ represents a linear or branched C ₁ -C ₁₈ alkylene radical such as methylene, butylene, propylene, ethylene, optionally interrupted by one or more heteroatom(s).

According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from alpha-methylstyryl-isocyanates of the following formula (X):
(X),

wherein R independently represents an alkyl group having from 1 to 24 carbon atoms, a cycloalkyl group having from 3 to 24 carbon atoms or an aryl group having 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 above.

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

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

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

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

“Alkyl group”, “cycloalkyl group” and “aryl group” are as defined above.

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

- X ₁ and X ₂ independently represent an oxygen atom;

- R ₁ and R ₂ , are independently selected from dialkylaminoalcohols, hydroxycarboxylic acid alkyl esters and (poly)alkylene glycol monoalkyl ethers, in which a hydroxy group has been removed, and mixtures thereof, preferably (poly)alkylene glycol monoalkyl ethers, in which a hydroxy group has been removed, more preferably, the compound of formula (VI) as described above in which R ₁₃ represents a C ₁ -C ₄ alkyl group or a phenyl, preferably a C ₁ -C ₄ alkyl group, more preferably a methyl, R ₁₄ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;

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

- L ₁ , when present, is chosen from a divalent C ₁ -C ₁₈ aliphatic hydrocarbon radical, a C ₃ -C ₁₅ cycloalkylene radical, a C ₃ -C ₁₂ heterocycloalkylene group, or a C ₆ -C ₁₄ arylene group, and mixtures thereof, preferably a C ₃ -C ₁₅ cycloalkylene radical;

- A, when present, is chosen from a divalent C ₁ -C ₁₈ aliphatic hydrocarbon radical, a C ₃ -C ₁₅ cycloalkylene radical, a C ₃ -C ₁₂ heterocycloalkylene group, or a C ₆ -C ₁₄ arylene group, and mixtures thereof, preferably a C ₃ -C ₁₅ cycloalkylene radical;

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

- -OR ₃ -O-; -SR ₄ -S-; -R ₅ -N(R ₆ )-R ₄ -N(R ₆ )-R ₅ -;

in which R ₃ and R ₄ are independently chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

- when R ₅ is not a covalent bond, R ₅ , when present, is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof; and

- R ₆ , when present, is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

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

- X ₁ and X ₂ independently represent an oxygen atom;

- R ₁ and R ₂ are independently chosen from dialkylaminoalcohols, hydroxycarboxylic acid alkyl esters and (poly)alkylene glycol monoalkyl ethers, in which a hydroxy 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;

- L ₁ is chosen from a divalent C ₁ -C ₁₈ aliphatic hydrocarbon radical, a C ₃ -C ₁₅ cycloalkylene radical, a C ₃ -C ₁₂ heterocycloalkylene group, or a C ₆ -C ₁₄ arylene group, and mixtures thereof;

- E independently represents a group chosen from:

- -OR ₃ -O-; -SR ₄ -S-; -R ₅ -N(R ₆ )-R ₄ -N(R ₆ )-R ₅ -;

in which R ₃ and R ₄ are independently chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

- when R ₅ is not a covalent bond, R ₅ is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof; and

- R ₆ is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

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

- X ₁ and X ₂ independently represent an oxygen atom;

- R ₁ and R ₂ , are independently monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed;

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

- L ₁ is a C ₃ -C ₁₅ cycloalkylene radical;

- E independently represents a group chosen from:

- -OR ₃ -O-; -SR ₄ -S-; -R ₅ -N(R ₆ )-R ₄ -N(R ₆ )-R ₅ -;

in which R ₃ and R ₄ are independently chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;

- when R ₅ is not a covalent bond, R ₅ is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof; and

- R ₆ is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

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

- X ₁ and X ₂ independently represent an oxygen atom;

- R ₁ and R ₂ , independently represent the compound of formula (VI) following:

R ₁₃ -[O-CH ₂ -C(H)(R ₁₄ )] _q - (VI),

in which R ₁₃ represents a C ₁ -C ₄ alkyl group or a phenyl, preferably a C ₁ -C ₄ alkyl group, more preferably a methyl, R ₁₄ represents a hydrogen atom or a C ₁ -C ₄ 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 equal to 1;

- L ₁ is a C ₃ -C ₁₅ cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane; and

- E represents a group -OR ₃ -O- in which R ₃ is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

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

- X ₁ and X ₂ independently represent an oxygen atom;

- R ₁ and R ₂ , independently represent the compound of formula (VI) following:

R ₁₃ -[O-CH ₂ -C(H)(R ₁₄ )] _q - (VI)

in which R ₁₃ represents a C ₁ -C ₄ alkyl group or a phenyl, preferably a C ₁ -C ₄ alkyl group, more preferably a methyl, R ₁₄ represents a hydrogen atom or a C ₁ -C ₄ 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 equal to 1;

- L ₁ is a C ₃ -C ₁₅ cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene, 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and

- E represents a group - -OR ₃ -O- in which R ₃ represents a linear or branched C ₁ -C ₁₈ alkylene radical such as methylene, propylene, butylene ethylene, optionally interrupted by one or more heteroatom(s).

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

in which L1 is 4,4-dicyclohexylene methane, n and z denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10, E represents a group -OR ₃ -O- in which R ₃ represents a linear or branched C ₁ -C ₁₈ alkylene radical such as methylene, propylene, butylene ethylene, optionally interrupted by one or more heteroatom(s), 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%, 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 acrylic polymer particles.

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

More preferably, 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 called monomers). This or these units are repeated at least twice and preferably at least 3 times.

By " film-forming polymer " is meant a polymer capable of forming, on its own or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, in particular on hair, 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), in particular of alkali metal, alkaline earth metal, ammonium or organic base.

The esters of (meth)acrylic acid (also called (meth)acrylates) are advantageously chosen from alkyl (meth)acrylates, in particular C ₁ to C ₃₀ alkyl, preferably C ₁ to C ₂₀ , better still C ₁ to C ₁₀ alkyl, aryl (meth)acrylates, in particular C ₆ to C ₁₀ aryl, hydroxyalkyl (meth)acrylates, in particular C ₂ to C ₆ hydroxyalkyl.

