FR3123567A1 - Hair coloring process comprising the application of a (poly)carbodiimide compound, a polymer containing a carboxylic group and a non-silicone fatty substance - Google Patents

Abstract

The present invention relates to a process for coloring hair, in particular the hair, comprising the application of a composition A and a composition B to the keratin fibers of the hair, in which: composition A comprises at least one compound (poly) carbodiimide, and composition B comprises at least one polymer, having at least one carboxylic acid group; composition A and/or composition B comprising at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof, and at least one non-silicone fatty substance, in which composition A and composition B are applied simultaneously or sequentially on hair keratin fibres. The present invention also relates to a hair coloring device.

Description

Hair coloring process comprising the application of a (poly)carbodiimide compound, a polymer containing a carboxylic group and a non-silicone fatty substance

The present invention relates to a hair dyeing process, comprising the application of a composition A and a composition B to the hair keratin fibres, in which the composition A comprises at least one (poly)carbodiimide compound, and the composition B comprises at least one polymer having at least one carboxylic acid group, composition A and/or composition B comprising at least one non-silicone fatty substance and at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof, and in which composition A and composition B are applied simultaneously or sequentially to the hair keratin fibres.

The present invention also relates to a hair coloring composition as well as a hair coloring device.

In the field of hair dyeing, in particular human hair dyeing, it is already known to dye keratin fibers by various techniques using direct dyes or pigments for non-permanent dyes or dye precursors for permanent dyes.

There are basically three types of hair coloring process:

a) so-called permanent coloring which has the function of bringing a significant modification of 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 process of oxidative condensation and resists 4 or 5 shampoos; consists in dyeing the keratin fibers with dye compositions containing direct dyes;

c) temporary coloring which gives rise to a modification of the natural color of the hair which holds from one shampoo to another and which serves to embellish or correct a shade already obtained. It can also be likened to a “make-up” process.

For this last type of coloring, it is known to use colored polymers formed by grafting one or more dyes of azo, triphenyl-methane, azinic, indoamine or anthraquinone nature onto a polymer chain. These colored polymers are not entirely satisfactory, in particular in terms of the homogeneity of the coloration obtained, of its resistance, not to mention the problems linked to their manufacture and in particular to their reproducibility.

Another coloring method is to use pigments. Indeed, the use of pigment on the surface of keratin fibers generally makes it possible to obtain visible colorings on dark hair since the pigment on the surface masks the natural color of the fiber. However, the colorings obtained by this method of coloring have the disadvantage of having a low resistance to shampoos as well as to external agents such as sebum, perspiration, brushing and/or rubbing.

In addition, the temporary hair coloring compositions may moreover have qualities of use which are not entirely satisfactory, in particular in terms of texture, ease and/or homogeneity of distribution on the hair.

There therefore remains a need to have a process for coloring hair, in particular hair, which has the advantage of obtaining a homogeneous and smooth colored coating on the hair, while forming a coating that is resistant to shampoos and to the various attacks that the hair can be subjected to such brushing and/or friction without degradation of the hair, and in which the compositions used in the context of the said method have good stability over time, as well as good qualities for use.

Thus, the object 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 that is resistant to shampoos and to the various attacks that can be subjected to the hair such as brushing and/or friction without degradation of the hair, and in which the compositions used in the context of the said process have good stability over time and good qualities of use, in particular in terms of texture, ease and/or homogeneity of distribution on the hair.

A subject of the present invention is therefore a hair dyeing process, comprising the application of a composition A and a composition B to the keratin fibers of the hair, in which:
composition A comprises at least one (poly)carbodiimide compound, and
composition B includes:
- at least one polymer having at least one carboxylic acid group, and
composition A and/or composition B comprising at least 0.1% by weight of one or more non-silicone fatty substances and at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof, and in which composition A and composition B are applied simultaneously or sequentially to the hair keratin fibres.

In a variant of the invention, a hair coloring composition C is obtained by extemporaneous mixing at the time of use of at least one composition A as defined above and at least one composition B as defined above. In this variant, the hair dye composition C, obtained by mixing composition A and composition B, is applied to the hair keratin fibres.

In another variant, composition A as defined above and composition B as defined above are applied simultaneously to the hair keratin fibres, without prior mixing.

In another variant, composition A and composition B are applied sequentially to the hair keratin fibres, it being possible for composition A to be applied to the hair keratin fibers before composition B or vice versa.

The present invention also relates to a hair coloring device, comprising at least two compartments containing
in a first compartment (E1), a composition A as defined previously, and
in a second compartment (E2), a composition B as defined above;
optionally in a third compartment (E3), a composition D as defined below.

By using this coloring process on the hair keratin fibres, colored coatings are obtained on the hair, making it possible to obtain a visible coloring on all types of hair in a shampoo-retentive manner while preserving the physical qualities of the hair keratin fibers . Such a sheathing can be resistant to the external aggressions that the hair can undergo, such as blow-drying and perspiration. In particular, it makes it possible to obtain a smooth and homogeneous deposit and an improvement in disentangling when drying the hair fibres.

In addition, the compositions used in the context of the process according to the invention have good qualities of use, in particular in terms of ease and homogeneity of distribution on the hair, minimizing any problems of drips.

By “ shampoo-resisting coloration ” is meant within the meaning of the present invention that the coloration obtained persists after one shampoo, preferably after 3 shampoos, more preferably after 5 shampoos.

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

The invention is not limited to the examples illustrated. The characteristics of the various examples can in particular be combined within variants that are not illustrated.

Within the meaning of the present invention and, unless otherwise indicated,

- an “ alkyl ” radical denotes a saturated linear or branched radical containing, for example, from 1 to 20 carbon atoms;

- an “ aminoalkyl ” radical denotes an alkyl radical as defined above, said alkyl radical comprising an NH ₂ group;

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

- an “ alkylene ” radical designates a divalent C ₂ -C ₄ saturated hydrocarbon group, linear or branched, such as methylene, ethylene or propylene;

- a " cycloalkyl " or " alicycloalkyl " radical denotes a mono or bicyclic saturated cyclic hydrocarbon group, preferably monocyclic, comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 24 carbon atoms, in particular comprising 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 a cyclohexyl. it being understood that the cycloalkyl radical can 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 designates a divalent cycloalkyl group with “ cycloalkyl ” as defined above, 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 ring with 6 carbon atoms such as phenyl, naphthlyl, , anthryl, phenanthryl and biphenyl, it being understood that the aryl radical can 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 designates a mono or polycyclic, saturated or unsaturated, non-aromatic or aromatic hydrocarbon radical, comprising one or more heteroatoms, preferably of 1 to 5 atoms chosen from O, S or N, comprising from 3 to 20 chains of preferably between 5 and 10 members such as imidazolyl, pyrrolyl and furanyl;

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

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

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

- 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.

By “hair keratinous fibres”, is meant particularly the hair.

(Poly)carbodiimide compound

Composition A according to the invention implemented in the context of the dyeing process according to the invention comprises at least one (poly)carbodiimide compound.

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 group(s), 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 between 100 and 150, more preferably around 100.

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

The (poly)carbodiimide compound(s) according to the invention may optionally comprise in their structure one or more reactive groups different from carbodiimide groups, chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane.

The reactive group(s) different from the carbodiimide groups can be pendent or terminal. Preferably, the (poly)carbodiimide compound(s) comprise(s) one or more terminal groups other than carbodiimide groups, preferably one or more terminal groups chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl groups. , hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane.

According to a particular embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) below:

(I),

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 group which may comprise one or more heteroatoms, in particular R ₁ and R ₂ independently represent a group chosen from a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatom(s) , un groupement choisi parmi les groupements alkoxysilyle, hydroxysilyle, acétoxysilyle, vinylsilyle, acrylalkylsilyle, méthacrylalkylsilyle, crotonylalkylsilyle, carboxyanhydridoalkylsilyle, carboxyalkylsilyle, hydroxyalkylsilyle, aldéhydoalkylsilyle, mercaptoalkylsilyle, norbornénylsilyle, acylpentadiénylalkylsilyle, maléimidoalkylsilyle, sulphonylalkylsilyle, (méth)acrylalkyle, crotonylalkyle, alkylépoxyde tels que propylépoxyde or butylepoxide, and azacyclopropane, and a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatom(s) and by one or more groups chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinyl silyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkylsilyl such as acycloepoxide or butylepoxide, propylepoxide and butylepoxide;

- n denotes an integer ranging from 1 to 1000; preferably 1 to 100 and

- A is a monomer chosen from the compounds below:




.

According to another embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (Ia) below:

in which :

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

- Y ₁ and Y ₂ represent, independently, a divalent organic radical chosen from a saturated aliphatic group in C ₁ to C ₃₆ or an aromatic or alkylaromatic group in C ₆ to C ₂₄ , the aliphatic or aromatic group possibly comprising one or more non-pendant heteroatoms, such as nitrogen atom, oxygen atom, sulfur atom, or combinations thereof;

- Z ₁ and Z ₂ represent, independently, a reactive terminal group or an inert terminal group;

- as an inert end group, Z ₁ and Z ₂ may represent, independently, a saturated, linear or branched or cyclic aliphatic group, C ₁ to C ₅₀ , or an aromatic group C ₆ to C ₁₈ , said aliphatic groups and aromatics optionally comprising from 1 to 10 heteroatoms chosen from nitrogen, oxygen, sulfur and their combinations, and the aliphatic or aromatic group can be partially or totally fluorinated; in this variant, Z ₁ and Z ₂ comprise a linking group CG linking Z ₁ to Y ₁ and Z ₂ to Y ₂ , the group CG possibly being a single covalent bond, a saturated CC bond, an unsaturated covalent CC bond, a amide group, ester group, carbonate group, thioester group, ether group, urethane group, thiourethane group or urea group;

- en tant que groupe terminal réactif, Z ₁ et Z ₂ peuvent être choisis parmi les groupements alcoxysilyle, hydroxysilyle, acétoxysilyle, vinylsilyle, acrylalkylsilyle, méthacrylalkylsilyle, crotonylalkylsilyle, carboxyanhydridoalkylsilyle, carboxyalkylsilyle, hydroxyalkylsilyle, aldéhydoalkylsilyle, mercaptoalkylsilyle, norbornénylsilyle, acylpentadiénylalkylsilyle, maléimidoalkylsilyle, sulfonylalkylsilyle , (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane;

- Q represents an organopolymer or an organo-oligomer comprising repeating units of saturated, linear or branched or cyclic aliphatic groups, or of aromatic groups or alkylaromatic groups, coupled by repeating carbonate, ester, ether, amide, urethane or urea bonds or combinations thereof;

- A represents a divalent aliphatic, aromatic, alkylaromatic or linear, saturated, branched or cyclic radical having from 2 to 30 carbon atoms, which can optionally comprise one or more non-pendant heteroatoms, such as the nitrogen atom, the atom oxygen, the sulfur atom, or their combinations, in the aliphatic chain or the aromatic chain;

- r denotes an integer equal to 0 or 1;

- m denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1;

- m' denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1;

- n designates an integer ranging from 0 to 1000, preferably equal to 0 or 1 with m+ (m’*n ) ≥ 2.

Preferably, Z ₁ and Z ₂ represent, independently, a reactive terminal group, more preferably, Z ₁ and Z ₂ represent, independently, a group chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl groups , carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide, and azacyclopropane.

Such (poly)carbodiimide compounds are, for example, marketed by the company Stahl B.V, under the name Permutex XR, or under the name RelcaLink10., under the name Picassian XL and Nisshinbo compounds marketed under the name CARBODILITE with the V-02 series , V-02-L2, SV-02, E-02, V-10, SW-12G, E-03A, E-04DG-T, E-05, V-04, V-02B, V-04PF, V -05.

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 C ₁ -C ₁₈ divalent 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 their mixtures;
- 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 can 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 group ( s) cationic(s) such as ammonium, anionic group(s) such as carboxylate, or zwitterionic(s), and/or comprising a metal ion which can 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 chosen independently from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, and mixtures thereof.

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

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

R ₇ -OC(O)-C(R ₈ )(H)- (III),

in which 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 a methyl and R ₈ is a hydrogen or a methyl.

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

R ₉ -[O-CH ₂ -C(H)(R ₁₀ )] _p - (IV),

in which 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 a methyl, ethyl or butyl and R ₁₀ is a hydrogen atom or a methyl and p is equal to 1.

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

(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 a methyl, ethyl or butyl and R ₁₂ is a hydrogen atom or a methyl.

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

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, 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 preferentially 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 a methyl, ethyl or butyl and R ₁₀ is a hydrogen atom or a methyl and p is equal to 1.

Preferably, in formula (VI), R ₁₃ is a methyl, ethyl or butyl and R ₁₄ is a hydrogen atom or a 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 alkyl group -C ₄ , 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 C ₁ -C ₁₈ divalent 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 can be chosen from a radical derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-diisocyanate dodecane, norbornane diisocyanate, 2 ,4-bis-(8-isocyanateoctyl)-1,3-dioctylcyclobutane, 4,4'-dicylclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-napththylene 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 C ₆ -C ₁₄ arylene group, L ₁ is not the m-tetramethylxylylene radical represented by the following formula (IX):

(IX).

As indicated above, 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 chosen independently 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 such as methylene and ethylene, optionally interrupted by one or more heteroatom(s) and mixtures thereof.

More preferably, R ₃ and R ₄ are chosen independently 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 such as methylene and ethylene, optionally interrupted by one or more heteroatom(s), and mixtures thereof.

Preferably, E represents an -OR ₃ -O- group 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 , optionally interrupted by one or more heteroatom(s), and mixtures thereof.

More preferably, E represents an -OR ₃ -O- group 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 formula (X) below:

(X),

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

n designates an integer ranging from 2 to 100.

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

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

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 formula (XI) below:

(XI),

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

The “alkyl group”, the “cycloalkyl group” and the “aryl group” are as previously defined.

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

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

- R ₁ and R ₂ are chosen independently from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, in which a hydroxy group has been removed, and mixtures thereof, preferably monoalkyl ethers (poly)alkylene glycol, in which a hydroxy group has been removed, more preferentially, 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 it is present, is chosen from a divalent aliphatic hydrocarbon radical in C ₁ -C ₁₈ , a cycloalkylene radical in C ₃ -C ₁₅ , a heterocycloalkylene group in C ₃ -C ₁₂ , or an arylene group in C ₆ -C ₁₄ , and mixtures thereof, preferably a C ₃ -C ₁₅ cycloalkylene radical;

- A, when it is present, is chosen from a C ₁ -C ₁₈ divalent aliphatic hydrocarbon radical, a C ₃ -C ₁₅ cycloalkylene radical, a C ₃ -C ₁₂ heterocycloalkylene group, or a C arylene group ₆ -C ₁₄ , 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 chosen independently 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 alkylene radical C ₁ -C ₁₈ , optionally interrupted by one or more heteroatom(s), and mixtures thereof; and

- R ₆ , when it is 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 a 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 chosen independently from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, 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 C ₁ -C ₁₈ divalent 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 chosen independently 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 their mixtures.

