FR3120531A1 - Hair coloring composition comprising a (poly)carbodiimide compound and a nonionic amine direct dye - Google Patents

Abstract

Hair coloring composition comprising a (poly)carbodiimide compound and a nonionic amine direct dye The present invention relates to a hair coloring composition comprising one or more (poly)carbodiimide compounds and one or more nonionic amine direct dyes. The invention also relates to a process for coloring hair keratin fibers such as the hair, implementing said composition, as well as its use for coloring hair keratin fibers such as the hair.

Description

Hair coloring composition comprising a (poly)carbodiimide compound and a nonionic amine direct dye

The subject of the present invention is a hair coloring composition, comprising one or more specific (poly)carbodiimide compounds and one or more specific amino dyes. The present invention also relates to a hair coloring process, using said hair coloring composition.

In the field of coloring hair keratinous fibers, in particular human hair, there are different types of hair coloring process, such as (i) so-called permanent coloring which has the function of bringing a significant modification of the natural color and which uses oxidation dyes that penetrate the hair fiber and form the dye through a process of oxidative condensation; (ii) non-permanent, semi-permanent or direct coloring, which does not involve the process of oxidative condensation and resists 4 or 5 shampoos; it consists in dyeing hair keratin fibers with dye compositions containing direct dyes; (iii) 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.

Oxidation coloring allows a wide variety of tones to be obtained, with durability to light and repeated washings. However, it involves an oxidation reaction in an alkaline medium often considered aggressive for the hair. Direct coloring avoids this type of drawback by using direct dyes with a strong affinity for keratin fibre. However, such coloring fades quickly, as the shampoos progress.

Although direct dyes are less aggressive for the hair, the color result does not have great durability. In particular, repeated shampoos cause rapid color fading.

The objective of the present invention is to propose a hair coloring composition not comprising an oxidation dye, and which makes it possible to obtain a permanent coloring after shampoos, more particularly after at least 3 shampoos, by improving the tenacity on the fiber from direct dyes, more particularly certain direct dyes.

The subject of the present invention is therefore a hair coloring composition comprising:

- one or more (poly)carbodiimide compounds, preferably corresponding to formula (I) as defined below, and

- one or more amino direct dyes, preferably nonionic.

The present invention also relates to a process for coloring hair, in particular for coloring hair keratin fibers such as the hair, in which the hair coloring composition as defined above is applied to said fibres.

By the use of this composition on hair keratin fibres, colored coatings are obtained on the hair making it possible to obtain a coloring visible on any type of hair in a shampoo-resisting 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.

Furthermore, this hair coloring composition makes it possible to obtain perfectly individualized hair, which can be styled without problem with good cosmetic properties, in particular as regards softness and feel.

In what follows, and unless otherwise indicated, the limits of a domain of values are included in this domain, in particular in the expressions "included between" and "ranging from ... to ...", expressions which have the same meaning and are interchangeable.

The expression “at least one” used in the present description is equivalent to the expression “one or more”, and can be substituted for it.

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

- an " alkyl " radical denotes a saturated, linear or branched saturated hydrocarbon radical containing from 1 to 24 carbon atoms, particularly from 1 to 20 carbon atoms, more particularly from 1 to 12 carbon atoms, preferably in C ₁ - C ₆ , even more preferably C ₂ -C ₄ .

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

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

- an “ alkylene ” radical denotes a divalent alkyl group with “ alkyl ” as defined above, preferably C ₂ -C ₄ , 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 , it being understood that the cycloalkyl radical may be substituted by one or more (C ₁ -C ₄ )alkyl groups such as methyl, preferably the cycloalkyl radical is then an isobornyl group;

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

- a stem "aryl» is an unsaturated and aromatic hydrocarbon-based 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 groups (C₁-VS₄)alkyl such as methyl, preferably tolyl, xylyl, or methylnaphthyl, preferably the aryl group represents phenyl;
- a stem "aryleneis a divalent aryl radical with "aryl» as previously defined 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 denotes an aryl-oxy or aryl-O- radical with " aryl " as defined above;

- an " alkoxy " radical denotes an alkyl-oxy or alkyl-O- radical with " alkyl ", as defined above;

- an " acyloxy " radical denotes an ester radical RC(O)-O- with R an alkyl group as defined above;

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

Polycarbodiimide compound

The hair coloring composition 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 150, more preferably 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 group chosen from a hydrocarbon radical, preferably alkyl, optionally interrupted by one or more heteroatom(s), a group chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl groups , carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide, and azacyclopropane, and an alkyl or hydrocarbon radical, optionally interrupted by an alkyl or hydrocarbon radical, preferably several heteroatom(s) and by one or more groups chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyal groups kylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulphonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide, and azacyclopropane;

- n denotes an integer ranging from 1 to 1000; 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:

(ia)

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.