Among the alkyl (meth)acrylates, we can cite methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate.

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

Among the aryl (meth)acrylates, we can cite benzyl acrylate and phenyl acrylate.

Particularly preferred esters of (meth)acrylic acid are alkyl (meth)acrylates, preferably C ₁ to C ₃₀ alkyl, more preferably C ₁ to C ₂₀ alkyl, even better C ₁ to C _{10 alkyl} , and even more particularly C ₁ to C _{4 alkyl} .

According to the present invention, the alkyl group of the esters may be fluorinated or even perfluorinated, that is to say that some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

Examples of amides of (meth)acrylic acid include (meth)acrylamides and N-alkyl (meth)acrylamides, particularly C ₂ to C ₁₂ alkyl. N-alkyl (meth)acrylamides include N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide and N-undecylacrylamide.

The acrylic polymer according to the invention may be a homopolymer or a copolymer, advantageously a copolymer, even better a copolymer of (meth)acrylic acid and (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) C ₁ to C ₃₀ alkyl (meth)acrylate, more preferably C ₁ to C ₂₀ , even better C ₁ to C ₁₀ , and even more particularly C ₁ to C ₄ .

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

The term " surfactant " means any agent 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 methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and 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 Copolymer sold under the trade name DAITOSOL 3000SLPN-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.

Examples of additional monomers that may be mentioned are styrenic monomers, in particular styrene and alpha-methylstyrene, and preferably styrene.

In particular, the acrylic polymer may be a styrene/(meth)acrylate copolymer, and in particular a polymer chosen from copolymers resulting from the polymerization of at least one styrene monomer and at least one C ₁ to C ₂₀ alkyl (meth)acrylate monomer, preferably C ₁ to C ₁₀ .

The C ₁ to C ₁₀ alkyl (meth)acrylate monomer may be chosen from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethyl hexyl acrylate.

Examples of acrylic polymers include styrene/(meth)acrylate(s) copolymers marketed under the name JONCRYL 77 by BASF, under the name YODOSOL GH41F by AKZO NOBEL and under the name SYNTRAN 5760 CG by INTERPOLYMER.

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

More preferably, 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) C ₁ to C ₃₀ alkyl (meth)acrylate, more preferably C ₁ to C ₂₀ , even better C ₁ to C ₁₀ , and even more particularly C ₁ to C ₄ .

Preferably, the aqueous dispersion of acrylic polymer particles has an acrylic polymer (or active material, or dry matter) content based on the weight of the dispersion of 20 to 60% by weight, more preferably of 22 to 55% by weight and more preferably of 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, more preferably from 0.5 to 30% by weight, better still 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 particles preferably ranges from 0.1 to 35% by weight, more preferably from 0.5 to 30% by weight, better still from 1 to 20% by weight, and even more preferably from 3 to 15% by weight relative to the total weight of composition C.

Coloring agent

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

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

The term "pigment" means all pigments that impart color to keratin materials. Their solubility in water at 25°C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

The pigments which can be used are chosen in particular from organic and/or mineral pigments known in the art, in particular those which are described in the Kirk-Othmer encyclopedia of chemical technology and in the Ullmann encyclopedia of industrial chemistry.

They can be natural, of natural origin, or not.

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

Pigments can, for example, be chosen from mineral pigments, organic pigments, lakes, special effect pigments such as mother-of-pearl or glitter, and mixtures thereof.

The pigment may be a mineral pigment. A mineral pigment is any pigment that meets the definition in the Ullmann Encyclopedia in the inorganic pigment chapter. Mineral pigments useful in the present invention include iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and titanium oxide.

The pigment may be an organic pigment. By "organic pigment" we mean any pigment that meets the definition in the Ullmann Encyclopedia in the organic pigment chapter.

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

In particular, the white or colored 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 Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 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, phenolic derivatives as described in patent FR 2 679 771.

As an example, we can also cite organic pigment pastes such as the products sold by the company HOECHST under the name:

- COSMENYL YELLOW IOG: Pigment YELLOW 3 (Cl 11710);

- COSMENYL YELLOW G: Pigment YELLOW 1 (Cl 11680);

- ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);

- COSMENYL RED R: Pigment RED 4 (Cl 12085);

- CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);

- VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);

- COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);

- VERT COSMENYL GG: Pigment GREEN 7 (Cl 74260);

- COSMENYL BLACK R: Pigment BLACK 7 (Cl 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 be composed in particular of particles comprising an inorganic core, at least one binder ensuring the fixing of the organic pigments on the core, and at least one organic pigment at least partially covering the core.

Organic pigment can also be a lake. Lake refers to dyes adsorbed onto insoluble particles, the resulting mixture remaining insoluble during use.

Inorganic substrates on which dyes are adsorbed include, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate, and aluminum.

Among the colorants, we can cite carminic acid. We can also cite the colorants 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 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).

Examples of lacquers include the product known as D & C Red 7 (CI 15850:1).

The pigment can also be a special effect pigment. Special effect pigments are pigments that generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) that is non-uniform and changes depending on the viewing conditions (light, temperature, viewing angles, etc.). They are therefore opposed to colored pigments that provide a conventional uniform opaque, semi-transparent or transparent shade.

There are several types of special effect pigments, those with a low refractive index such as fluorescent or photochromic pigments, and those with a higher refractive index such as pearlescent pigments, interference pigments or glitter.

Examples of special effect pigments include pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxides, mica coated with iron oxide, mica coated with titanium and in particular ferric blue or chromium oxide, mica coated with titanium and an organic pigment as defined above, and pearlescent pigments based on bismuth oxychloride. Pearlescent pigments include Cellini pearlescent pigments marketed by BASF (Mica-TiO ₂ -lake), Prestige pearlescent pigments marketed by Eckart (Mica-TiO ₂ ), Prestige Bronze pearlescent pigments marketed by Eckart (Mica-Fe ₂ O ₃ ) and Colorona pearlescent pigments marketed by Merck (Mica-TiO ₂ -Fe ₂ O ₃ ).