More preferentially, 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 chosen independently 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 their mixtures.

Even more preferentially, 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) below:

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 alkyl group -C ₄ , preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;

- n and z denote an integer ranging from 2 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; and

- E represents an -OR ₃ -O- group 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 preferentially, the (poly)carbodiimide compound is chosen from the compounds of formula (I) in which:

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

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

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 alkyl group -C ₄ , 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, 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and

- E represents an -OR ₃ -O- group 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 formula (XII) below:

(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 -OR ₃ -O- group 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.

The total quantity of the (poly)carbodiimide compound(s), present in composition A according to the invention, preferably ranges from 0.01 to 40% by weight, more preferably from 0.1 to 30% by weight, better still from 0 5 to 25% by weight, better still from 2 to 20% by weight relative to the total weight of composition A.

The total quantity of the (poly)carbodiimide compound(s), present in the hair coloring composition C according to the invention, preferably ranges from 0.01 to 30% by weight, more preferably from 0.1 to 25% by weight, better from 0.2 to 20% by weight, better still from 1 to 10% by weight relative to the total weight of composition C.

Polymer having at least one carboxylic acid group

Composition B according to the invention used in the context of the hair dyeing process according to the invention comprises at least one polymer having at least one carboxylic acid group.

Preferably, the polymer having at least one carboxylic acid group is chosen from silicone compounds comprising at least one carboxylic group, polyurethanes, acrylic polymers and mixtures thereof.

Polyurethanes and acrylic polymers:

According to a preferred embodiment, composition B comprises one or more polymers having at least one carboxylic acid group chosen from polyurethanes, acrylic polymers and mixtures thereof.

Preferably, the polymer(s) having at least one carboxylic acid group are in the form of aqueous dispersions of particles of polymer(s) chosen from polyurethanes, acrylic polymers, and mixtures thereof.

Preferably, composition B comprises one or more polymers having at least one carboxylic acid group in the form of aqueous dispersions of particles of polyurethanes, acrylic polymers, and mixtures thereof.

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

The aqueous dispersion or dispersions of polymer particles can be chosen from aqueous dispersions of polyurethane particles.

More particularly, the polyurethane(s) present in the aqueous dispersions used in the present invention result from the reaction of

- a prepolymer of formula (A) below:

(HAS),

in which

- R ₁ represents a divalent radical of a dihydroxy compound;

- R ₂ represents a radical of an aliphatic or cycloaliphatic polyisocyanate;

- R ₃ represents a radical of a low molecular weight diol, optionally substituted by one or more ionic groups;

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

- m is greater than 1;

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

H ₂ NR ₄ -NH ₂ (B),

in which R ₄ represents an alkylene or alkylene oxide radical which is not substituted by one or more ionic or potentially ionic groups; and

- at least one chain extender according to the following formula (C):

H ₂ NR ₅ -NH ₂ (C),

in which R ₅ represents an alkylene radical substituted by one or more ionic or potentially ionic groups.

Among the dihydroxylated compounds that can be used according to the present invention, mention may be made in particular of compounds having two hydroxy groups and a number molecular weight of approximately 700 to approximately 16,000, and preferably of approximately 750 to approximately 5,000. example of dihydroxylated compounds having a high molecular weight, mention may be made of polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadienes, polyhydroxylated polythioethers and their mixtures. Preferably, the hydroxylated compounds are chosen from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates and mixtures thereof.

The polyisocyanates which can be used according to the present invention are chosen in particular from organic diisocyanates having a molecular weight of approximately 112 to 1000, and preferably of approximately 140 to 400.

Preferably, the polyisocyanates are chosen from diisocyanates and more particularly from those represented by the general formula R ₂ (NCO) ₂ , in which R ₂ represents a divalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, a cycloaliphatic hydrocarbon group divalent hydrocarbon group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

Preferably, R ₂ represents an organic diisocyanate. By way of example of organic diisocyanates, it is possible in particular to choose tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane, 1,3-bis(isocyanatomethyl)-cyclohexane, 1,4-bis( isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, toluene diisocyanate (TDI) isomers such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate and their mixtures, hydrogenated toluene diisocyanate, 4,4'-diisocyanate diphenyl methane and mixtures with its isomers 2,4-diisocyanate of diphenylmethane and optionally 2,2'-diisocyanate of diphenylmethane, naphthalene-1,5-diisocyanate , and mixtures thereof.

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

By “ low molecular weight diol ” is meant, according to the present invention, a diol having a molecular weight of approximately 62 to 700, and preferably of 62 to 200. These diols can comprise aliphatic, alicyclic or aromatic groups. Preferably, they comprise only aliphatic groups.

Preferably, R ₃ represents a low molecular weight diol having more than 20 carbon atoms, more preferably chosen from ethylene glycol, diethylene glycol, propane 1,2-diol, propane 1,3-diol, butane 1,4-diol, butylene 1,3-glycol, neopentyl glycol, butyl-ethyl-propane diol, cyclohexane diol, 1,4-cyclohexane dimethanol, hexane 1,6-diol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), and mixtures thereof.

Low molecular weight diols may optionally include ionic or potentially ionic groups. Examples of low molecular weight diols containing ionic or potentially ionic groups are in particular described in US Pat. No. 3,412,054. Such compounds are preferably chosen from dimethylol butanoic acid, dimethylol propionic acid, polycaprolactone diols containing a carboxyl group and mixtures thereof.

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

The prepolymer is extended using two families of chain extenders. The first family of chain extenders corresponds to the compounds of general formula (B).

The chain extenders of formula (B) are preferably chosen from alkylene diamines, such as hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine; alkylene oxide diamines, such as 3-{2-[2-(3-aminopropoxy)ethoxy]-ethoxy}propylamine (also called dipropylamine diethylene glycol or DPA-DEG available from Tomah Products, Milton, Wis.) , 2-methyl-1,5-pentanediamine (Dytec A from DuPont), hexane diamine, isophorone diamine, 4,4-methylenedi-(cyclohexylamine), DPA series ether-amines available from Tomah Products, Milton, Wis., such as Dipropylamine Propylene Glycol, Dipropylamine Dipropylene Glycol, Dipropylamine Tripropylene Glycol, Dipropylamine Poly(propylene glycol), Dipropylamine Ethylene Glycol, Dipropylamine Poly(ethylene glycol), Dipropylamine 1,3-propane diol, dipropylamine 2-methyl-1,3-propane diol, dipropylamine 1,4-butane diol, dipropylamine 1,3-butane diol, dipropylamine 1,6-hexane diol and dipropylamine cyclohexane-1,4-dimethanol; and their mixtures.

The second family of chain extenders corresponds to the compounds of general formula (C). Such compounds preferably have one ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Such compounds may optionally comprise two groups reactive with isocyanate groups and an ionic group or capable of forming an ionic group.

The ionic or potentially ionic group can preferably be selected from ternary or quaternary ammonium groups or groups convertible into such groups, a carboxyl group, a carboxylate group, a sulphonic acid group and a sulphonate group. The conversion, at least partial, of the groups convertible into the salt of ternary or quaternary ammonium groups can take place before or during the mixing with water.

The chain extenders of formula (C) are preferably chosen from diaminosulphonates, such as for example the sodium salt of N-(2-aminoethyl)-2-aminoethane sulphonic acid (AAS), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid, and mixtures thereof.

The polyurethane which can be used according to the present invention may optionally also comprise compounds which are respectively located at the ends of the chains and terminate said chains (chain terminators). Such compounds are described in particular in U.S. patents 7,445,770 and/or U.S. 7,452,770.

Preferably, the aqueous dispersion of polyurethane particles has a viscosity of less than 2000 mPa.s at 23° C., more preferably less than 1500, and better still less than 1000. Even more preferably, the aqueous polyurethane dispersion has a glass transition temperature below 0°C.

Also preferably, the aqueous polyurethane dispersion has a polyurethane content (or active material, or dry matter) based on the weight of the dispersion of 20 to 60% by weight, more preferably from 25 to 55% by weight and more preferably from 30 to 50% by weight. By this is meant that the polyurethane content (dry matter) of the aqueous dispersion is preferably from 20% to 60% by weight, more preferably from 25% to 55% by weight and even better from 30% to 50% by weight. , relative to the total weight of the dispersion.

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

The polyurethane particles can have an average diameter ranging up to about 1000 nm, for example from about 50 nm to about 800 nm, better still from about 100 nm to about 500 nm. These particle sizes can be measured with a laser particle sizer (eg Brookhaven BI90).

By way of non-limiting example of aqueous dispersions of polyurethane, mention may be made of those sold under the name Baycusan® by Bayer such as, for example, Baycusan® C1000 (INCI name: polyurethane-34), Baycusan® C1001 (INCI name: polyurethane-34), Baycusan® C1003 (INCI name: polyurethane-32), Baycusan® C1004 (INCI name: polyurethane-35) and Baycusan® C1008 (INCI name: polyurethane-48).

Mention may also be made of aqueous polyurethane dispersions of isophthalic acid/adipic acid/hexylene glycol/neopentyl glycol/dimethylol acid/isophorone-diisocyanate copolymer (INCI name: Polyurethane-1, such as Luviset® PUR, BASF), polyurethane polycarbonate, polyurethane and aliphatic polyurethane aliphatic polyester (such as NEOREZ®, DSM series, such as NEOREZ® R989, NEOREZ® and R-2202).

According to a preferred embodiment, the aqueous dispersion of polyurethane particles can be chosen from aqueous dispersions of particles of compounds having the INCI name polyurethane-35 or compounds having the INCI name polyurethane-34.

Preferably, the polymer(s) having at least one carboxylic acid group are in the form of aqueous dispersions of acrylic polymer particles, more preferably in the form of aqueous dispersions of film-forming acrylic polymer particles.

By " polymer " is meant within the meaning of the invention a compound corresponding to the repetition of one or more units (these units being derived from compounds called monomers). This or these patterns are repeated at least twice and preferably at least 3 times.

The term “film- forming polymer ” is understood to mean 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 keratin materials, and preferably a cohesive film.

By “ acrylic polymer ”, is meant within the meaning of the present invention a polymer synthesized from at least one monomer chosen from (meth)acrylic acid and/or (meth)acrylic acid ester and/or acid amide (meth)acrylic.

The unit or units 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 (meth)acrylic acid esters (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 , aryl (meth)acrylates, in particular C ₆ to C ₁₀ aryl, hydroxyalkyl (meth)acrylates, in particular C ₂ to _C6 .

Among the alkyl (meth) acrylates, mention may be made of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylate, 2-ethylhexyl 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, mention may be made of benzyl acrylate and phenyl acrylate.

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

According to the present invention, the alkyl group of the esters can 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.

As amides of (meth)acrylic acid, mention may for example be made of (meth)acrylamides, as well as N-alkyl (meth)acrylamides, in particular of C ₂ to C ₁₂ alkyl. Among the N-alkyl (meth)acrylamides, mention may be made of N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide and N-undecylacrylamide.

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

The term “ surfactant ” is understood to mean 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 than the compound sold under the trade name LUVIMER MAE by the company BASF, or the Polyacrylate-2 crosspolymer compound sold under the trade name FIXATE SUPERHOLD POLYMER by the company LUBRIZOL, or the Acrylate Copolymer compound sold under the trade name DAITOSOL 3000VP3 by the company DAITO KASEI KOGYO, or else the Acrylate Copolymer compound 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 (meth)acrylic acid and/or (meth)acrylic acid ester and/or (meth)acrylic acid amide monomers.

As additional monomer, mention will be made, for example, of styrene monomers, in particular styrene and 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-alkyl (meth)acrylate monomer ₁ to C ₂₀ , preferably C ₁ to C ₁₀ .

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

As acrylic polymer, mention may be made of the styrene/(meth)acrylate(s) copolymers marketed under the name JONCRYL 77 by the company BASF, under the name YODOSOL GH41F by the company AKZO NOBEL and under the name SYNTRAN 5760 CG by the company INTERPOLYMER .

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

More preferably, composition B 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 matter, or dry matter) content based on the weight of the dispersion of 20 to 60% by weight, more preferably 22 to 55% by weight. weight and more preferably from 25 to 50% by weight.

The total amount of polymer(s) having at least one carboxylic acid group, present in composition B, preferably ranges from 0.2 to 60% by weight, more preferably from 1 to 55% by weight, better still from 5 to 50% by weight, and even more preferably from 10 to 45% by weight relative to the total weight of composition B.

The total quantity of the polymer(s) having at least one carboxylic acid group preferably ranges from 0.1 to 35% by weight, more preferably from 0.5 to 30% by weight, better still from 1 to 25% by weight, and even more preferentially from 3 to 25% by weight, and even better from 5 to 25% by weight relative to the total weight of the hair coloring composition C.

The total quantity of the aqueous dispersion(s) of particles of polymer(s) chosen from polyurethanes, acrylic polymers, and mixtures thereof preferably ranges from 0.2 to 60% by weight, more preferably from 1 to 55% by weight, better still from 5 to 50% by weight, and even more preferably from 10 to 45% by weight relative to the total weight of composition B.

According to a particular embodiment, the total quantity of the aqueous dispersion(s) of particles of acrylic polymer(s) preferably ranges from 0.2 to 60% by weight, more preferably from 1 to 55% by weight, better still from 5 to 50% by weight, and even more preferably from 10 to 45% by weight relative to the total weight of composition B.

The total amount of the aqueous dispersion(s) of particles of polymer(s) chosen from polyurethanes, acrylic polymers, and mixtures thereof preferably ranges from 0.1 to 35% by weight, more preferably from 0.5 to 30% by weight, even more preferably from 1 to 25% by weight, and even more preferably from 3 to 25% by weight, and even better from 10 to 25% by weight relative to the total weight of composition C.

According to a particular embodiment, the total quantity of the aqueous dispersion(s) of particles of acrylic polymer(s) preferably ranges from 0.1 to 35% by weight, more preferably from 0 5 to 30% by weight, better still from 1 to 25% by weight, and even more preferably from 3 to 25% by weight, and even better from 10 to 25% by weight relative to the total weight of the coloring composition capillary c.

Non-silicone fatty substances

According to the present invention, composition A and/or B comprise at least one non-silicone fatty substance, that is to say a fatty substance not comprising any silicon atoms, in a total content greater than or equal to 0, 1% by weight relative to the total weight of composition A and/or B.

By non-silicone fatty substance is meant an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mm Hg) (solubility less than 5% by weight and preferably 1% by even more preferably at 0.1% by weight). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms. In addition, non-silicone fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as chloroform, ethanol, benzene, petroleum jelly or decamethylcyclopentasiloxane.

By “oil” is meant a “fatty substance” which is liquid at ambient temperature (25° C.), and at atmospheric pressure (760 mm Hg or 1.013.105 Pa).

More particularly, the non-silicone fatty substances are chosen from C6-C16 hydrocarbons, hydrocarbons with more than 16 carbon atoms, non-silicone oils of animal origin, triglycerides of vegetable or synthetic origin, fluorinated oils, fatty alcohols, fatty acids, fatty acid and/or fatty alcohol esters different from triglycerides, non-silicone waxes, different from solid fatty alcohols and solid synthetic esters, and mixtures thereof.

It is recalled that within the meaning of the invention, the alcohols, esters and fatty acids have more particularly at least one hydrocarbon group, linear or branched, saturated or unsaturated, comprising 6 to 30 carbon atoms, optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds can comprise one to three carbon-carbon double bonds, conjugated or not.

The linear or branched hydrocarbons, of mineral or synthetic origin, with more than 16 carbon atoms, are preferably chosen from paraffin or petroleum jelly oils, polydecenes, hydrogenated polyisobutene such as Parléam, and mixtures thereof.

As regards the lower C6-C16 alkanes, the latter are linear, branched, possibly cyclic. By way of example, mention may be made of hexane, cyclohexane, undecane, dodecane, tridecane, isoparaffins such as isohexadecane, isodecane, isododecane and their mixtures.

The triglycerides of vegetable or synthetic origin are preferably chosen from liquid triglycerides of fatty acids comprising from 6 to 30 carbon atoms such as triglycerides of heptanoic or octanoic acids or, more particularly, from those present in vegetable oils such as as, for example, sunflower, corn, soya, pumpkin, grapeseed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado, jojoba oil, shea butter oil or synthetic triglycerides of caprylic/capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, and their mixtures.

The fluorinated oils can be chosen from perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, sold under the names “FLUTEC® PC1” and “FLUTEC® PC3” by the company BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names “PF 5050®” and “PF 5060®” by the company 3M, or else bromoperfluorooctyl sold under the name “FORALKYL®” by the company Atochem; nonafluoro-methoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name "PF 5052®" by the company 3M.

The fatty alcohols suitable for the implementation of the invention are more particularly chosen from saturated or unsaturated, linear or branched alcohols, comprising from 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, preferably from 12 to 22 carbon atoms, better from 14 to 18 carbon atoms. Mention may be made, for example, of cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol, linolenic alcohol, ricinoleic alcohol, undecylenic alcohol or linoleic alcohol and mixtures thereof.

The fatty acids which can be used in the context of the invention are more particularly chosen from carboxylic acids, saturated or unsaturated, comprising from 6 to 30 carbon atoms, in particular from 8 to 30 carbon atoms. They are advantageously chosen from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid, caprylic acid, capric acid, lauric acid.

Preferably, the fatty acid(s) are in the non-salified form with organic or mineral bases in the composition of the invention.

As regards the esters of fatty acids and/or fatty alcohols, different from the triglycerides mentioned above and vegetable waxes, mention may be made in particular of the esters of saturated or unsaturated aliphatic mono or polyacids, linear C1-C26, or branched C3-C26 and saturated or unsaturated aliphatic mono or polyalcohols, linear C1-C26, or branched C3-C26, the total carbon number of the esters being greater than or equal to 6, more advantageously greater than or equal to 10.

Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl acetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate , mirystyl, stearyl hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and mixtures thereof.

Still within the framework of this variant, it is also possible to use the esters of di or tricarboxylic acids in C4-C22 and of alcohols in C1-C22 and the esters of mono di or tricarboxylic acids and of alcohols di, tri, tetra or pentahydroxy C2-C26.

Mention may in particular be made of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate, tridecyl erucate; triisopropyl citrate; triisotearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisanonate; and polyethylene glycol distearates and mixtures thereof.

Among the esters mentioned above, it is preferred to use ethyl, isopropyl, myristyl, cetyl, stearyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, myristates of alkyls such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate, cetyl octanoate and mixtures thereof.

The composition may also comprise, as fatty ester, esters and di-esters of sugars of C6-C30 fatty acids, preferably C12-C22. It is recalled that the term "sugar" means oxygenated hydrocarbon compounds which have several alcohol functions, with or without an aldehyde or ketone function, and which contain at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.

Suitable sugars include, for example, sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and derivatives thereof. in particular alkylated, such as methylated derivatives such as methylglucose.

The esters of sugars and fatty acids can be chosen in particular from the group comprising the esters or mixtures of esters of sugars described previously and of C6-C30 fatty acids, preferably C12-C22, linear or branched, saturated or unsaturated. If they are unsaturated, these compounds can comprise one to three carbon-carbon double bonds, conjugated or not.

The esters according to this variant can also be chosen from mono-, di-, tri- and tetra-esters, polyesters and mixtures thereof.

These esters can be for example oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonates, or their mixtures such as in particular the mixed oleo-palmitate, oleo-stearate, palmito-stearate esters.

More particularly, the mono- and di-esters and in particular the mono- or di-oleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, of sucrose, of glucose or of methylglucose are used.

Mention may be made, by way of example, of the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

Mention may also be made, by way of examples of esters or mixtures of fatty acid sugar esters:

- the products sold under the names F160, F140, F110, F90, F70, SL40 by the company Crodesta, respectively designating sucrose palmito-stearates formed from 73% monoester and 27% di- and tri-ester, from 61 % monoester and 39% di-, tri-, and tetra-ester, 52% monoester and 48% di-, tri-, and tetra-ester, 45% monoester and 55% di-, tri-, and tetra-ester, 39% monoester and 61% di-, tri-, and tetra-ester, and sucrose monolaurate;

the products sold under the name Ryoto Sugar Esters, for example referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% di-triester-polyester;

the sucrose mono-di-palmito-stearate marketed by the company Goldschmidt under the name Tegosoft® PSE.

The non-silicone wax or waxes different from solid fatty alcohols and solid synthetic esters are chosen in particular from Carnauba wax, Candelila wax, and Alfa wax, paraffin wax, ozokerite, waxes vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax or absolute flower waxes such as the essential wax of blackcurrant flower sold by the company BERTIN (France), animal waxes such as waxes of bees, or modified beeswax (cerabellina); other waxes or waxy raw materials that can be used according to the invention are in particular marine waxes such as that sold by the company SOPHIM under the reference M82, polyethylene or polyolefin waxes in general.

The fatty substance(s) do not comprise any C2-C3 oxyalkylenated unit, in particular they do not contain oxyethylenated, oxypropylene and/or glycerolated units.

The non-silicone fatty substances are preferably chosen from C6-C16 hydrocarbons, hydrocarbons with more than 16 carbon atoms, non-silicone oils of animal origin, triglycerides of vegetable or synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, fatty acids or mixtures thereof, more preferably among fatty alcohols, fatty acids and fatty acid and/or fatty alcohol esters and mixtures thereof, preferably C12-C22, preferably C14-C18.

Advantageously, the total content of the non-silicone fatty substance(s) ranges from 0.1 to 20% by weight, preferably from 0.25 to 15% by weight, preferably from 0.5 to 10% by weight relative to the total weight of composition A and/or composition B.

According to a particular embodiment, the fatty substance or substances are present in composition B, preferably only in composition B.

When composition C resulting from the mixture of composition A and composition B is applied to the hair, the total content of the non-silicone fatty substance(s) ranges from 0.05 to 10% by weight, preferably from 0. 1 to 8% by weight, preferably from 0.2 to 5% by weight relative to the total weight of composition C.

Coloring agents

Composition A and/or composition B used in the context of the treatment process according to the invention comprises at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof. According to one particular embodiment, composition A and/or B comprises at least one pigment, optionally one or more direct dyes.

According to a particular embodiment, the coloring agent is present in composition B. According to a preferred variant, the coloring agent is present only in composition B.

Preferably, composition B according to the invention comprises one or more pigments. According to a preferred variant, composition B contains at least one pigment, optionally one or more direct dyes. According to a second preferred variant, composition B is as defined previously and composition A contains neither pigment nor direct dye.

Pigments

By “pigment”, is meant all the pigments providing color to keratin materials. Their solubility in water at 25° C. and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

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

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.

The pigments can for example be chosen from mineral pigments, organic pigments, lakes, special effect pigments such as nacres or glitter, and mixtures thereof.

The pigment can be an inorganic pigment. By mineral pigment, we mean any pigment that meets the definition of the Ullmann encyclopedia in the chapter inorganic pigment. Mention may be made, among the mineral pigments useful in the present invention, of 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 of the Ullmann encyclopedia in the organic pigment chapter.

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

In particular, the white or colored organic pigments can 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, orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, 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.

By way of example, mention may also be made of organic pigment pigment pastes such as the products sold by the company HOECHST under the name:

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

- COSMENYL G YELLOW: 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);

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

- COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

The pigments in accordance with the invention can also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments can be composed in particular of particles comprising an inorganic core, at least one binder ensuring the fixing organic pigments on the core, and at least one organic pigment at least partially covering the core.

The organic pigment can also be a lake. By lacquer, we mean the dyes adsorbed on insoluble particles, the assembly thus obtained remaining insoluble during use.

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

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

As examples of lacquers, mention may be made of the product known under the following name: D & C Red 7 (CI 15 850:1).

The pigment may also be a special effect pigment. By special effect pigments, we mean pigments that generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) which is not uniform and changes according to the conditions of observation (light, temperature , viewing angles, etc.). They are therefore opposed to colored pigments which provide a uniform opaque, semi-transparent or classic 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 nacres, interference pigments or glitter.

As examples of special effect pigments, mention may be made of pearlescent pigments such as mica covered with titanium, or bismuth oxychloride, colored pearlescent pigments such as mica covered with titanium and iron oxides, mica covered with iron oxide, mica covered with titanium and in particular with ferric blue or chromium oxide, mica covered with titanium and an organic pigment as defined previously as well as pearlescent pigments based on bismuth oxychloride. As pearlescent pigments, mention may be made of Cellini nacres marketed by BASF (Mica-TiO ₂ -lacquer), Prestige marketed by Eckart (Mica-TiO ₂ ), Prestige Bronze marketed by Eckart (Mica-Fe ₂ O ₃ ) Colorona marketed by Merck (Mica-TiO ₂ -Fe ₂ O ₃ ).

Mention may also be made of the gold-colored nacres marketed by the company BASF under the name of Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne) ; the mother-of-pearl bronzes 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 nacres sold 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); the brown nacres in particular marketed by the company BASF under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); mother-of-pearl with a copper sheen in particular marketed by the company BASF under the name Copper 340A (Timica); nacres with a red sheen in particular marketed by the company MERCK under the name Sienna fine (17386) (Colorona); nacres with a yellow sheen in particular marketed by the company BASF under the name Yellow (4502) (Chromalite); nacres of a red tint with a gold sheen in particular marketed by the company BASF under the name Sunstone G012 (Gemtone); the pink nacres in particular marketed by the company BASF under the name Tan opale G005 (Gemtone); black mother-of-pearl with a gold sheen in particular marketed by the company BASF under the name Nu antique bronze 240 AB (Timica), blue mother-of-pearl in particular marketed by the company MERCK under the name Matte blue (17433) (Microna), white mother-of-pearl with sheen silver in particular marketed by the company MERCK under the name Xirona Silver and the orange-pink golden-green nacres in particular marketed by the company MERCK under the name Indian summer (Xirona) and mixtures thereof.

Still by way of example of nacres, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

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

Finally, as examples of nacres, mention may also be made of polyethylene terephthalate flakes, in particular those marketed by the company Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver flakes). One can also consider multilayer pigments based on synthetic substrates such as alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

The special effect pigments can also be chosen from reflective particles, that is to say in particular particles whose size, structure, in particular the thickness of the layer or layers which constitute it and their physical and chemical natures, and the surface finish, allow them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create on the surface of the composition or mixture, when the latter is applied to the support to be made up, highlights visible to the naked eye, that is i.e. brighter points that contrast with their surroundings by seeming to shine.

The reflective particles can 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, in particular be in the form of platelets or globular, in particular spherical.

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

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

When the reflective particles have a multilayer structure, these 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 of at least one metal or metallic material . The substrate can be monomaterial, multimaterial, 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 mixtures thereof, this list not being limiting.

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

Reflective particles are described in particular in the 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, mention may also be made of particles comprising a borosilicate substrate coated with silver.

Particles with a glass substrate coated with silver, in the form of platelets, are sold under the name MICROGLASS METASHINE REFSX 2025 PS by the company TOYAL. Particles with a glass substrate coated with a nickel/chromium/molybdenum alloy are sold under the name CRYSTAL STAR GF 550, GF 2525 by this same company.

It is also possible to use particles comprising a metal 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 metal oxide such as titanium oxide, aluminum oxide, iron oxide, cerium, chromium oxide, silicon oxides and mixtures thereof.

Mention may be made, by way of example, of the aluminum, bronze or copper powders coated with SiO ₂ marketed under the name VISIONAIRE by the company ECKART.

Mention may also be made of pigments with an interference effect not fixed on a substrate, such as liquid crystals (Helicones HC from Wacker), holographic interference flakes (Geometric Pigments or Spectra f/x from Spectratek). Special effect pigments also include fluorescent pigments, whether fluorescent in daylight or which produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, marketed for example by the Quantum Dots Corporation.

The variety of pigments which 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 their agglomeration or flocculation. This dispersing agent may be a surfactant, an oligomer, a polymer or a mixture of several of them, bearing one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can cling physically or chemically to the surface of the pigments. These dispersants also have at least one functional group that is compatible or soluble in the continuous medium. In particular, use is made of esters of 12-hydroxystearic acid in particular and of C8 to C20 fatty acid and of polyol such as glycerol, diglycerin, such as poly(12-hydroxystearic) acid stearate of molecular weight of approximately 750 g/mole such as that sold under the name Solsperse 21,000 by the company Avecia, polygyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel or polyhydroxystearic acid such as than that sold under the reference Arlacel P100 by the company Uniqema and their mixtures.

As other dispersant which can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17000 sold by the company Avecia, mixtures of polydimethylsiloxane/oxypropylene 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 pigments previously surface-treated useful in the context of the invention are pigments which have undergone totally or partially a surface treatment of a chemical, electronic, electro-chemical, mechano-chemical or mechanical nature, with an organic agent such as those which are 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 can for example be 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 aluminum salts of fatty acids, for example aluminum 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 in commerce.

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 molecules of the surfactant or creation of a covalent bond between the surfactant and the pigments.

The 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 the fillers. This method is described in particular in US patent 4,578,266.

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

The surface treatment agent can 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. weight of the total weight of surface-treated pigment.

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

- a PEG-Silicone treatment such as 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 copolymer/dimethicone and perfluoalkyl phosphate 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 such as 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 such as 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 in composition B.

By “sub-micronic” or in English “sub-micronic” is meant pigments whose particle size has been micronized by the 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 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) can therefore have a silicone backbone, such as silicone polyether and dispersants of the amino-silicone type. 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 one particular embodiment, the dispersing agent(s) are of the amino-silicone type and are cationic.