We can also cite the gold-colored mother-of-pearls marketed in particular by the company BASF under the name Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze mother-of-pearls marketed in particular 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 mother-of-pearls marketed in particular 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); brown mother-of-pearls marketed in particular by BASF under the name Nu-antique Copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); copper-toned mother-of-pearls marketed in particular by BASF under the name Copper 340A (Timica); red-toned mother-of-pearls marketed in particular by MERCK under the name Sienna Fine (17386) (Colorona); yellow-toned mother-of-pearls marketed in particular by BASF under the name Yellow (4502) (Chromalite); red-toned mother-of-pearls with a gold tint marketed in particular by BASF under the name Sunstone G012 (Gemtone); pink mother-of-pearls marketed in particular by BASF under the name Tan opale G005 (Gemtone); black mother-of-pearl with a gold sheen, notably marketed by BASF under the name Nu antique bronze 240 AB (Timica), blue mother-of-pearl notably marketed by MERCK under the name Matte Blue (17433) (Microna), white mother-of-pearl with a silver sheen, notably marketed by MERCK under the name Xirona Silver and pinkish-orange, golden-green mother-of-pearl notably marketed by MERCK under the name Indian Summer (Xirona) and their mixtures.

Still as an example of nacres, we can also cite particles comprising a borosilicate substrate coated with titanium oxide.

Particles with a glass substrate coated with titanium oxide are sold in particular under the name METASHINE MC1080RY by the company TOYAL.

Finally, examples of pearlescent agents include polyethylene terephthalate flakes, particularly those marketed by Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver flakes). Multi-layer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate, and aluminum can also be considered.

Special effect pigments may also be chosen from reflective particles, that is to say in particular particles whose size, structure, in particular the thickness of the layer(s) constituting them and their physical and chemical nature, and surface condition, enable them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create on the surface of the composition or mixture, when it is applied to the support to be made up, highlights visible to the naked eye, that is to say brighter points which contrast with their environment by appearing to shine.

The reflective particles may be selected so as not to significantly alter the coloring effect generated by the coloring agents associated with them and more particularly so as to optimize this effect in terms of color rendering. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or copper color or reflection.

These particles can have various shapes, including being platelet-shaped or globular, particularly spherical.

The reflective particles, whatever their shape, may have a multi-layer structure or not and, in the case of a multi-layer structure, for example at least one layer of uniform thickness, in particular of a reflective material.

When the reflective particles do not have a multi-layer structure, they can be composed, for example, of metal oxides, in particular titanium or iron oxides obtained by synthesis.

When the reflective particles have a multi-layer structure, they may, for example, comprise a natural or synthetic substrate, in particular a synthetic substrate at least partially coated with at least one layer of a reflective material, in particular at least one metal or metallic material. The substrate may be single-material, multi-material, organic and/or inorganic.

More particularly, it can be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica and their mixtures, this list not being limiting.

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

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

Still as an example of reflective particles comprising a mineral substrate coated with a layer of metal, we can also cite particles comprising a borosilicate substrate coated with silver.

Platelet-shaped particles with a silver-coated glass substrate are sold under the name MICROGLASS METASHINE REFSX 2025 PS by TOYAL. Particles with a nickel/chromium/molybdenum alloy-coated glass substrate are sold under the name CRYSTAL STAR GF 550, GF 2525 by the same company.

It is also possible to use particles comprising a metallic substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, titanium, said substrate being coated with at least one layer of at least one metallic oxide such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

Examples include aluminium, bronze or copper powders coated with SiO ₂ marketed under the name VISIONAIRE by the ECKART company.

Other examples include interference pigments that are not fixed to a substrate, such as liquid crystals (Helicones HC from Wacker), and holographic interference flakes (Geometric Pigments or Spectra f/x from Spectratek). Special effect pigments also include fluorescent pigments, whether they are substances that fluoresce in daylight or produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments, and quantum dots, marketed for example by the company Quantum Dots Corporation.

The variety of pigments that can be used in the present invention makes it possible to obtain a rich palette of colors, as well as particular optical effects such as metallic and interference effects.

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

The pigments can be dispersed in the composition using a dispersing agent.

The dispersing agent serves to protect the dispersed particles against agglomeration or flocculation. This dispersing agent may be a surfactant, an oligomer, a polymer or a mixture of several of them, carrying one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can attach physically or chemically to the surface of the pigments. These dispersants also have at least one functional group compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of C8 to C20 fatty acid and polyol such as glycerol, diglycerin, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750g/mol such as that 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 polyhydroxystearic acid such as that sold under the reference Arlacel P100 by the company Uniqema and their mixtures are used.

As another dispersant that can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17 000 sold by the company Avecia, poly dimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185, DC2-5225 C.

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

Thus, the previously surface-treated pigments useful in the context of the invention are pigments which have undergone totally or partially a surface treatment of a chemical, electronic, electrochemical, mechanochemical or mechanical nature, with an organic agent such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, p. 53-64 before being dispersed in the composition in accordance with the invention. These organic agents may be, for example, chosen from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; 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 polymethylmethacrylates; polymers and copolymers containing acrylate units; alkanoamines; silicone compounds, for example silicones, in particular polydimethylsiloxanes; fluorinated organic compounds, for example perfluoroalkyl ethers; fluoro-silicone compounds.

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

The surface-treated pigments useful in the context of the present invention can be prepared according to surface treatment techniques well known to those skilled in the art or found as such commercially.

Preferably, the surface-treated pigments are covered by an organic layer.

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

Surface treatment can thus be carried out, for example, by chemical reaction of a surfactant with the surface of the pigments and creation of a covalent bond between the surfactant and the pigments or fillers. This method is described in particular in US patent 4,578,266.

Preferably, an organic agent covalently bound to the pigments will be used.