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

In a 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 or pigments are mineral pigments.

Direct dye

By “direct dye”, we mean natural and/or synthetic dyes, different from oxidation dyes. These are dyes that will diffuse superficially on the fiber. Direct dyes are generally at least partially soluble in water and/or solvent.

They can be ionic or nonionic, preferably cationic or nonionic.

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

The direct dyes are preferably cationic direct dyes. Mention may be made of the cationic hydrazono dyes of formulas (III) and (IV), the cationic azo dyes (V) and (VI) below:

(III),

(IV),

(V),

(VI),

formulas (III) to (VI) in which:

- Het+ represents a cationic heteroaryl radical, preferably with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally substituted preferably by at least one (C ₁ -C ₈ )alkyl group such as methyl;

- Ar+ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge, preferably ammonium, particularly tri(C ₁ -C ₈ )alkyl-ammonium such as trimethylammonium;

- Ar represents an aryl group, in particular phenyl, optionally substituted, preferably by one or more electron-donating groups such as i) (C ₁ -C ₈ )alkyl optionally substituted, ii) (C ₁ -C ₈ )alkoxy optionally substituted, iii) (di)(C ₁ -C ₈ )(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(C ₁ -C ₈ )alkylamino, v) N-(C ₁ -C ₈ ) alkyl-N-aryl (C ₁ -C ₈ ) alkylamino optionally substituted or else Ar represents a julolidine group;

- Ar'' represents an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl optionally substituted, preferably by one or more (C ₁ -C ₈ )alkyl, hydroxyl, (di)(C ₁ -C ₈ )(alkyl )amino, (C ₁ -C ₈ )alkoxy or phenyl;

- Ra and Rb, identical or different, representing a hydrogen atom or a (C ₁ -C ₈ )alkyl group optionally substituted, preferably by a hydroxyl group;

or else the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar form together with the atoms which carry them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group optionally substituted by a hydroxyl group;

- Q- represents an organic or inorganic anionic counterion such as a halide or an alkyl sulfate.

In particular, mention may be made of direct dyes with an endocyclic cationic charge, azoic and hydrazono, of formula (III) to (VI) as defined above; more particularly, the cationic direct dyes with an endocyclic cationic charge described in patent applications WO 95/15144, WO 95/01772 and EP-714954; preferably the following direct dyes:

(VII),

(VIII),

Formulas (VII) and (VIII) in which:

- R ¹ represents a (C ₁ -C ₄ )alkyl group such as methyl;

- R ² and R ³ , which are identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl; and

- R ⁴ represents a hydrogen atom or an electron-donating group such as (C ₁ -C ₈ )alkyl optionally substituted, (C ₁ -C ₈ )alkoxy optionally substituted, (di)(C ₁ -C ₈ )(alkyl) amino optionally substituted on the alkyl group(s) by a hydroxyl group; particularly R ⁴ is a hydrogen atom,

- Z represents a CH group or a nitrogen atom, preferably CH,

- Q- is an anionic counter ion as defined above, particularly a halide such as chloride or an alkyl sulphate such as methyl sulphate or mesytyl.

In particular, the dyes of formula (V) and (VI) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives with Q′ an anionic counterion as defined previously, particularly halide such as chloride or a alkyl sulfate such as methyl or mesyl sulfate.

The direct dyes can 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. By anionic direct dyes is meant any direct dye comprising in its structure at least one CO ₂ R or SO ₃ R substituent with R designating a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion . The anionic dyes can 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 acid dyes useful in the invention, mention may be made of the dyes of formulas (IX), (IX′), (X), (X′), (XI), (XI′), (XII), (XII) '), (XIII), (XIV), (XV) and (XVI) following:

diaryl anionic azo dyes of formula (IX) or (IX')
(IX),

(IX'),

formulas (IX) and (IX') in which:

- R ₇ , R ₈ , R ₉ , R ₁₀ , R' ₇ , R' ₈ , R' ₉ and R' ₁₀ , which are identical or different, represent a hydrogen atom or a group chosen from: alkyl, alkoxy, alkylthio , hydroxy, mercapto, nitro, nitroso;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;

- (O)CO--, M+ with M+ as defined previously;

- R''-S(O) ₂ -, with R'' representing a hydrogen atom, an alkyl group, an aryl group, (di) (alkyl) amino, aryl (alkyl) amino; preferably a phenylamino or phenyl group;

- R'''-S(O) ₂ -X'- with R''' representing an optionally substituted alkyl or aryl group, X' as defined above;

- (di)(alkyl)amino;

- aryl(alkyl)amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O-)-, M+ and iv) alkoxy with M+ as defined previously;

- optionally substituted heteroaryl; preferentially a benzothiazolyl group;

- cycloalkyl, in particular cyclohexyl;

- Ar-N=N- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl, (O) ₂ S(O-)-, M+ or phenylamino groups;

- or else two contiguous groups R ₇ with R ₈ or R ₈ with R ₉ or R ₉ with R ₁₀ together form a fused benzo A'group; and R' ₇ with R' ₈ or R' ₈ with R' ₉ or R' ₉ with R' ₁₀ together form a fused group benzo B'; with A' and B' optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O-)-, M+; iv) hydroxy; (v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X', X'' and Ar as defined previously;

- W represents a sigma σ bond, an oxygen or sulfur atom, or a divalent radical i) –NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb identical or different, representing a hydrogen atom or an aryl group, or else Ra and Rb form together with the carbon atom which carries them a cycloalkyl spiro; preferentially W represents a sulfur atom or Ra and Rb together form a cyclohexyl;

it being understood that the formulas (IX) and (IX') comprise at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical (O)CO--, M+ on one of the rings A, A ', B, B' or C; preferentially sodium sulfonate.

Examples of dyes of formula (IX) include: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, 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; and by way of example of dyes of formula (IX′), mention may be made of: Acid Red 111, Acid Red 134, Acid yellow 38;

b) the anionic azo pyrrazolone dyes of formula (X) and (X'):

(X),

(X'),

formulas (X) and (X') in which:

- R ₁₁ , R ₁₂ and R ₁₃ , which are identical or different, represent a hydrogen or halogen atom, an alkyl group or -(O) ₂ S(O-), M+ with M+ as defined previously;

- R ₁₄ represents a hydrogen atom, an alkyl group or a -C(O)O- group, M+ with M+ as defined above;

- R ₁₅ represents a hydrogen atom;

- R ₁₆ represents an oxo group in which case R' ₁₆ is absent, or else R ₁₅ with R ₁₆ together form a double bond;

- R ₁₇ and R ₁₈ , identical or different, represent a hydrogen atom, or a group chosen from:

- (O) ₂ S(O-)-, M+ with M+ as defined previously;

- Ar-OS(O) ₂ - with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups;

- R ₁₉ and R ₂₀ together form either a double bond or a benzo group D', optionally substituted;

- R′ ₁₆ , R′ ₁₉ and R′ ₂₀ , which are identical or different, represent a hydrogen atom or an alkyl or hydroxy group;

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

- Ra and Rb which are identical or different, are as defined above, preferably Ra represents a hydrogen atom and Rb represents an aryl group;

- Y represents either a hydroxy group or an oxo group;

- represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group;

it being understood that the formulas (X) and (X') comprise at least one sulphonate radical (O)2S(O-)-, M+ or a carboxylate radical -C(O)O-, M+ on one of the rings D or E ; preferentially sodium sulfonate;

By way of example of dyes of formula (X), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and by way of example of dyes of formula (X'), mention may be made of: Acid Yellow 17;

c) anthraquinone dyes of formula (XI) and (XI'):

(XI),

(XI'),

formulas (XI) and (XI') in which:

- R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ , identical or different, represent a hydrogen atom, halogen atom, or a group chosen from:

- alkyl;

- hydroxy, mercapto;

- alkoxy, alkylthio;

- optionally substituted aryloxy or arylthio, preferentially substituted by one or more groups chosen from alkyl and (O) ₂ S(O-)-, M+ with M+ as defined previously;

- aryl(alkyl)amino optionally substituted by one or more groups chosen from alkyl and (O) ₂ S(O-)-, M+ with M+ as defined above;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino

- (O) ₂ S(O-)-, M+ with M+ as defined above;

- Z' represents a hydrogen atom or an NR ₂₈ R ₂₉ group with R ₂₈ and R ₂₉ , which are identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- polyhydroxyalkyl such as hydroxyethyl;

- aryl optionally substituted by one or more particularly i) alkyl groups such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O-)-, M+ with M+ as previously defined; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R°, X, X' and X'' as defined above, preferably R° represents an alkyl group;

- cycloakyl, in particular cyclohexyl;

- Z represents a group chosen from hydroxy and NR′ ₂₈ R′ ₂₉ with R′ ₂₈ and R′ ₂₉ , which are identical or different, represent the same atoms or groups as R ₂₈ and R ₂₉ as defined previously;

it being understood that the formulas (XI) and (XI') comprise at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferably sodium sulfonate;

Examples of dyes of formula (XI) include: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT purple #2; and by way of example of dyes of formula (XI′), mention may be made of: Acid Black 48;

d) nitro dyes of formula (XII), (XII'):

(XII),

(XII'),

formulas (XII) and (XII') in which:

- R ₃₀ , R ₃₁ and R ₃₂ , which are identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl;

- alkoxy optionally substituted by one or more hydroxy groups, alkylthio optionally substituted by one or more hydroxy groups;

- hydroxy, mercapto;

- nitro, nitroso;

- polyhaloalkyl;

- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’- with R°; X, X' and X'' as previously defined;

- (O) ₂ S(O-)-, M+ with M+ as defined above;

- (O)CO--, M+ with M+ as defined above;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

- heterocycloalkyl such as piperidino, piperazino or morpholino; particularly R ₃₀ , R ₃₁ and R ₃₂ represent a hydrogen atom;

- Rc and Rd, identical or different, represent a hydrogen atom or an alkyl group;

- W is as defined above; W particularly represents an –NH– group;

- ALK represents a divalent linear or branched, C ₁ -C ₆ alkylene group; particularly ALK represents a -CH ₂ -CH ₂ - group;

- n is 1 or 2;

- p represents an integer comprised inclusively between 1 and 5;

- q represents an integer comprised inclusively between 1 and 4;

- u is 0 or 1;

- when n is 1, J represents a nitro or nitroso group; especially nitro;

- when n is 2, J represents an oxygen or sulfur atom, or a divalent radical –S(O)m– with m representing an integer 1 or 2; preferably J represents a –SO ₂ – radical;

- M' represents a hydrogen atom or a cationic counterion;

- present or absent represents a benzo group optionally substituted by one or more R ₃₀ groups as defined above,

it being understood that the formulas (XII) and (XII') comprise at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferentially sodium sulfonate.

By way of example of dyes of formula (XII), mention may be made of: Acid Brown 13; Acid Orange 3; as examples of dyes of formula (XII'), mention may be made of: Acid Yellow 1, Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino 5-nitro benzene acid 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;

e) triarylmethane dyes of formula (XIII):

(XIII),

formula (XIII) in which:

- R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ , which are identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted by an (O)mS(O-)-, M+ group with M+ and m as defined previously;

- R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ , identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- (di)(alkyl)amino;

- hydroxy, mercapto;

- nitro, nitroso;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;

- (O)CO--, M+ with M+ as defined above;

- or else two contiguous groups R ₄₁ with R ₄₂ or R ₄₂ with R ₄₃ or R ₄₃ with R ₄₄ together form a fused benzo group: I'; with I′ optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O-)-, M+; iv) hydroxy; (v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; with M+, R°, X, X', X'' as defined previously;

in particular R ₃₇ to R ₄₀ represent a hydrogen atom, and R ₄₁ to R ₄₄ , which are identical or different, represent a hydroxy or (O) ₂ S(O-)-, M+ group; and when R ₄₃ with R ₄₄ together form a benzo group, it is preferentially substituted by an (O) ₂ S(O-)- group;

it being understood that at least one of the rings G, H, I or I' comprises at least one sulphonate radical (O) ₂ S(O-)- or a carboxylate radical -C(O)O-; preferentially sulfonate.

By way of example of dyes of formula (XIII), mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50.

f) dyes derived from xanthene of formula (XIV):

(XIV),

formula (XIV) in which:

- R ₄₅ , R ₄₆ , R ₄₇ and R ₄₈ , identical or different, represent a hydrogen atom or a halogen atom;

- R ₄₉ , R ₅₀ , R ₅₁ and R ₅₂ , which are identical or different, represent a hydrogen or halogen atom, or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxy, mercapto;

- nitro, nitroso;

- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;

- (O)CO--, M+ with M+ as defined above;

particularly R ₄₉ , R ₅₀ , R ₅₁ and R ₅₂ represent a hydrogen or halogen atom;

- G represents an oxygen or sulfur atom or an NRe group with Re as defined previously; particularly G represents an oxygen atom;

- L represents an alcoholate O-, M+; an S-, M+ thioalcoholate or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined previously; M+ is particularly sodium or potassium;

- L' represents an oxygen or sulfur atom or an ammonium group: N+RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an optionally substituted alkyl or aryl group; L' represents in particular an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (O)mS(O-)-, M+ with m and M+ as defined above;

- Q and Q', identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;

- M+ is as defined above.

By way of example of dyes of formula (XIV), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

g) dyes derived from indole of formula (XV):

(XV),

formula (XV) in which:

- R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ and R ₆₀ , identical or different, represent a hydrogen atom or a group chosen from:

- alkyl;

- alkoxy, alkylthio;

- hydroxy, mercapto;

- nitro, nitroso;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;

- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;

- (O)CO--, M+ with M+ as defined above;

- G represents an oxygen or sulfur atom or an NRe group with Re as defined previously; particularly G represents an oxygen atom;

- Ri and Rh, identical or different, represent a hydrogen atom or an alkyl group;

it being understood that formula (XIII) comprises at least one sulphonate radical (O)2S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferentially sodium sulphonate.

By way of example of dyes of formula (XV), mention may be made of: Acid Blue 74;

h) dyes derived from quinoline of formula (XVI):

(XVI),

formula (XVI) in which:

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

- R ₆₂ , R ₆₃ , and R ₆₄ , identical or different, represent a hydrogen atom or a (O) ₂ S(O-)- group, M+ with M+ representing a hydrogen atom or a cationic counterion ;

or else R ₆₁ with R ₆₂ , or R ₆₁ with R ₆₄ , together form a benzo group optionally substituted by one or more (O) ₂ S(O-)- groups, M+ with M+ representing a hydrogen atom or a counter -cationic ion;

it being understood that formula (XVI) comprises at least one sulphonate radical (O) ₂ S(O-)-, M+, preferably sodium sulphonate.

Examples of dyes of formula (XVI) 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, purpurogalline, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine, orceins. It is also possible to use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

Preferably, the direct dyes are chosen from anionic direct dyes.