The surface treatment agent may represent from 0.1 to 50% by weight of the total weight of the surface-treated pigment, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 20% by weight of 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 like the AQ surface treatment marketed by LCW;

- a Methicone treatment such as the SI surface treatment marketed by LCW;

- a Dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW;

- a Dimethicone / Trimethylsiloxysilicate treatment such as the Covasil 4.05 surface treatment marketed by LCW;

- a Magnesium Myristate treatment such as the MM surface treatment marketed by LCW;

- an Aluminum Dimyristate treatment such as the MI surface treatment marketed by Miyoshi;

- a Perfluoropolymethylisopropyl ether treatment such as the FHC surface treatment marketed by LCW;

- an Isostearyl Sebacate treatment such as the HS surface treatment marketed by Miyoshi;

- a Perfluoroalkyl Phosphate treatment such as the PF surface treatment marketed by Daito;

- an acrylate/Dimethicone and Perfluoroalkyl Phosphate Copolymer treatment such as the FSA surface treatment marketed by Daito;

- a Polymethylhydrogen siloxane / Perfluoroalkyl Phosphate treatment such as the FS01 surface treatment marketed by Daito;

- an Acrylate/Dimethicone Copolymer treatment such as the ASC surface treatment marketed by Daito;

- an Isopropyl Titanium Triisostearate treatment like the ITT surface treatment marketed by Daito;

- an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito;

- a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment like the PF + ITT surface treatment marketed by Daito.

According to a particular embodiment of the invention, the dispersing agent is present with organic or inorganic pigments in particulate form of sub-micron size.

By "sub-micronic" or in English " sub-micronic " is meant pigments whose particle size has been micronized by micronization method and whose average particle size is less than one micrometer (µm), in particular between 0.1 and 0.9 µm, and preferably between 0.2 and 0.6 µm.

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

The dispersing agent(s) may therefore have a silicone backbone, such as silicone polyether and amino-silicone dispersants. Suitable dispersing agents include:

- amino-silicones i.e. silicones comprising one or more amino groups such as those marketed 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, marketed by Genesee polymers,

- silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik,

- polydimethylsiloxane (PDMS) silicones with carboxylic groups such as X-22162 and X-22370 by Shin-Etsu, silicone epoxy 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 dispersing agent(s) are of the amino-silicone type and are cationic.

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

In one variant of the invention, the pigment(s) are organic pigments, preferably 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, in particular red, brown or black. As an example of iron oxide, mention may be made of 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 dye(s).

By "direct dye" we mean natural and/or synthetic dyes, different from oxidation dyes. These are dyes that will diffuse superficially on the fiber. They can be ionic, for example cationic or anionic, or non-ionic.

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 as mixtures.

The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly called “acid” direct dyes for their affinity with alkaline substances. Anionic direct dyes means any direct dye comprising in its structure at least one CO ₂ R or SO ₃ R 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 acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and acid natural dyes.

As an example of acid dyes we can cite: 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;

Examples of anionic azo pyrazolone dyes include: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, Acid Yellow 17;

As an example of anthraquinonic dyes, we can cite: 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;

Examples of nitrated dyes include: Acid Brown 13; Acid Orange 3; examples of dyes of formula (XXII') include: Acid Yellow 1, 2,4-dinitro-1-naphthol-7-sulfonic acid sodium salt, 2-piperidino 5-nitro benzene sulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzene sulfonic acid; EXT D&C yellow 7;

Examples of triarylmethane dyes include: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50.

Examples of xanthene dyes include: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9.

Examples of indole dyes include: Acid Blue 74;

Examples of quinoline dyes include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

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

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

The pigment(s) may be present in a total amount ranging from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, better still 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, preferably from 0.005 to 5% by weight relative to the total weight of composition C.

Non-carboxylic anionic thickening agent

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

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

For the purposes of the present invention, the term "thickening agent" means a compound which increases the viscosity of a composition into which it is introduced at 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 can be measured using a cone/plate viscometer, Haake R600 Rheometer or the like).

Preferably, the non-carboxylic anionic thickening agent(s) are chosen from non-carboxylic anionic polymers, more preferably from anionic polymers with 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 a cationic or cationizable group.

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

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

These polymers can be associative or not, preferably non-associative.

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

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

By "hydrophobic group" is meant a radical or polymer with a hydrocarbon chain, saturated or unsaturated, linear or branched, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms.

Preferably, the hydrocarbon group comes from a monofunctional compound. For example, the hydrophobic group can come from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It can also designate a hydrocarbon polymer such as, for example, polybutadiene.

The ethylenically unsaturated monomers with a sulfonic group are chosen in particular from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(C ₁ -C ₂₂ )alkylsulfonic acids, N-(C ₁ -C ₂₂ )alkyl(meth)acrylamido-(C ₁ -C ₂₂ )alkylsulfonic acids such as undecyl-acrylamido-methane-sulfonic acid as well as their partially or totally neutralized forms.

More preferably, (meth)acrylamido(C ₁ -C ₂₂ ) alkylsulfonic acids will be used, such as, for example, acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, as well as their partially or totally neutralized forms.

More specifically, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or totally neutralized forms will be used.

Among the copolymers of 2-acrylamido-2-methylpropane sulfonic acid, mention may be made of crosslinked copolymers of 2-acrylamido-2-methylpropane sulfonic acid and partially or totally neutralized acrylamide, and mention may be made in particular of the product described in example 1 of document EP 503 853 and reference may be made to this document with regard to these polymers.

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

The associative AMPS polymers may in particular be chosen from random associative AMPS polymers modified by reaction with a C ₆ -C ₂₂ 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 their esters 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 at least one hydrophobic monomer with ethylenic unsaturation.

Preferably, the non-carboxylic anionic thickening agent(s) are chosen from the sodium 2-acrylamido-2-methylpropanesulfonate/hydroxyethylacrylate copolymer, marketed by the company SEPPIC (INCI name: hydroxyethylacrylate/sodium acryloyldimethyl taurate copolymer).

Advantageously, the total content of the non-carboxylic anionic thickening agent(s) ranges from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight, better still from 0.1 to 5% by weight, and better still 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 further comprise at least one associative polymer different from the acrylic polymer and different from the non-carboxylic anionic thickening agent as defined previously.

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

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

By " hydrophobic group " is meant a radical or polymer with a hydrocarbon chain, saturated or unsaturated, linear or branched, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms.

Associative polymers can be non-ionic, anionic, cationic or amphoteric in 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 α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkylenated fatty alcohol.

Preferably, these compounds also comprise as monomer an ester of carboxylic acid with α,β-monoethylenic unsaturation and of C ₁ -C ₄ alcohol.