The coloring agent(s) may be present in a total content ranging from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, relative to the total weight of composition A and/or of composition B.

The pigment(s) may be present in a total content ranging from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, better still from 5 to 15% by weight relative to the total weight of the composition A and/or composition B.

The direct dye(s) may be present in a total content ranging from 0.001 to 10% by weight of the total weight of the composition, preferably from 0.005 to 5% by weight of the total weight of composition A and/or of composition B .

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

The pigment(s) may be present in a total content 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 content ranging from 0.001 to 10% by weight of the total weight of the composition, preferably from 0.005 to 5% by weight of the total weight of composition C.

Silicones

According to a particular embodiment, one and/or the other of compositions A and B also comprise at least one silicone, different from the polymer(s) having at least one carboxylic acid group described above.

This silicone can be chosen from non-amino silicones, amino silicones and mixtures thereof.

The silicones can be solid or liquid at 25° C. and atmospheric pressure (1.013.105 Pa), volatile or non-volatile.

The silicones which may be used may be soluble or insoluble in the composition according to the invention; they can be in the form of oil, wax, resin or gum; silicone oils are preferred.

Silicones are in particular described in detail in Walter NOLL's work "Chemistry and Technology of Silicones" (1968), Academie Press.

Preferably, one and/or the other of compositions A and B contains one or more silicones that are liquid at 25° C. and atmospheric pressure (1.013.105 Pa).

The volatile silicones can be chosen from those having a boiling point of between 60 and 260° C. (at atmospheric pressure), more particularly from:
i) cyclic polydialkylsiloxanes comprising from 3 to 7 silicon atoms, preferably 4 to 5, such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

Mention may be made of the products marketed under the name "VOLATILE SILICONE 7207" by UNION CARBIDE or "SILBIONE 70045 V 2" by RHODIA, "VOLATILE SILICONE 7158" by UNION CARBIDE, "SILBIONE 70045 V 5" by RHODIA.

- cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type with a chemical structure:

Preferably cyclomethylsiloxane.

Mention may be made of "VOLATILE SILICONE FZ 3109" marketed by the company UNION CARBIDE.

- mixtures of cyclic silicones with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1'-(hexa-2, 2,2',2',3,3'-trimethylsilyloxy) bis-neopentane;

ii) linear polydialkylsiloxanes having 2 to 9 silicon atoms, which generally have a viscosity less than or equal to 5×10 ⁻⁶ m ² /s at 25° C., such as decamethyltetrasiloxane.

Other silicones falling into this class are described in the article published in Cosmetics and toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics"; mention may be made of the product marketed under the name "SH 200" by the company TORAY SILICONE.

Among the non-volatile silicones, mention may be made, alone or as a mixture, of polydialkylsiloxanes and in particular polydimethylsiloxanes (PDMS), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, as well as organopolysiloxanes (or organomodified polysiloxanes, or even organomodified silicones) which are polysiloxanes comprising in their structure one or more organofunctional groups, generally attached via a hydrocarbon group, and preferably chosen from aryl groups, amino groups, alkoxy groups and polyoxyethylenated groups, or polyoxypropylene. Preferably, the non-volatile silicones are chosen from optionally oxyethylenated and oxypropylene polydimethyl/methylsiloxanes.

The organomodified silicones can be polydiarylsiloxanes, in particular polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned above. The polyalkylarylsiloxanes are particularly chosen from polydimethyl/methylphenylsiloxanes, linear and/or branched polydimethyl/diphenylsiloxanes.

Among the organomodified silicones, mention may be made of organopolysiloxanes comprising:
- polyoxyethylene and/or polyoxypropylene groups optionally comprising C ₆ -C ₂₄ alkyl groups such as dimethicone-copolyols, and in particular those marketed by DOW CORNING under the name DC 1248 or SILWET® L 722, L 7500 oils , L 77, L 711 from UNION CARBIDE; or alternatively (C12)alkyl-methicone-copolyols, and in particular those marketed by the company DOW CORNING under the name Q2-5200;
- substituted or unsubstituted amino groups, in particular C1-C4 aminoalkyl groups; mention may be made of the products marketed under the name GP4 Silicone Fluid and GP7100 by the company GENESEE, or under the names Q2-8220 and DC929 or DC939 by the company DOW CORNING;
- thiol groups, such as the products marketed under the names "GP 72 A" and "GP 71" from GENESEE;
- alkoxylated groups, such as the product marketed under the name "SILICONE COPOLYMER F-755" by SWS SILICONES and ABIL WAX® 2428, 2434 and 2440 by the company GOLDSCHMIDT;
- hydroxyl groups, such as polyorganosiloxanes with a hydroxyalkyl function;
- acyloxyalkyl groups such as the polyorganosiloxanes described in US-A-4957732.
- anionic groups of the carboxylic acid type, as for example described in EP186507, or of the alkyl-carboxylic type such as the product X-22-3701E from the company SHIN-ETSU; or else of the 2-hydroxyalkylsulfonate or 2-hydroxyalkylthiosulfate type, such as the products marketed by the company GOLDSCHMIDT under the names "ABIL® S201" and "ABIL® S255",
- hydroxyacylamino groups, such as the polyorganosiloxanes described in application EP342834; mention may be made, for example, of the product Q2-8413 from the company DOW CORNING.

The silicones may also be chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups. Among these polydialkylsiloxanes, mention may be made of the following commercial products:
- SILBIONE® oils of the 47 and 70 047 series or MIRASIL® oils marketed by RHODIA such as, for example oil 70 047 V 500 000;
- the oils of the MIRASIL® series marketed by the company RHODIA;
- the oils of the 200 series from the company DOW CORNING such as DC200 having a viscosity of 60,000 mm2/s;
- VISCASIL® oils from GENERAL ELECTRIC and certain oils from the SF series (SF 96, SF 18) from GENERAL ELECTRIC.

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known under the name of dimethiconol (CTFA), such as the oils of the 48 series from the company RHODIA.

In this class of polydialkylsiloxanes, mention may also be made of the products marketed under the names “ABIL WAX® 9800 and 9801” by the company GOLDSCHMIDT, which are polydialkyl (C1-C20) siloxanes.

Products which can be used more particularly in accordance with the invention are mixtures such as:
- the mixtures formed from a polydimethylsiloxane hydroxylated at the end of the chain, or dimethiconol (CTFA) and a cyclic polydimethylsiloxane also called cyclomethicone (CTFA) such as the product Q2-1401 marketed by the company DOW CORNING,
- mixtures formed from a polydimethylsiloxane hydroxylated at the end of the chain, or dimethiconol (CTFA) and a polydimethylsiloxane also called dimethicone (CTFA) such as the product Xiameter® PMX-1503 Fluid marketed by the company DOW CORNING.

The polyalkylarylsiloxanes are particularly chosen from polydimethyl/methylphenylsiloxanes, linear and/or branched polydimethyl/diphenylsiloxanes with a viscosity ranging from 1.10 ^-5 to 5.10 ^-2 m²/s at 25°C.

Among these polyalkylarylsiloxanes, mention may be made of the products marketed under the following names:
- SILBIONE® oils of the 70 641 series from RHODIA;
- oils of the RHODORSIL® 70 633 and 763 series from RHODIA;
- DOW CORNING 556 COSMETIC GRAD FLUID oil from DOW CORNING;
- BAYER's PK series silicones such as the PK20 product;
- the silicones of the PN and PH series from BAYER such as the PN1000 and PH1000 products;
- certain oils from GENERAL ELECTRIC's SF series such as SF 1023, SF 1154, SF 1250, SF 1265.

Preferably, one and/or the other of compositions A and B comprises at least one amino silicone. The term " amino silicone " denotes any silicone comprising at least one primary, secondary, tertiary amine or a quaternary ammonium group.

The weight average molecular masses of these amino silicones can be measured by Gel Permeation Chromatography (GPC) at ambient temperature (25° C.) in polystyrene equivalent. The columns used are μ styragel columns. The eluent is THF, the flow rate is 1 ml/min. 200 μl of a 0.5% by weight solution of silicone in THF are injected. Detection is done by refractometry and UVmetry.

Preferably, the amino silicone(s) capable of being used in the context of the invention are chosen from:

a) the polysiloxanes corresponding to the formula (A):

in which x' and y' are integers such that the weight-average molecular weight (Mw) is between 5,000 and 500,000 approximately;

b) amino silicones corresponding to formula (B):

R'aG3-a-Si(OSiG2)n-(OSiGbR'2-b)m-O-SiG3-a-R'a (B)

in which :
- G, identical or different, denotes a hydrogen atom, a phenyl group, OH, C ₁ -C ₈ alkyl, for example methyl, or C ₁ -C ₈ alkoxy, for example methoxy,
- a, identical or different, designates 0 or an integer from 1 to 3, in particular 0,
- b denotes 0 or 1, in particular 1,
- m and n are numbers such that the sum (n + m) varies from 1 to 2000, in particular from 50 to 150, n being able to designate a number from 0 to 1999, and in particular from 49 to 149 and m being able to designate a number from 1 to 2000, and in particular from 1 to 10;
- R', identical or different, denotes a monovalent radical of formula -CqH2qL in which q is a number ranging from 2 to 8, and L is an optionally quaternized amino group chosen from the groups: -N(R")2; - N+(R")3 A-; -NR"-QN(R")2 and -NR"-Q-N+(R")3 A-, in which R", identical or different, denotes hydrogen, phenyl, benzyl, or a monovalent saturated hydrocarbon radical, by example a C ₁ -C ₂₀ alkyl radical; Q denotes a group of formula C _r H _2r , linear or branched, r being an integer ranging from 2 to 6, preferably from 2 to 4; and A- represents an anion cosmetically acceptable, in particular halide such as fluoride, chloride, bromide or iodide.

Preferably, the amino silicone(s) are chosen from the amino silicones of formula (B). Preferably, the amino silicones of formula (B) are chosen from the amino silicones corresponding to the following formulas (C), (D), (E), (F) and/or (G).

According to a first embodiment, the amino silicones corresponding to formula (B) are chosen from silicones called "trimethylsilylamodimethicone" corresponding to formula (C):

in which m and n are numbers such that the sum (n + m) varies from 1 to 2000, in particular from 50 to 150, n possibly denoting a number from 0 to 1999, and in particular from 49 to 149 and m possibly denoting a number from 1 to 2000, and in particular from 1 to 10.

According to a second embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of formula (D) below:

in which :
- m and n are numbers such that the sum (n+m) varies from 1 to 1000, in particular from 50 to 250 and more particularly from 100 to 200; n possibly denoting a number from 0 to 999 and in particular from 49 to 249 and more particularly from 125 to 175 and m possibly denoting a number from 1 to 1000, in particular from 1 to 10, more particularly from 1 to 5;
- R ₁ , R ₂ , R ₃ , identical or different, represent a hydroxy or C ₁ -C ₄ alkoxy radical, at least one of the radicals R ₁ to R ₃ designating an alkoxy radical.

Preferably the alkoxy radical is a methoxy radical.

The hydroxy/alkoxy molar ratio preferably ranges from 0.2:1 to 0.4:1 and preferably from 0.25:1 to 0.35:1 and more particularly is equal to 0.3:1.

The weight-average molecular mass (Mw) of these silicones preferably ranges from 2,000 to 1,000,000, more particularly from 3,500 to 200,000.

According to a third embodiment, the amino silicones corresponding to formula (B) are chosen from the following silicones of formula (E):

in which :
- p and q are numbers such that the sum (p+q) varies from 1 to 1000, in particular from 50 to 350, and more particularly from 150 to 250; p possibly denoting a number from 0 to 999 and in particular from 49 to 349 and more particularly from 159 to 239 and q possibly denoting a number from 1 to 1000, in particular from 1 to 10 and more particularly from 1 to 5;
- R ₁ , R ₂ , different, represent a hydroxy or alkoxy radical in C ₁ -C ₄ , at least one of the radicals R ₁ or R ₂ designating an alkoxy radical.

Preferably the alkoxy radical is a methoxy radical.

The hydroxy/alkoxy molar ratio generally ranges from 1:0.8 to 1:1.1 and preferably from 1:0.9 to 1:1 and more particularly is equal to 1:0.95.

The weight-average molecular mass (Mw) of the silicone preferably ranges from 2000 to 200000 and even more particularly from 5000 to 100000 and more particularly from 10000 to 50000.

Commercial products comprising silicones of structure (D) or (E) can include in their composition one or more other amino silicones whose structure is different from formulas (D) or (E).

A product containing amino silicones of structure (D) is offered by WACKER under the name BELSIL® ADM 652.

A product containing amino silicones of structure (E) is offered by WACKER under the name Fluid WR 1300® or else under the name Belsil ADM Log 1.

When these amino silicones are implemented, a particularly advantageous embodiment is their use in the form of an oil-in-water emulsion. The oil-in-water emulsion can comprise one or more surfactants. The surfactants can be of any kind, but preferably cationic and/or nonionic. The number average size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nanometers. Preferably, in particular as amino silicones of formula (E), use is made of microemulsions whose mean particle size ranges from 5 nm to 60 nanometers (limits included) and more particularly from 10 nm to 50 nanometers (limits included). Thus, it is possible to use, according to the invention, the amino silicone microemulsions of formula (E) offered under the names FINISH CT 96 E® or SLM 28020® by the company WACKER.

According to a fourth embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of following formula (F):

in which :
- m and n are numbers such that the sum (n + m) varies from 1 to 2000 and in particular from 50 to 150, n being able to designate a number from 0 to 1999 and in particular from 49 to 149 and m being able to designate a number from 1 to 2000, and in particular from 1 to 10;
- A denotes a linear or branched alkylene radical having from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably linear.

The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 2000 to 1000000 and even more particularly from 3500 to 200000.

Another silicone corresponding to formula (B) is for example XIAMETER MEM 8299 EMULSION from DOW CORNING (INCI name amodimethicone and trideceth-6 and cetrimonium chloride).

According to a fifth embodiment, the amino silicones corresponding to formula (B) are chosen from the silicones of following formula (G):

in which :
- m and n are numbers such that the sum (n + m) varies from 1 to 2000 and in particular from 50 to 150, n being able to designate a number from 0 to 1999 and in particular from 49 to 149 and m being able to designate a number from 1 to 2000, and in particular from 1 to 10;
- A denotes a linear or branched alkylene radical having from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably branched.

The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 500 to 1,000,000 and even more particularly from 1,000 to 200,000.

A silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from DOW CORNING.

c) amino silicones corresponding to the formula (H):

in which :
- R ₅ represents a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, and in particular a C ₁ -C ₁₈ alkyl radical, or a C ₂ -C ₁₈ alkenyl radical, for example methyl;
- R ₆ represents a divalent hydrocarbon radical, in particular a C ₁ -C ₁₈ alkylene radical or a divalent C ₁ -C ₁₈ alkyleneoxy radical, for example C ₁ -C ₈ linked to Si by an SiC bond;
- Q- is an anion such as a halide ion, in particular chloride or an organic acid salt, in particular acetate;
- r represents an average statistical value ranging from 2 to 20, in particular from 2 to 8;
- s represents an average statistical value ranging from 20 to 200, in particular from 20 to 50.