Examples of this type of compound include ACULYN 22® sold by ROHM and HAAS, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer, as well as ACULYN 88, also sold by ROHM and HAAS.

Advantageously, the associative polymer(s), different from acrylic polymers and different from the non-carboxylic anionic thickening agents previously described, are chosen from copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkylenated fatty alcohol.

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

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, more preferably from 20 to 75% by weight relative to the total weight of composition C.

In addition, composition C may comprise one or more organic solvents.

Examples of organic solvents that may be mentioned are C ₁ -C ₄ lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and aromatic alcohols, in particular aromatic monoalcohols such as benzyl alcohol, 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 preferably inclusively 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, anti-foaming agents, moisturizing agents, UV filters, peptizers, perfumes, anionic, cationic, non-ionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers previously described, preservatives, silicones, oils, waxes other than silicones in wax form, and mixtures thereof.

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

The person skilled in the art will be able to choose the appropriate galenic form, as well as its method of preparation, on the basis of his general knowledge, taking into account on the one hand the nature of the constituents used, in particular their solubility in the support, and on the other hand the application envisaged for the composition.

Protocol

Composition T as defined above can be applied to dry or damp hair, as well as to all hair types, light or dark, natural or colored, permed, bleached or straightened.

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

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

The application of composition T can be carried out at room temperature (between 15 and 25°C).

After applying composition T and foaming the composition, you can wait between 1 minute and 30 minutes, preferably up to 15 minutes, or even 10 minutes before rinsing off composition T.

According to this embodiment, after washing then rinsing, and optionally wringing and/or drying the hair, it is possible to wait 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.

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

Composition C described above can be used on dry or damp hair, as well as on all hair types, light or dark, natural or colored, permed, bleached or straightened.

Preferably, a washing, rinsing, wringing and/or drying step is carried out after applying composition C to the hair.

More preferably, a drying step is carried out after the application of composition C to the hair.

The application of composition C to the hair can be carried out by any conventional means, in particular by means of a comb, a brush, a brush, a sponge or with the fingers.

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

After applying composition C to the hair, you can wait between 1 minute and 6 hours, in particular between 1 minute and 2 hours, more particularly between 1 minute and 1 hour, more preferably between 1 minute and 30 minutes, before, for example, a washing, rinsing, wringing and/or drying step.

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

The method according to the invention can thus comprise a step of applying heat to the hair using a heating tool.

The heat application step can be implemented using a helmet, a hair dryer, a straightener or curling iron, a climazon, etc.

Preferably, the heat application step is carried out using a hair dryer.

When the method of the invention implements a step of applying heat to the hair, the step of applying heat to the hair takes place after the application of composition C to the hair.

During the heat application stage on the hair, a mechanical action on the strands can be carried out such as combing, brushing, or passing the fingers through.

When the step of applying heat to the hair is carried out using a helmet or a hair dryer, the temperature is preferably between 30 and 110°C, preferably between 50 and 90°C.

When the step of applying heat to the hair is carried out using a hair straightener, the temperature is preferably between 110 and 220°C, preferably between 140 and 200°C.

In a particular variant, the method of the invention implements a step (c1) of applying heat using a helmet, a hair dryer or a climazon, preferably a hair dryer and a step (c2) of applying heat using a straightening or curling iron, preferably a straightening iron.

Step (c1) can be done before step (c2).

During step (c1), also called the drying step, the hair may be dried, for example at a temperature 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 is dried, it is dried with a flow of air in addition to heat. This airflow during drying helps to improve the individualization of the sheathing.

During drying, mechanical action can be applied to the strands, such as combing, brushing, or passing the fingers through them.

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

After the heating step, a shaping step can be carried out with, for example, a hair straightener, the temperature for the shaping step can be between 110 and 220°C, preferably between 140 and 200°C.

According to one embodiment, the invention is a hair coloring method comprising the following steps:

i) the application to the hair of a composition T comprising at least one surfactant chosen from anionic surfactants, amphoteric or zwitterionic surfactants and their mixtures, and having a basic pH, as defined previously;

ii) optionally a time for leaving said composition T on the hair of 1 minute to 1 hour, preferably of 1 minute to 30 minutes;

iii) optionally a step of rinsing, wringing and/or drying said hair, preferably rinsing; then

iv) the application to the hair 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 coloring agent chosen from pigments, direct dyes, and their mixtures as described above; then

v) optionally a time for leaving said composition C on the hair of 1 minute to 30 minutes, preferably 1 to 20 minutes; then

vi) optionally a step of washing, rinsing, wringing and/or drying said hair.

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

According to a preferred embodiment, step b) of the process according to the invention consists of mixing extemporaneously at the time of use at least two compositions A and B to obtain a composition C and applying composition C to the hair, 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 coloring agent chosen from pigments, direct dyes, and their mixtures 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 coloring agent chosen from pigments, direct dyes, and their mixtures as described previously.

According to a preferred embodiment, step b) of the process according to the invention consists of mixing extemporaneously at the time of use at least two compositions A and B to obtain a composition C and applying composition C to the hair, 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 coloring agent chosen from pigments, direct dyes, and their mixtures as defined previously.

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

According to this embodiment, compositions A and B are preferably mixed less than 15 minutes before application to the hair, more preferably 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, preferably from 0.2 to 5, 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, better still from 0.5 to 20% by weight, even more preferably 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, better still from 1 to 30% by weight, and even more preferably from 2 to 20% by weight relative to the total weight of composition B.

According to a preferred embodiment, the invention is a hair coloring process comprising the following steps:

i) the application to the hair of a composition T as defined previously comprising water, at least one surfactant chosen from anionic surfactants, amphoteric or zwitterionic surfactants and their mixtures, and having a basic pH;

ii) optionally a time for leaving said composition T on the hair of 1 minute to 30 minutes, preferably of 1 minute to 10 minutes;

iii) a step of rinsing, optionally wringing and/or drying said hair; then

iv) the application to the hair of at least one composition C comprising:

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

- at least one acrylic polymer as defined above; and

- at least one coloring agent chosen from pigments, direct dyes, and their mixtures as described above; then

v) optionally a time for leaving said composition C on the hair of 1 minute to 30 minutes, preferably 1 to 20 minutes; then

vi) optionally a step of washing, rinsing, wringing and/or drying said hair.