Such amino silicones are described in particular in US Pat. No. 4,185,087.

- d) quaternary ammonium silicones of formula (I):

in which :
- R ₇ , which are identical or different, represent a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, and in particular a C ₁ -C ₁₈ alkyl radical, a C ₂ -C ₁₈ alkenyl radical or a ring comprising 5 or 6 carbon atoms, for example methyl;
- R ₆ represents a divalent hydrocarbon radical, in particular a C ₁ -C ₁₈ alkylene radical or a divalent C ₁ -C ₁₈ alkyleneoxy radical, for example C ₁ -C ₈ linked to Si by an SiC bond;
- R ₈ , which are identical or different, represent a hydrogen atom, a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, and in particular a C ₁ -C ₁₈ alkyl radical, a C ₂ -C ₁₈ alkenyl radical , an -R ₆ -NHCOR ₇ radical;
- X- is an anion such as a halide ion, in particular chloride or an organic acid salt, in particular acetate;
- r represents an average statistical value ranging from 2 to 200, in particular from 5 to 100.

These silicones are for example described in application EP-A-0530974.

e) amino silicones of formula (J):

in which :
- R ₁ , R ₂ , R ₃ and R ₄ , which are identical or different, denote a C ₁ -C ₄ alkyl radical or a phenyl group,
- R ₅ denotes a C ₁ -C ₄ alkyl radical or a hydroxyl group,
- n is an integer ranging from 1 to 5,
- m is an integer ranging from 1 to 5, and
- x is chosen such that the amine number varies from 0.01 to 1 meq/g.

f) multiblock polyoxyalkylenated amino silicones, of (AB) _n type, A being a polysiloxane block and B being a polyoxyalkylenated block comprising at least one amine group.

Said silicones preferably consist of repeating units of the following general formulas:

[-(SiMe ₂ O) _x SiMe ₂ - R -N(R")- R'-O(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b -R'-N(H)-R- ]

or

[-(SiMe ₂ O)xSiMe ₂ - R -N(R")- R' - O(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b -]

in which :
- a is an integer greater than or equal to 1, preferably ranging from 5 to 200, more particularly ranging from 10 to 100;
- b is an integer between 0 and 200, preferably ranging from 4 and 100, more particularly between 5 and 30;
- x is an integer ranging from 1 to 10000, more particularly from 10 to 5000;
- R" is a hydrogen atom or a methyl;
- R, identical or different, represent a divalent hydrocarbon radical C ₂ -C ₁₂ , linear or branched, optionally comprising one or more heteroatoms such as oxygen; preferably, R denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical, or a CH ₂ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ - radical; preferably R denotes a CH ₂ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ - radical;
- R′, which are identical or different, represent a C ₂ -C ₁₂ divalent hydrocarbon radical, linear or branched, optionally comprising one or more heteroatoms such as oxygen; preferably, R' denotes an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical, or a CH ₂ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ - radical; preferably R' denotes -CH(CH ₃ )-CH ₂ -.

The siloxane blocks preferably represent 50 and 95% by mole of the total weight of the silicone, more particularly from 70 to 85% by mole.

The amine content is preferably between 0.02 and 0.5 meq/g of copolymer in a 30% solution in dipropylene glycol, more particularly between 0.05 and 0.2.

The weight-average molecular mass (Mw) of the silicone is preferably between 5,000 and 1,000,000, more particularly between 10,000 and 200,000.

Mention may in particular be made of the silicones marketed under the names Silsoft A-843 or Silsoft A+ by Momentive.

g) and mixtures thereof.

Preferably, the amino silicones of formula (B) are chosen from the amino silicones corresponding to the formula (E).

Preferably, the composition according to the invention comprises at least one amino silicone with INCI name amodimethicone, preferably introduced in the form of an emulsion or microemulsion with surfactants.

Preferably, the composition according to the invention comprises at least one amino silicone with INCI name amodimethicone in emulsion or microemulsion with surfactants with INCI name trideceth-5 and trideceth-10.

The silicone(s) may be present in a total amount varying from 0.01% to 20% by weight, preferably from 0.05 to 15% by weight, more preferably from 0.1 to 10% by weight, more preferably still from 0.5 to 5% by weight relative to the total weight of composition A and/or of composition B.

The silicone(s) may be present in a total amount varying from 0.01% to 20% by weight, preferably from 0.05 to 15% by weight, more preferably from 0.1 to 10% by weight, more preferably still from 0.5 to 5% by weight relative to the total weight of the hair coloring composition C.

The amino silicone(s) may be present in a total amount varying from 0.01% to 20%, preferably from 0.05 to 15%, more preferably from 0.1 to 10%, more preferably still from 0.5 to 5% by weight relative to the total weight of the hair coloring composition C.

Organic solvents

One and/or the other of compositions A and B used in the context of the process according to the invention may comprise one or more organic solvents.

By way of organic solvent, mention may be made, for example, of the lower C ₁ -C ₄ alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

Preferably, the composition comprises one or more organic solvents chosen from C ₁ -C ₄ lower alkanols, more preferably ethanol.

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

Composition A and/or composition B according to the invention is preferably aqueous. The water content can range from 20 to 99% by weight, preferably from 50 to 98% by weight, more preferably from 60 to 95% by weight relative to the total weight of composition A and/or composition B.

Scent

Composition A and/or composition B according to the invention may also comprise one or more perfumes. We mean any perfume or aroma likely to give off a pleasant odor.

Perfumes are compositions containing in particular the raw materials described in S. Arctander, Perfume and Flavor Chemicals ( Montclair , NJ, 1969 ), in S. Arctander, Perfume and Flavor Materials of Natural Origin ( Elizabeth, NJ, 1960 ) and in “ Flavor and Fragrance Materials – 1991”, Allured Publishing Co. Wheaton, Ill.

These can be natural products, such as essential oils, absolutes, resinoids, resins, concretes, and/or synthetic products, such as terpene or sesquiterpene hydrocarbons, alcohols, phenols, aldehydes, ketones, ethers, acids, esters, nitriles, peroxides, saturated or unsaturated, aliphatic or cyclic.

According to the definition given in the international standard ISO 9235 and adopted by the European Pharmacopoeia Commission, an essential oil is an odorous product generally of complex composition, obtained from a botanically defined plant raw material, either by steam distillation of water, either by dry distillation or by an appropriate mechanical process without heating (cold expression). The essential oil is most often separated from the aqueous phase by a physical process that does not lead to a significant change in composition.

The choice of the method of obtaining essential oils depends mainly on the raw material: its original state and its characteristics, its nature itself. The “essential oil/vegetable raw material” yield can be extremely variable depending on the plant: 15 ppm to more than 20%. This choice conditions the characteristics of the essential oil, in particular viscosity, color, solubility, volatility, enrichment or impoverishment in certain constituents.

Steam distillation corresponds to the vaporization in the presence of water vapor of a substance that is not very miscible with water. The raw material is placed in the presence of boiling water or steam in a still. The water vapor drives the essential oil vapor which is condensed in the cooler to be recovered in the liquid phase in a Florentine vase (or essence) where the essential oil is separated from the water by decantation. We call "aromatic water" or "hydrosol" or "floral distilled water", the aqueous distillate which remains after steam distillation, once the separation of the essential oil has been carried out.

Obtaining by dry distillation consists in obtaining the essential oil by distillation of wood, bark or roots, without adding water or water vapor in a closed enclosure designed so that the liquid is recovered in its lower part. Cade oil is the best-known example of this mode of production.

The method of obtaining by cold expression only applies to citrus fruits (Citrus spp) by mechanical processes at room temperature. The principle of the method is as follows: the peels are chopped up and the contents of the secretory pockets which have been ruptured are recovered by a physical process. The classic process consists of exerting an abrasive action under a stream of water on the entire surface of the fruit. After removal of solid waste, the essential oil is separated from the aqueous phase by centrifugation. Most industrial installations actually allow the simultaneous or sequential recovery of fruit juices and essential oil.

Essential oils are generally volatile and liquid at room temperature, which differentiates them from so-called fixed oils. They are more or less colored and their density is generally lower than that of water. They have a high refractive index and most bend polarized light. They are fat-soluble and soluble in the usual organic solvents, entrainable with water vapour, very slightly soluble in water.

Among the essential oils that can be used according to the invention, mention may be made of those obtained from plants belonging to the following botanical families: Abietaceae or Pinaceae, for example conifers; Amaryllidaceae; Anacardiaceae; Anonaceae, for example ylang; Apiaceae, for example Umbelliferae, in particular dill, angelica, coriander, samphire, carrot or parsley; Araceae; Aristolochiaceae; Asteraceae for example yarrow, mugwort, chamomile, and helichrysum; Betulaceae; Brassicaceae; Burseraceae, for example frankincense; Caryophyllaceae; Canellaceae; Caesalpiniaceae, for example copaïfera (copahu); Chenopodaceae; Cistaceae for example the cistus; Cyperaceae; Dipterocarpaceae; Ericaceae eg wintergreen (wintergreen); Euphorbiaceae; Fabaceae; Geraniaceae for example geranium; Guttiferae; Hamamelidaceae; Hernandiaceae; Hypericaceae, for example St. John's wort; Iridaceae; Juglandaceae; Lamiaceae, e.g. thyme, oregano, monarda, savory, basil, marjoram, mint, patchouli, lavender, sage, catnip, rosemary, hyssop, lemon balm, rosemary ; Lauraceae, for example ravensara, laurel, rosewood, cinnamon, litsea; Liliaceae, for example garlic; Magnoliaceae, for example the magnolia; Malvaceae; Meliaceae; Monimiaceae; Moraceae, for example hemp, or hops; Myricaceae; Mysristicaceae, for example nutmeg; Myrtaceae, for example eucalyptus, tea tree, niaouli, cajeput, backousia, cloves, myrtle; Oleaceae; Piperaceae, for example pepper; Pittosporaceae; Poaceae, for example lemongrass, lemongrass, vetiver; Polygonaceae; Ranunculaceae; Rosaceae, for example roses; Rubiaceae; Rutaceae, for example all citrus; Salicaceae; Santalaceae, for example sandalwood; Saxifragaceae; Schisandraceae; Styracaceae, for example benzoin; Thymelaceae, for example agarwood; Tilliaceae; Valerianaceae, for example valerian, nard; Verbenaceae, for example lantana, verbena; Purplish; Zingiberaceae, for example galangal, turmeric, cardamom, ginger; Zygophyllaceae.

We can also mention essential oils extracted from flowers (lily, lavender, rose, jasmine, ylang-ylang, neroli), stems and leaves (patchouli, geranium, petitgrain), fruits (coriander, anise, cumin, juniper), fruit peels (bergamot, lemon, orange), roots (angelica, celery, cardamom, iris, sweet flag, ginger), wood (pine wood, sandalwood, guaiac wood, pink cedar, camphor), d herbs and grasses (tarragon, rosemary, basil, lemongrass, sage, thyme), needles and branches (spruce, fir, pine, dwarf pine), resins and balms (galbanum, elemi, benzoin, myrrh , olibanum, opopanax).

Examples of fragrancing substances entering into the constitution of perfumes are in particular: geraniol, geranyl acetate, farnesol, borneol, bornyl acetate, linalool, linalyl acetate, linalyl propionate, linalyl butyrate, tetrahydrolinalool, citronellol, citronellyl acetate, citronellyl formate, citronellyl propionate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol, terpineol, terpinyl acetate, nopol, nopyl acetate, nerol, neryl acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicylate, dimethylbenzyl-carbinol, trichloromethylphenylcarbinyl acetate, p-tert-butylcyclohexyl acetate, isononyl acetate, vetiveryl acetate, vetiverol, alpha-hexylcinnamaldehyde, 2-methyl-3-(p-tert-butylphenyl)propanal, 2-methyl-3-(p-isopropylphenyl)propanal, 3-(p-tert-butylphenyl)-propanal, 2,4-dimethylcyclohex-3-enyl-carboxaldehyde, tricyclodecenyl acetate, tricyclodecenyl propionate , 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde, 4-(4-methyl-3-pentenyl)-3-cyclohexenecarboxaldehyde, 4-acetoxy-3-pentyl-tetrahydropyran, 3-carboxymethyl -2-pentylcyclopentane, 2-n-4-heptylcyclo-pentanone, 3-methyl-2-pentyl-2-cyclopentenone, menthone, carvone, tagetone, geranyl acetone, n-decanal, n- dodecanal, 9-decenol-1, phenoxyethyl isobutyrate, phenyl-acetaldehyde dimethyl-acetal, phenylacetaldehyde diethylacetal, geranonitrile, citronellonitrile, cedaryl acetate, 3-isocamphylcyclohexanol, cedaryl methyl ether, l isolongifolanone, hawpinonitrile, hawthorn, heliotropin, coumarin, eugenol, vanillin, diphenyl ether, citral, citronellal, hydroxycitronellal, damascone, ionones, me thylionones, isomethylionones, solanone, irones, cis-3-hexenol and its esters, musks-indanes, musks-tetralins, musks-isochromans, macrocyclic ketones, musks-macrolactones, aliphatic musks, ethylene brassylate and mixtures thereof.

According to a preferred embodiment of the invention, a mixture of different perfuming substances is used which together generate a pleasant note for the user.

Thus, according to a preferred embodiment, the perfumed composition comprises at least 1% by weight of a mixture of fragrant substances, in particular of at least two distinct fragrant substances, relative to the total weight of the composition, and preferably of at least three distinct fragrant substances.

The fragrant substances will preferably be chosen so that they produce notes (head, heart and base) in the following families: citrus fruits, aromatics, floral notes, in particular pink flowers and white flowers, spices, woody , gourmands, chypres, ferns, leathers, and musks.

In general, a perfumed composition useful in the invention comprises between 0.01% and 10% by weight of perfuming substance(s), preferably from 0.05 to 5%, preferentially between 0.1 and 3% by weight of fragrancing substance(s).

Additives

One and/or the other of compositions A and B used in the context of the process according to the invention may contain any adjuvant or additive usually used.

Among the additives which may be used, mention may be made of reducing agents, softeners, anti-foaming agents, moisturizing agents, UV filters, peptizers, solubilizers, perfumes, anionic or cationic surfactants, nonionic or amphoteric, proteins, vitamins, polymers other than the polymers described above, thickening, associative or non-associative polymers, preservatives, oils, waxes and mixtures thereof.

One and/or the other of compositions A and B may (may) be present in particular in the form of a suspension, dispersion, gel, emulsion, in particular an oil-in-water emulsion (O/W) or water -in-oil (W/O), or multiple (W/O/W or polyol/O/W or O/W/O), in the form of cream, mousse, stick, dispersion of vesicles, in particular lipids ionic or not, biphase or multiphase 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 of the intended application for the composition.