Multi-compartment device (kit)

The present invention also relates to a device for coloring hair comprising several compartments containing:

- a first compartment comprising the 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 way of examples, which are in no way limiting of the scope of the invention. However, the examples make it possible to support specific characteristics, variations, and preferred embodiments of the invention.

EXAMPLES

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

More particularly, the process for preparing the (poly)carbodiimides of the invention uses, during a first step, a diisocyanate reagent (1):
O=C=NL ₁ -N=C=O (1),

formula (1) in which L ₁ is as defined above which reacts in the presence of a carboimidation catalyst (2) such as those described in US 4,284,730 in particular phosphorus catalysts particularly chosen from phospholene oxides and phospholene sulfoxides, diaza and oxazaphospholanes, preferably under an inert atmosphere (nitrogen or Argon), and in particular in a polar solvent, preferably aprotic, such as THF, glyme, diglyme, 1,4-dioxane, and DMF, at a temperature between room temperature and solvent reflux, preferably around 140°C; to yield the carbodiimide diisocyanate compound (3):
O=C=NL ₁ -(N=C=NL ₁ ) _n -N=C=O (3),

formula (3) in which L ₁ and n are as defined above. Halogenated benzoyl 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 R ₁ -X ₁ -H, then 0.5 eq. of HEH reagent with R ₁ , X ₁ and E as defined previously, to lead to the “symmetrical” compound according to the invention (4):
[R ₁ -X ₁ -C(O)-NH-L ₁ -(N=C=NL ₁ ) _n -NH-C(O)] ₂ -E (4),

formula (4) in which R ₁ , X ₁ , L ₁ , n, and E are as defined previously. According to a variant to obtain compound (4) from (3) it is possible to first add 0.5 eq. of HEH reagent, then 1 eq. of R ₁ -X ₁ -H reagent.

To obtain “asymmetric” (poly)carbodiimides, during the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq) of nucleophilic reagent R ₁ -X ₁ -H then 1 eq. of HEH reagent with R ₁ , X ₁ and E as defined previously, to lead to compound (5):
R ₁ -X ₁ -C(O)-NH-L ₁ -(N=C=NL ₁ ) _n -NH-C(O)-EH (5),

formula (5) in which R ₁ , X ₁ , L ₁ , n, and E are as defined previously.

According to a variant to obtain compound (5) from (3) it is possible to first add 1 eq. of reagent R ₁ -X ₁ -H, then 0.5 eq. of reagent HEH.

In a third step, compound (5) reacts with 1 eq. of compound (6)
R ₂ -X ₂ -C(O)-NH-L ₁ -(N=C=NL ₁ ) _z -N=C=O (6), said compound (6) is prepared beforehand from compound (3'): O=C=NL ₁ -(N=C=NL ₁ ) _z -N=C=O (3'),

formula (3') in which L ₁ and z are as defined previously which reacts with 1 eq of nucleophilic reagent R ₂ -X ₂ -H with L ₁ , R ₂ , X ₂ , and z as defined previously, to lead to the asymmetric compound (7): R ₁ -X ₁ -C(O)-NH-L ₁ -(N=C=NL ₁ ) _n -NH-C(O)-EC(O)-NH-L ₁ --(N=C=NL ₁ ) _z -NH-C(O)-X ₂ -R ₂ (7),

formula (7) in which R ₁ , X ₁ , L ₁ , R ₂ , X ₂ , n, z and E are as defined previously.

It is also possible to react 1 molar equivalent of compound O=C=NL ₁ -(N=C=NL ₁ ) _z -N=C=O (3') with 1/w molar equivalent of HEH, then 1 eq. of nucleophilic reagent R ₂ -X ₂ -H to lead to compound (8):
H-[EC(O)-NH-L ₁ -(N=C=NL ₁ ) _z ] _w -NH-C(O)-X ₂ -R ₂ (8),

formula (8) in which L ₁ , R ₂ , X ₂ , z and E are as defined previously, and w is an integer between 1 and 3, more preferably w = 1.

This last compound (8) can then react with 1 eq of compound (4'):
R ₁ -X ₁ -C(O)-NH-L ₁ -(N=C=NL ₁ ) _n -N=C=O (4'), (said compound (4') can be synthesized by reaction of 0.5 eq. of nucleophilic reagent R ₁ -X ₁ -H with 1 equivalent of compound (3)), to lead to the (poly)carbodiimide of the invention (9):

R ₁ -X ₁ -C(O)-NH-L ₁ -(N=C=NL ₁ ) _n -NH-C(O)-[EC(O)-NH-L ₁ -(N=C=NL ₁ ) _z ] _w -NH C(O)-X ₂ -R ₂ (9),

formula (9) in which L ₁ , R ₁ , X ₁ , R ₂ , X ₂ , n, z, w, and E are as defined previously.

The (poly)carbodiimide compounds as well as all reaction intermediates and reagents can be purified with 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 the synthesis of the compound (poly)carbodiimide

In a 500 mL three-necked flask equipped with a thermometer, a stirrer and a reflux tube, 50 g of dicyclohexylmethane 4,4'-diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphole 1-oxide were introduced under stirring.

The reaction medium was heated to 140°C under nitrogen for 4 hours, following the reaction by infrared spectroscopy through the absorption of the isocyanate functions between 2200 and 2300 cm ^-1 , then cooled to 120°C.

A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol is introduced into the reaction medium with stirring. The temperature of 120°C is maintained until the isocyanate functions have completely disappeared, monitored by infrared spectroscopy at 2200-2300 cm ^-1 , 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 yield 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 quantities are expressed in g of active ingredient/100g, unless otherwise stated.

Compositions T1 T2 Sodium laureth sulfate 19.8 19.8 Cocamidopropyl betaine 3.9 3.9 Conservatives qs qs Sodium chloride 0.5 0.5 Lactic acid Qs pH 4.2 - Sodium hydroxide - Qs pH 9.4 Water Qsp 100 Qsp 100

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

Compositions A and B as described below in Tables 2 and 3 were prepared: the quantities are expressed in g of raw material as is/100g, unless otherwise stated.

Composition HAS Polycarbodiimide ⁽¹⁾ 17.5 Hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer ⁽²⁾ 3 Ethanol 20 Water qsp 100

(1) synthesized according to the synthesis process described in example 1 (at 40% active material in water),

(2) sold by the company SEPPIC under the name SEPINOV EMT10 (90% active ingredient).

Composition B Acrylates copolymer ⁽³⁾ 29.2 Red Iron Oxide (CI 77491) 12 Divinyldimethicone/dimethicone (and) C ₁₂ - ₁₃ Pareth-3 (and) C ₁₂ - ₁₃ Pareth-23 ⁽⁴⁾ copolymer 10.2 Amino silicone 8.8 Acrylates/Steareth-20 methacrylate copolymer ⁽⁵⁾ 2.2 Water qsp 100

(3) acrylic polymer sold by the company DAITO KASEI KOGYO under the trade name DAITOSOL 3000SLPN-PE1 (aqueous dispersion with 30% active ingredient),

(4) sold by the company DOW CORNING under the name DOW CORNING HMW 2220 NON-IONIC EMULSION (Divinyldimethicone/dimethicone block copolymer in aqueous emulsion) (60% active ingredient),

(5) associative polymer sold by the company ROHM and HAAS under the trade name ACULYN 22® (methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer with 30% active ingredient).

Composition A was then mixed with composition B at a mass ratio of 50/50 to obtain a composition C according to the invention.

Protocol

Two different processes were implemented.

According to methods 1 and 2, compositions T1 or T2, respectively, were first applied to sensitized locks of hair subsequently called SA20. Each of these compositions was applied to locks of hair, at a rate of 0.8 g of composition per gram of lock. Then the locks of hair were rinsed.

Composition C was then applied to the strands previously treated with composition T1 or composition T2, at a rate of 0.8 g of composition per gram of strand. The strands of hair were then detangled and dried with a hairdryer.

The process using composition T1 and then composition C is a comparative process since composition T1 does not have a basic pH. It is referred to below as process P1. The process using composition T2 and then composition C is a process according to the invention. In the following, it is referred to as process P2.

The processes applied are summarized in Table 4 below:

Processes P1 (comparative) P2 (invention) Application of the compositions T1 + C T2 + C

The locks of hair treated by processes P1 to P2 were then subjected to a test of several repeated shampoos in order to evaluate the tenacity (the persistence) of the coloring obtained from the shampoos, according to the shampoo protocol described below.

Shampoo protocol

The colored hair strands are combed, moistened under 35°C water before being passed between the fingers 5 times for 5 seconds. The hair strands are then wrung out between two fingers.

A standard shampoo (Garnier Ultra Doux) is applied evenly to the colored strands at a rate of 0.4g of standard shampoo per gram of strands, gently kneading the strands of hair lengthwise (6 strokes) for 15 seconds, from root to tip.

The strands of hair are then placed in a watch glass and left to rest for 1 minute.

Then, the hair strands are rinsed with water by passing the strand between the fingers (15 passes). The hair strands are then wrung out between two fingers before the next shampoo.

Once several shampoos have been tested, the hair strands are combed and dried with a hairdryer.

Results

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

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

Color retention is assessed by the color difference ΔE between the colored strands before shampooing, then after undergoing 5 shampoos according to the protocol described above. The lower the ΔE value, the more the color is persistent after shampooing.

The value of ΔE is calculated according to the following equation:

In this equation, L*, a*, b* represent the values measured after hair coloring and after shampooing, and L ₀ *, a ₀ *, b ₀ * represent the values measured after hair coloring but before shampooing.

The results are summarized in Table 5 below.

Processes Number of shampoos L* has* b* ΔE 1 (comparative) 0 32.8 26.8 22.1 - 5 49.2 15.9 26.4 20.1 2 (invention) 0 32.9 28.0 23.0 - 5 47.3 18.5 25.1 17.4

The hair strands treated with the method according to the invention and washed with five shampoos have a lower ΔE value than the hair strands treated with the comparative method.

Thus, the colored coating obtained with the process according to the invention has improved persistence to shampooing.

Example 3

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

The results are reported in Table 6 below.

pH of the
Shampoo
Hair type Color persistence % (ΔE after sh/ΔE before sh*100) pH = 5.3 BN 85.2 pH = 9.5 (inv) BN 91.4 pH = 5.3 SA80 58.5 pH = 9.5 (inv) SA80 73.3

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

Claims (17)