In the process of the invention, according to a particular embodiment, composition A comprises a polycarbodiimide compound and composition B comprises at least one polymer comprising at least one carboxylic group and at least one pigment, optionally at least one direct dye. According to a variant, composition B comprises at least one polymer comprising at least one carboxylic group, at least one fatty substance and at least one pigment, optionally at least one direct dye.

According to a variant, composition A does not contain any coloring agent and composition B is as defined previously.

According to one embodiment, one and/or the other of compositions A and B comprise at least one non-volatile silicone, preferably an amino silicone, for example of the amodimethicone type or a hydroxylated silicone, for example of the dimethiconol type, or a silicone amino and hydroxylated. According to one particular embodiment, composition A comprises a (poly)carbodiimide compound and an aminated and/or hydroxylated silicone. According to another embodiment, composition B comprises a coloring agent, at least 0.1% of non-silicone fatty substance, at least one non-silicone polymer containing a carboxylic group.

Optional application of a composition D

The hair dyeing process according to the invention may also comprise a step of applying to the hair keratin fibers a composition D comprising at least one silicone polymer comprising at least one carboxylic group.

Silicone compounds with carboxylic functions

The term "carboxylic group" means a COOH or COO ^- functional group, the counter-ion of the COO ^- group being able to be chosen from alkali metals, alkaline-earth metals, quaternary ammoniums.

The silicones that can be used can be soluble or insoluble in composition D; they can be in the form of oil, wax, resin or gum; silicone oils and gums are preferred.

Silicones are in particular described in detail in Walter NOLL's work "Chemistry and Technology of Silicones" (1968), Academie Press.

Preferably, the silicone compound(s) comprising at least one carboxylic group are chosen from the organosiloxanes of formula (XXVII) below:

(XXVII)

in which :
- R1 independently represent an alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms; a hydroxy group; an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms;
- R2 independently represents an R4-COOM group with R4 representing a linear or branched alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from the atom of sulfur, the nitrogen atom, the oxygen atom and their mixtures, and M representing a hydrogen atom; an alkali or alkaline-earth metal or a quaternary ammonium NR′3, with identical or different R′ representing H or alkyl having from 1 to 4 carbon atoms; a pyrrolidone radical comprising a carboxylic group COOH or a Ra-(ORb)x-COOM group with Ra representing a linear or branched alkylene group having from 1 to 4 carbon atoms, Rb representing an alkyl group having from 1 to 4 atoms carbon, x being an integer ranging from 1 to 200; and M representing a hydrogen atom, an alkali or alkaline-earth metal or a quaternary ammonium NR′ ₃ , with identical or different R′ representing H or an alkyl having from 1 to 4 carbon atoms;
- R3 independently represent an alkyl group having 1 to 20 carbon atoms; a hydroxy group; an R4-COOM group with R4 representing a linear or branched alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from the sulfur atom, the nitrogen atom, oxygen atom and mixtures thereof, and M representing a hydrogen atom; an alkali or alkaline-earth metal or a quaternary ammonium NR′ ₃ , with identical or different R′ representing H or alkyl having from 1 to 4 carbon atoms; an alkoxy group having 1 to 20 carbon atoms; an aryl group having from 6 to 12 carbon atoms or an R _a -(OR _b ) _x -COOM group with R _a representing a linear or branched alkylene group having from 1 to 4 carbon atoms, R _b representing a group alkyl having 1 to 4 carbon atoms, x being an integer ranging from 1 to 200; and M representing a hydrogen atom, an alkali or alkaline-earth metal or a quaternary ammonium NR′ ₃ , with identical or different R′ representing H or an alkyl having from 1 to 4 carbon atoms;
- n denotes an integer ranging from 1 to 1000;
- p denotes an integer ranging from 0 to 1000;
it being understood that at least one of the radicals R2 and/or R3 comprises a carboxylic group COOH or COOM with M representing an alkali or alkaline-earth metal or a quaternary ammonium NR′ ₃ , with R′ identical or different, representing H or a alkyl having 1 to 4 carbon atoms.

In particular, the silicone compound(s) comprising at least one carboxylic group can be chosen from the organosiloxanes of formula (XXVIII) below:

(XXVIII),

in which :
- R1 independently represents an alkyl group, linear or branched, having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms even better from 1 to 6 carbon atoms; preferentially methyl;
- R4 independently represents a linear or branched alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from the sulfur atom, the nitrogen, the oxygen atom and their mixtures; or else a divalent group R _a -(OR _b ) _x - with R _a representing a linear or branched alkylene group having from 1 to 4 carbon atoms, R _b representing an alkylene group having from 1 to 4 carbon atoms, and x being an integer ranging from 1 to 200;
- M independently represents a hydrogen atom, an alkali or alkaline-earth metal or a quaternary ammonium NR′ ₃ , with R′ identical or different, representing H or an alkyl having from 1 to 4 carbon atoms;
- n denotes an integer ranging from 1 to 1000;

- the organosiloxanes of the following formula (XXIX):

(XXIX)

in which :
- R1 independently represents an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably a methyl;
- R4 represents a linear or branched, saturated or unsaturated alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from the sulfur atom, the nitrogen atom, oxygen atom and their mixtures; or else a divalent group R _a -(OR _b ) _x - with R _a representing a linear or branched alkylene group having from 1 to 4 carbon atoms, R _b representing an alkylene group having from 1 to 4 carbon atoms, and x being an integer ranging from 1 to 200;
- M represents a hydrogen atom; an alkali or alkaline-earth metal or a quaternary ammonium NR' ₃ , with identical or different R' , representing H or an alkyl having from 1 to 4 carbon atoms;
- p denotes an integer ranging from 1 to 1000;
- n denotes an integer ranging from 1 to 1000;

- the organosiloxanes of the following formula (XXX):

(XXX)

in which :
- R1 independently represents an alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, even better from 1 to 6 carbon atoms; preferentially methyl;
- R4 represents a linear or branched alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from sulfur atom, nitrogen atom , the oxygen atom and their mixtures; or else a divalent group R _a -(OR _b ) _x - with R _a representing a linear or branched alkylene group having from 1 to 4 carbon atoms, R _b representing an alkylene group having from 1 to 4 carbon atoms, and x being an integer ranging from 1 to 200;
- R3 represents an alkyl group having 1 to 20 carbon atoms; an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms;
- M independently represents a hydrogen atom, an alkali or alkaline-earth metal or a quaternary ammonium NR′ ₃ , with R′ identical or different, representing H or an alkyl having from 1 to 4 carbon atoms;
- n denotes an integer ranging from 1 to 1000;

- the organosiloxanes of formula (XXXI) below:

(XXXI)

in which :
- R8 represents an alkyl group having 1 to 6 carbon atoms, preferably a methyl;
- m denotes an integer ranging from 1 to 1000;
- n designates an integer ranging from 1 to 1000.

-and mixtures thereof.

Among the organosiloxanes of formula (XXVIII), mention may be made of polydimethylsiloxanes (PDMS) with a carboxy terminal function such as the compounds sold by the company Momentive under the trade name SILFORM INX (INCI name: Bis-Carboxydecyl dimethicone).

Among the organosiloxanes of formula (XXIX), mention may be made of polydimethylsiloxanes (PDMS) with a pendent carboxy function such as the compounds sold by the company Shin Etsu under the trade name X-22-3701E.

Among the organosiloxanes of formula (XXX), mention may be made of polydimethylsiloxanes (PDMS) with a carboxy terminal function such as the compounds sold by the company Shin Etsu under the trade name X-22-3710.

Among the organosiloxanes of formula (XXXI), mention may be made of the compounds sold by the company Grant Industries under the trade name Grandsil SiW-PCA-10 (INCI name: Dimethicone (and) PCA Dimethicone (and) Butylene Glycol (and) Decyl Glucoside ).

The silicone compounds comprising a carboxylic group can for example correspond to the compounds described in patent application EP186507 in the name of Chisso Corporation introduced here by reference.

Preferably, the silicone compound(s) comprising at least one carboxylic group are chosen from organopolysiloxanes of formula (XXVIII), organopolysiloxanes of formula (XXIX) and mixtures thereof.

More preferentially, the silicone compound(s) comprising at least one carboxylic group are chosen from the organopolysiloxanes of formula (XXIXa) below:

(XXIXa)

in which :
- R4 represents a linear or branched, saturated or unsaturated alkylene group, having from 1 to 20 carbon atoms, preferably from 4 to 16 carbon atoms, optionally interrupted by at least one heteroatom chosen from the sulfur atom, the nitrogen atom, oxygen atom and their mixtures, even from 8 to 12 carbon atoms;
- p denotes an integer ranging from 1 to 1000;
- n denotes an integer ranging from 1 to 1000.

The total amount of silicone compound(s) comprising at least one carboxylic group, present in composition D, preferably ranges from 0.01 to 20% by weight, more preferably from 0.1 to 15% by weight, and better still from 0.5 to 10% by weight, relative to the total weight of composition D.

Composition D comprises one or more oil(s). More preferentially, composition D comprises one or more oil(s) chosen from alkanes.

By “ oil ”, is meant a fatty substance that is liquid at ambient temperature (25° C.) and at atmospheric pressure (760 mm Hg or 1.013 10 5 Pa).

The oil can be volatile or non-volatile.

By “ volatile oil ”, is meant an oil capable of evaporating on contact with the skin in less than one hour, at ambient temperature and atmospheric pressure. Volatile oil is a volatile cosmetic oil, liquid at room temperature. More specifically, a volatile oil has an evaporation rate of between 0.01 and 200 mg/cm ² /min, limits included (see protocol for measuring the evaporation rate indicated in the text below).

By “ non-volatile oil ”, is meant an oil remaining on the skin or the keratin fiber at ambient temperature and atmospheric pressure. More specifically, a non-volatile oil has an evaporation rate strictly lower than 0.01 mg/cm2/min.

Preferably, the composition comprises one or more oil(s) chosen from C ₆ -C ₁₆ alkanes and/or mixtures thereof. the latter can be linear, branched, possibly cyclic.

Mention may in particular be made of branched C ₈ -C ₁₆ alkanes such as C ₈ -C ₁₆ iso-alkanes (also called isoparaffins), isododecane, isodecane, isohexadecane and, for example, the oils sold under the names commercial Isopars or Permetyls, and mixtures thereof.

Mention may also be made of linear alkanes, preferably of plant origin, comprising from 7 to 15 carbon atoms, in particular from 9 to 14 carbon atoms, and more particularly from 11 to 13 carbon atoms.

By way of example of a linear alkane suitable for the invention, mention may be made of n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14), -pentadecane (C15), and mixtures thereof, and in particular the mixture of n -undecane (C11) and n-tridecane (C13) described in example 1 of application WO2008/155059 from Cognis.

Mention may also be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97, as well as their mixtures.

By way of example of alkanes suitable for the invention, mention may be made of the alkanes described in patent applications WO 2007/068371 and WO2008/155059. These alkanes are obtained from fatty alcohols, themselves obtained from copra or palm oil.

According to a particular embodiment, the composition comprises isododecane. Such a compound is for example isododecane sold under the reference ISODODECANE by INEOS.

Preferably, composition D comprises one or more oil(s) chosen from C ₈ -C ₁₆ alkanes, more preferably from isododecane, isohexadecane, tetradecane and/or mixtures thereof.

More preferentially, composition D comprises isododecane.

Composition D may comprise one or more oils present in a total amount of between 30% and 99% by weight, preferably between 50% and 99% by weight, better still between 70% and 99% by weight relative to the total weight of composition D.

Composition D may comprise at least at least one coloring agent as described previously.

Protocols

As indicated above, compositions A and B can be applied to the hair keratin fibres, such as the hair, sequentially, in any order, or even simultaneously.

According to a variant of the invention, compositions A and B are applied sequentially to the hair keratin fibres, such as the hair, in any order, that is to say that composition A can be applied to the hair keratin fibers before composition B or vice versa.

According to a particular embodiment, the invention is a hair coloring process, comprising:
i) the application to the hair keratin fibers of composition A or of composition B, in which:
composition A comprises at least one (poly)carbodiimide compound as described above,

composition B includes:
- at least 0.1% by weight of one or more non-silicone fatty substance(s) and;

- at least one polymer having at least one carboxylic acid group, as described above, preferably a polymer containing a carboxylic or carboxylate function, in particular a poly(meth)acrylate as described above; and

- at least at least one coloring agent chosen from pigments and direct dyes;

ii) the application to said hair keratin fibers of composition B, if composition A was applied during step i) or of composition A if composition B was applied during step i).

Preferably, the invention is a hair coloring process, comprising:
i) the application to the hair keratin fibers of composition A or of composition B, in which:
composition A comprises at least one (poly)carbodiimide compound as described above, at least one non-volatile silicone,

composition B includes:
- at least 0.1% by weight of one or more non-silicone fatty substances chosen from fatty acids, fatty alcohols, fatty acid and/or fatty alcohol esters, preferably C12-C-22;

- at least one polymer having at least one carboxylic acid group, as described above, preferably a polymer containing a carboxylic or carboxylate function, in particular a poly(meth)acrylate as described above;

- at least at least one pigment;

ii) optionally an exposure time of said composition A or of said composition B on the fibers from 1 minute to 30 minutes, preferably from 1 to 20 minutes; then

iii) optionally a step of washing, rinsing, spinning or drying said fibers, preferably a drying step, then

iv) the application to said hair keratin fibers of composition B, if composition A was applied during step i) or of composition A if composition B was applied during step i), then

v) optionally a step of washing, rinsing, spinning or drying said fibers, preferably a drying step, then

vi) the application to said hair keratin fibers of a composition D comprising at least one silicone polymer comprising at least one carboxylic group as described previously; then
viii) optionally, an exposure time for said composition D on the fibers of from 1 minute to 30 minutes, preferably from 1 to 20 minutes; then
viii) optionally a step of washing, rinsing, spinning or drying said fibers.

According to another variant of the invention, and preferably, compositions A and B are applied simultaneously.

According to another embodiment, the compositions A and B are mixed extemporaneously at the time of use to obtain the hair coloring composition C.

Hair coloring composition C and optional composition D described above can be used on dry or wet keratin hair fibers, as well as on all types of fibers, light or dark, natural or colored, permed, bleached or straightened.

According to a preferred embodiment, the hair dye composition C and the composition D are applied simultaneously to the hair keratin fibers.

According to another preferred embodiment, composition D is applied to the hair keratin fibers after applying hair dye composition C to the hair keratin fibers.

According to another preferred embodiment, composition D is applied to the hair keratin fibers before applying hair dye composition C to the hair keratin fibers.

According to a particular embodiment of the invention, the hair keratin fibers are washed before application of the hair coloring composition C and of the possible composition D.

Preferably, a step of washing, rinsing, spinning or drying is implemented after the application of the hair coloring composition C to the hair keratin fibers and before the application of the composition D to the keratin fibers capillaries.

More preferably, a drying step is implemented after the application of the hair dye composition C to the hair keratin fibers and before the application of the composition D to the hair keratin fibers.

The application to the fibers can be implemented by any conventional means, in particular by means of a comb, a brush, a brush, a sponge or the fingers.

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

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

Preferably, there is no leave-in time after the application of the hair dye composition C to the hair keratin fibers and before the application of the composition D to the hair keratin fibers.

After the application of the hair coloring composition C and of the possible composition D, the fibers 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 may thus comprise a step of applying heat to the hair keratin fibers using a heating tool.

The heat application step of the method of the invention can be implemented using a helmet, a hair dryer, a straightening or curling iron.

Preferably, the heat application step of the method of the invention is implemented using a hair dryer.

When the method of the invention implements a step of applying heat to the hair keratin fibers, the step of applying heat to the hair keratin fibers takes place after the application of the hair dye composition C and of composition D, if any, on the hair keratin fibres.

During the step of applying heat to the hair keratinous fibres, a mechanical action can be exerted on the locks, such as combing, brushing, passing the fingers.

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

When the step of applying heat to the hair keratin fibers is carried out using a straightening iron, 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 (b1) of applying heat using a helmet, a hair dryer or a climazon, preferably a hair dryer and a step (b2) of applying heat using a straightening or curling iron, preferably a straightening iron.

Step (b1) can be performed before step (b2).

During step (b1), also called the drying step, the fibers can 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 fibers are dried, they are dried, in addition to a supply of heat, with a flow of air. This flow of air during drying improves the individualization of the sheathing.

During drying, a mechanical action on the locks can be exerted such as combing, brushing, the passage of the fingers.

During step (b2), the passage of the straightening or curling iron, preferably the straightening iron, can be carried out at a temperature ranging from 110 and 220°C, preferably between 140 and 200°C.

After the heating step, a shaping step can be implemented with, for example, a straightening iron, the temperature for the shaping step is between 110 and 220°C, preferably between 140 and 200°C.

Preferably, the invention is a hair coloring process, comprising the mixing of a composition A and a composition B to obtain a hair coloring composition C then:
i) the application to the hair keratin fibers of the hair dye composition C, in which the compositions A and B are as defined above.

More preferably, the invention is a hair coloring process, comprising mixing a composition A and a composition B to obtain a hair coloring composition C then:
i) the application to the hair keratin fibers of the hair coloring composition C, in which
composition A comprises at least one (poly)carbodiimide compound as described above,

composition B includes:
- at least 0.1% by weight of one or more non-silicone fatty substances as described above;

- at least one non-silicone polymer having at least one carboxylic acid group, as described previously;

- at least one coloring agent chosen from pigments, direct dyes and mixtures thereof, preferably one or more pigments.

Preferably, the step of applying the hair dye composition C to the hair keratin fibers is repeated several times.

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 present invention also relates to a hair coloring device, comprising at least two compartments containing:

- in a first compartment (E1), a composition A according to the invention as defined above;

- in a second compartment (E2), a composition B according to the invention as defined above;

- optionally in a third compartment (E3), a composition D as described above.

The present invention will now be described more specifically by means of examples, which are in no way limiting of the scope of the invention. However, the examples support specific features, variations, and preferred embodiments of the invention.

Examples

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

More particularly, the process for preparing the (poly)carbodiimides of the invention uses, in 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 Pat. preferably under an inert atmosphere (nitrogen or Argon), and in particular in a preferably aprotic polar solvent such as THF, glyme, diglyme, 1,4-dioxane, and DMF, at a temperature between room temperature and reflux solvent, preferably around 140°C; to lead to 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. Benzoyl halogen such as benzoyl chloride can be added to deactivate the catalyst.

To obtain “symmetrical” (poly)carbodiimides, during the second stage 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 above. According to a variant to obtain the compound (4) from (3) it is possible to add first 0.5 eq. of HEH reagent, then 1 eq. of reagent R ₁ -X ₁ -H.

To obtain “dissymmetrical” (poly)carbodiimides, during the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq) of nucleophilic reagent R ₁ -X ₁ -H then 1 eq. of HEH reagent with R ₁ , X ₁ and E as defined above, to yield 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 the compound (5) from (3) it is possible to add first 1 eq. of reagent R ₁ -X ₁ -H, then 0.5 eq. of HHE reagent.

During a third step, compound (5) reacts with 1 eq. 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 L₁and z are as previously defined which reacts with 1 eq of nucleophilic reagent R₂-X₂-H with L₁, R₂, X₂, and z as defined previously, to lead to the asymmetrical compound (7):
R₁-X₁-C(O)-NH-L₁-(N=C=N-L₁)_not-NH-C(O)-E-C(O)-NH-L₁--(N=C=N-L₁)_z-NH-C(O)-X₂-R₂(7),

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

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 yield 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 above, 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') being able to be synthesized by reaction of 0 .5 eq of nucleophilic reagent R ₁ -X ₁ -H with 1 equivalent of compound (3)), to yield 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, like all the reaction intermediates and reagents, can be purified using standard methods known to those skilled in the art, such as extraction with water and an organic solvent immiscible in water, 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 with stirring.

The reaction medium was heated at 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 are introduced into the reaction medium with stirring. The temperature of 120° C. is maintained until the total disappearance of the isocyanate functions, monitored by infrared spectroscopy at ^2200-2300 cm ⁻¹ , then cooled to room temperature.

After cooling to room temperature, the reaction medium is poured drop by drop 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 A1, B2.1, B2.2, B2.3 and C2 as described below were prepared: the quantities are expressed in g of raw material as it is/100g.

Compositions A1 Polycarbodiimide ⁽¹⁾ 24 Hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer ⁽²⁾ 1 Amodimethicone (and) Trideceth-5 (and) Trideceth-10 ⁽³⁾ 5 Curator(s) qs Water Qsp 100

(1) synthesized according to the synthesis process described in Example 1 (at 40% of active ingredient in water),
(2) sold by the company SEPPIC under the name SEPINOV EMT10

(3) sold by WACKER under the name BELSIL ADM LOG 1 (at 15% active ingredient).

Composition B2.1 B2.2 C2 Copolymer acrylates ⁽⁴⁾ 40 40 40 Ethanol 5 5 5 Stearic acid 1 2 - Red iron oxide (CI 77491) 12 12 12 Preservative(s), neutralizer qs qs qs Water Qsp 100 Qsp 100 Qsp 100

(4) sold by DAITO KASEI KOGYO under the trade name DAITOSOL 3000SLPN-PE1 (aqueous dispersion with 30% active ingredient)

Composition A1, and B2.1 -B2.3 are compositions used in the context of the process according to the invention. Composition C2 is a comparative composition.

Example 3:

Compositions A1, B3.1, B3.2, B3.3 and C3 as described below were prepared: the quantities are expressed in g of raw material as it is/100g.

Compositions A1 Polycarbodiimide ⁽¹⁾ 24 Hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer ⁽²⁾ 1 Amodimethicone (and) Trideceth-5 (and) Trideceth-10 ⁽³⁾ 5 Curator(s) qs Water Qsp 100

(1) synthesized according to the synthesis process described in Example 1 (at 40% of active ingredient in water),
(2) sold by the company SEPPIC under the name SEPINOV EMT10
(3) sold by WACKER under the name BELSIL ADM LOG 1 (at 15% active ingredient).

Composition B3.1 B3.2 B3.3 C3 Acrylate copolymer ⁽⁴⁾ 40 40 40 40 Ethanol 5 5 5 5 Cetylstearyl alcohol 0.5 1 2 0 Red iron oxide (CI 77491) 12 12 12 12 Preservative(s), neutralizer qs qs qs qs Water Qsp 100 Qsp 100 Qsp 100 Qsp 100
(4) sold by DAITO KASEI KOGYO under the trade name DAITOSOL 3000SLPN-PE1 (aqueous dispersion with 30% active ingredient)

Thus, composition A1, and B3.1 -B3.3 are compositions used in the context of the method according to the invention. Composition C3 is a comparative composition.

Test protocol:

Composition A1, and each of the compositions BX.X described above or C2 and C3 described above are mixed in a 50/50 mass ratio.

The various mixtures are then applied to locks of 90% white natural hair at the rate of 0.8 g of the mixture per 1 g of hair. The locks are then combed and dried with a hair dryer.

The composition below D is then applied to each lock at the rate of 0.5 g of composition D per 1 g of hair. The locks are disentangled and dried with a hair dryer.

The locks are stored at room temperature for 24 hours before evaluation.

Composition D (the quantities are expressed in g of raw material as it is/100g).

Composition D Organopolysiloxane with carboxyl group ⁽⁷⁾ 2 Isododecane qsp 100 (7) Sold by SHIN ETSU company under the trade name X-22-3701E

The locks of hair thus colored have good tenacity to repeated shampooing.

After washing, the locks of hair are combed and dried with a hair dryer.

Assessment :

The locks of hair were evaluated in terms of quality of use, more specifically in terms of ease of combing by measuring the ease of combing during the drying step after coloring and washing the locks of hair.

Ease of combing was evaluated sensorially and was scored between 0 and 3 with:

0 representing difficult combing, 3 representing no resistance combing

Compositions Ease of combing during the drying step A1+C2 0 A1+B2.1 1 A1+B2.2 1 A1+C3 0 A1+B3.1 2 A1+B3.2 2 A1+B3.3 2

These results show an improvement in disentangling at the time of drying when composition B contains a fatty substance. This allows in particular greater comfort when styling, for example when brushing.

Claims (25)

Hair dyeing process comprising the application of a composition A and a composition B to the hair keratin fibres, in which:
- composition A comprises at least one (poly)carbodiimide compound, and
- composition B comprises at least one polymer having at least one group containing a carboxylic acid function, and
composition A and/or composition B comprising at least 0.1% by weight of one or more non-silicone fatty substances
composition A and/or B comprising at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof, and
composition A and composition B are applied simultaneously or sequentially to the hair keratin fibres. Process according to Claim 1, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (I) below:
(I)
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 group which may comprise one or more heteroatoms;
- n denotes an integer ranging from 1 to 100; and
- A is a monomer chosen from the compounds below:



. Process according to Claim 1, characterized in that 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 C ₁ -C ₁₈ divalent 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 their mixtures;
- 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). Process according to Claim 3, 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 chosen independently from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acid and monoalkyl ethers of (poly)alkylene glycol, 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 C ₁ -C ₁₈ divalent 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 their mixtures;
- 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 chosen independently 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 heteroatoms ( 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 their mixtures. Process according to either of Claims 3 and 4, 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 chosen independently 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 their mixtures. Process according to any one of Claims 3 to 5, 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) below:
R₁₃-[O-CH₂-C(H)(R)₁₄)]_q- (VI),
in which R₁₃represents a C-alkyl group₁-VS₄or phenyl, preferably C-alkyl₁-VS₄, more preferably a methyl, R₁₄represents a hydrogen atom or a C-alkyl group₁-VS₄, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30;
- n and z denote an integer ranging from 2 to 20, with n+z ranging from 4 to 10 and w is equal to 1;
- L₁is a C cycloalkylene radical₃-VS₁₅such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, and
- E represents an -O-R group₃-O- in which R₃is selected from a C arylene radical₆-VS₁₄, a C cycloalkylene radical₃-VS₁₂, a linear or branched C alkylene radical₁-VS₁₈, optionally interrupted by one or more heteroatom(s), and mixtures thereof. Process according to any one of Claims 3 to 6, 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) below:
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 alkyl group -C ₄ , 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 an -OR ₃ -O- group 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 Claims 3 to 7, 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 -OR ₃ -O- group 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 quantity of the (poly)carbodiimide compound(s) ranges from 0.01 to 40% by weight, preferably from 0.1 to 30% by weight , better still from 0.5 to 25% by weight, and still better still from 2 to 20% by weight, relative to the total weight of composition A. Process according to any one of the preceding claims, characterized in that the non-silicone fatty substance or substances are chosen from fatty acids, fatty alcohols, fatty acid and/or fatty alcohol esters, preferably C12- C22, preferably C14-C18. Process according to any one of the preceding claims, characterized in that the total quantity of the non-silicone fatty substance(s) ranges from 0.1 to 20% by weight, preferably from 0.25 to 15% by weight, preferably from 0, 5 to 10% by weight relative to the total weight of composition A and/or composition B. Process according to any one of the preceding claims, in which the fatty substance or substances are present in composition B. Process according to any one of the preceding claims, characterized in that the polymer or polymers having at least one carboxylic acid group are chosen from silicone compounds comprising at least one carboxylic group, polyurethanes, acrylic polymers and mixtures thereof, preferably among polyurethanes, acrylic polymers and mixtures thereof. Process according to the preceding claim, characterized in that the polymer(s) having at least one carboxylic acid group are in the form of aqueous dispersions of particles of polymer(s) chosen from polyurethanes, acrylic polymers and mixtures thereof, preferably in form of aqueous dispersions of acrylic polymer particles, more preferably in the form of aqueous dispersions of film-forming acrylic polymer particles. Process according to the preceding claim, characterized in that the acrylic polymer or polymers 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 . Process according to any one of the preceding claims, characterized in that the total quantity of the polymer(s) having at least one carboxylic acid group ranges from 0.2 to 60% by weight, more preferentially from 1 to 55% by weight, better again from 5 to 50% by weight, and even more preferably from 10 to 45% by weight, relative to the total weight of composition B. Process according to any one of the preceding claims, characterized in that the coloring agent comprises at least one pigment and optionally at least one direct dye. Process according to any one of the preceding claims, characterized in that the coloring agent comprises at least one direct dye and optionally at least one pigment. Process according to any one of the preceding claims, in which the coloring agent is present in composition B. Process according to any one of the preceding claims, in which the coloring agent(s) range from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, relative to the total weight of composition A and/or of composition B. Process according to any one of the preceding claims, characterized in that the total content of pigment(s) ranges from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, better still from 0.5 at 10% by weight relative to the total weight of composition A and/or of composition B. Process according to any one of the preceding claims, characterized in that one and/or the other of compositions A and B also comprises at least one non-volatile silicone, preferably chosen from non-amino silicones, amino silicones and mixtures thereof, preferably composition A. Process according to any one of the preceding claims, characterized in that it further comprises a step of applying to the hair keratin fibers a composition D comprising at least one silicone polymer comprising at least one carboxylic group. Process according to the preceding claim, characterized in that the total quantity of silicone compound(s) comprising at least one carboxylic group present in composition D ranges from 0.01 to 20% by weight, more preferably from 0.1 to 15% by weight, and better still from 0.5 to 10% by weight, relative to the total weight of composition D. Hair coloring device comprising at least two compartments containing:
- in a first compartment (E1), a composition A as defined in any one of the preceding claims 1 to 22;
- in a second compartment (E2), a composition B as defined in any one of the preceding claims 1 to 22;
- optionally in a third compartment (E3), a composition D as defined in any one of claims 23 to 24.