Hair coloring process comprising:
(a) a step of washing the hair with a composition T comprising at least one surfactant chosen from anionic surfactants, amphoteric or zwitterionic surfactants and their mixtures, and having a basic pH; then
(b) applying to the hair a hair coloring composition C comprising:
- at least one (poly)carbodiimide compound chosen from the compounds of the following formula (II):
(II),
in which:
- X ₁ and X ₂ represent, independently, an oxygen atom O, a sulfur atom S or an NH group;
- R ₁ and R ₂ independently represent a hydrocarbon radical optionally interrupted by one or more heteroatom(s);
- 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;
- L ₁ independently represents a divalent C ₁ -C ₁₈ aliphatic hydrocarbon radical, a C ₃ -C ₁₅ cycloalkylene radical, a C ₃ -C ₁₂ heterocycloalkylene group, or a C ₆ -C ₁₄ arylene group, and mixtures thereof;
- E independently represents a group chosen from:
-OR ₃ -O-; -SR ₄ -S-; -R ₅ -N(R ₆ )-R ₄ -N(R ₆ )-R ₅ -,
in which R ₃ and R ₄ independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s);
- R ₅ independently represents a covalent bond or a divalent saturated hydrocarbon radical, optionally interrupted by one or more heteroatom(s);
- R ₆ independently represents a hydrogen atom, or a hydrocarbon radical optionally interrupted by one or more heteroatom(s);
- at least one polymer comprising at least one reactive group chosen from carboxylic acids; and
- at least one coloring agent chosen from pigments, direct dyes and their mixtures. Method according to claim 1, characterized in that the composition T has a pH ranging from 7.5 to 13, more preferably from 8 to 10. Process according to claim 1 or 2, characterized in that the composition T comprises at least one alkaline agent, preferably chosen from hydroxides of alkali or alkaline earth metals, ammonium, alkanolamines, and mixtures thereof, preferably sodium hydroxide. 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 alkyl(C ₁₀ -C ₂₂ )sulfates, alkyl(C ₁₀ -C ₂₂ )ether sulfates and their mixtures, more preferably from sodium alkyl(C ₁₀ -C ₂₂ )ether sulfates and their mixtures. Process according to any one of the preceding claims, characterized in that the amphoteric or zwitterionic surfactant(s) of composition T are chosen from alkyl(C ₈ -C ₂₀ )betaines, alkyl(C ₈ -C ₂₀ )sulfobetaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₆ -C ₈ )sulfobetaines, and mixtures thereof, more preferably chosen from alkyl(C ₈ -C ₂₀ )betaines, alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines and mixtures thereof, more preferably still from alkyl(C ₈ -C ₂₀ )amidoalkyl(C ₃ -C ₈ )betaines and their mixtures. Process according to any one of claims 1 to 5 in which the composition T comprises an amount of surfactant(s) chosen from anionic surfactants, amphoteric or zwitterionic surfactants and their mixtures 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 the composition T. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) in which:
- X ₁ and X ₂ independently represent an oxygen atom;
- R ₁ and R ₂ are independently chosen from dialkylaminoalcohols, hydroxycarboxylic acid alkyl esters and (poly)alkylene glycol monoalkyl ethers, in which a hydroxy 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;
- L1 is chosen from a divalent C ₁ -C ₁₈ aliphatic hydrocarbon radical, a C ₃ -C ₁₅ cycloalkylene radical, a C ₃ -C ₁₂ heterocycloalkylene group, or a C ₆ -C ₁₄ arylene group, and mixtures thereof;
- E independently represents a group chosen from:
- -OR ₃ -O-; -SR ₄ -S-; -R ₅ -N(R ₆ )-R ₄ -N(R ₆ )-R ₅ -;
in which R3 and R4 are independently chosen from a _C6 - _C14 arylene radical, a _C3 - _C12 cycloalkylene radical, a linear or branched _C1 - _C18 alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;
- when R ₅ is not a covalent bond, R ₅ is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof; and
- R ₆ is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) in which:
- X ₁ and X ₂ independently represent an oxygen atom;
- R ₁ and R ₂ , are independently monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed;
- n and z denote an integer ranging from 1 to 20, with n+z ≥ 2 and w is equal to 1;
- L ₁ is a C ₃ -C ₁₅ cycloalkylene radical;
- E independently represents a group chosen from:
-OR ₃ -O-; -SR ₄ -S-; -R ₅ -N(R ₆ )-R ₄ -N(R ₆ )-R ₅ -;
in which R ₃ and R ₄ are independently chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof;
- when R ₅ is not a covalent bond, R ₅ is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof; and
- R ₆ is chosen from a C ₆ -C ₁₄ arylene radical, a C ₃ -C ₁₂ cycloalkylene radical, a linear or branched C ₁ -C ₁₈ alkylene radical, optionally interrupted by one or more heteroatom(s), and mixtures thereof. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) in which:
- X₁ and X₂independently represent an oxygen atom;
- R₁and R₂, independently represent the compound of formula (VI) following:
R₁₃-[O-CH₂-C(H)(R₁₄)]_q- (VI),
in which R₁₃represents a C alkyl group₁-C₄or a phenyl, preferably a C 1 -C 2 alkyl group₁-C₄, more preferably a methyl, R₁₄represents a hydrogen atom or a C alkyl group₁-C₄, 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 equal to 1;
- L₁is a C cycloalkylene radical₃-C₁₅such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, and
- E represents a -O-R group₃-O- in which R₃is chosen from a C arylene radical₆-C₁₄, a C cycloalkylene radical₃-C₁₂, a linear or branched C alkylene radical₁-C₁₈, possibly interrupted by one or more heteroatom(s), and mixtures thereof. Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) in which:
- X ₁ and X ₂ independently represent an oxygen atom;
- R ₁ and R ₂ , independently represent the compound of formula (VI) following:
R ₁₃ -[O-CH ₂ -C(H)(R ₁₄ )] _q - (VI),
in which R ₁₃ represents a C ₁ -C ₄ alkyl group or a phenyl, preferably a C ₁ -C ₄ alkyl group, more preferably a methyl, R ₁₄ represents a hydrogen atom or a C ₁ -C ₄ 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;
- L ₁ is a C ₃ -C ₁₅ cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and
- E represents a group - -OR ₃ -O- in which R ₃ represents a linear or branched C ₁ -C ₁₈ alkylene radical such as methylene, propylene, butylene, ethylene, optionally interrupted by one or more heteroatom(s). Process according to any one of the preceding claims, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (XII) below:
(XII),
in which L ₁ is 4,4-dicyclohexylene methane, n and z denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10, E represents a group - -OR ₃ -O- in which R ₃ represents a linear or branched C ₁ -C ₁₈ alkylene radical such as methylene, propylene, butylene ethylene, optionally interrupted by one or more heteroatom(s), and r and s denote an integer ranging from 4 to 30. 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, better still from 1 to 6% by weight relative to the total weight of composition C. 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) C ₁ to C ₃₀ alkyl (meth)acrylate, more preferably C ₁ to C ₂₀ , even better C ₁ to C ₁₀ , and even more particularly C ₁ to C ₄ . 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, more preferably from 0.5 to 30% by weight, better still from 1 to 20% by weight, and even more preferably from 3 to 15% by weight relative to the total weight of composition C. Process according to any one of the preceding claims, characterized in that the total content of coloring agent(s) ranges from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight relative to the total weight of composition C, preferably the coloring agent(s) are chosen from pigments. Method according to any one of the preceding claims, characterized in that step (b) consists of mixing extemporaneously at the time of use at least two compositions A and B to obtain a composition C and applying composition C to the hair, 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 coloring agent as defined in claim 1. Device for coloring hair comprising several compartments containing:
- a first compartment comprising the 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.