“ 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 or compounds, present in the composition according to the invention, preferably ranges from 0.01 to 40% by weight, better still from 0.01 to 30% by weight, more preferentially from 0, 1 to 30% by weight, more preferably 0.1 to 25% by weight, more preferably 0.5 to 25% by weight, more preferably 1 to 12% by weight, more preferably 1 to 10% by weight, relative to the total weight of the composition.

2/ Amino direct dye

The hair coloring composition according to the invention also comprises one or more amine direct dyes, preferably nonionic.

By “direct dye”, we mean natural or synthetic dyes, different from oxidation dyes. These are dyes that will diffuse superficially on the fiber.

Preferably, the direct amine dye comprises one or more primary amine radical(s), preferably not directly linked to the aromatic nucleus if there is one, and/or one or more secondary amine radical(s). s), with no particular location constraint in the chemical structure.

Preferably, the chemical structure does not include a phenolic, carboxylic or quinone (and more particularly anthraquinone) type unit.

The amine direct dye is preferably nonionic (or neutral).

In particular, the amino direct dyes according to the invention can be chosen from nitro amino benzene dyes, better still from the following nitro amino benzene dyes, alone or as a mixture:

- HC Yellow No. 9, with the formula:

- 2-Nitro-5-Glyceryl Methylaniline, of formula:

- HC Orange n°2 with formula:

- 2-hydroxyethylamino-5-nitroanisole of formula:

- the compounds of the following formulas:

as well as their acid or base salts, organic or inorganic and their optical and geometric isomers.

Preferably, the hair coloring composition comprises one or more nonionic amino direct dyes chosen from the following compounds: HC Yellow No. 9, HC Orange No. 2 and 2-NITRO-5-GLYCERYL METHYLANILINE, as well as their mixtures.

The hair coloring composition may comprise the nonionic amine direct dye(s) in a total content ranging from 0.001 to 15% by weight, preferably from 0.01 to 10% by weight, better still from 0.02 to 5% by weight , preferably from 0.05 to 2% by weight, even better still from 0.2 to 1% by weight, relative to the total weight of the hair coloring composition.

Preferably, the hair coloring composition may comprise the nitrated amine benzene direct dye(s) in a total content ranging from 0.001 to 15% by weight, preferably from 0.01 to 10% by weight, better still from 0.02 to 5% by weight, preferably from 0.05 to 2% by weight, even better from 0.2 to 18% by weight, relative to the total weight of the hair coloring composition.

The hair coloring composition according to the invention may comprise water, preferably at a content ranging from 10 to 99% by weight, better still from 30 to 98% by weight, even better still from 50 to 97% by weight relative to the total weight of the hair coloring composition.

The hair coloring composition according to the invention may also comprise one or more organic solvents, in particular chosen from, alone or as a mixture, C ₁ -C ₄ monoalcohols such as ethanol and isopropanol; polyols and polyol ethers such as glycerol, 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol and phenoxyethanol.

The organic solvents may be present in the hair coloring composition in a total amount of between 0.1 and 20% by weight, preferably between 0.5 and 15% by weight, better still between 1 and 10% by weight relative to the total weight of the hair coloring composition.

The hair coloring composition according to the invention may also comprise any adjuvant or additive usually used in the cosmetic field, in particular hair.

Mention may in particular be made of reducing agents, thickening agents, softeners, antifoaming agents, moisturizing agents, UV filters, peptizers, solubilizers, perfumes, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, anionic, non-ioinic, cationic or amphoteric polymers, preservatives, and mixtures thereof.

The hair coloring composition according to the invention may in particular be in the form of a suspension, dispersion, gel, emulsion, in particular oil-in-water (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 a cream, foam, stick, dispersion of vesicles in particular of ionic or non-ionic lipids, biphase lotion or multiphase. Preferably, it is in the form of an aqueous solution.

A person skilled in the art will be able to choose the appropriate galenic form, as well as its method of preparation and its ingredients, 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 hair coloring composition.

The hair coloring composition according to the invention is preferably a hair composition for coloring hair keratin fibers such as the hair.

The present invention also relates to a process for dyeing hair keratin fibers such as the hair, in which the hair dye composition as defined above is applied to said fibres.

The hair coloring composition according to the invention can be applied to dry or wet keratin hair fibers, as well as to any type of fiber, light or dark, natural or colored, permed, bleached or straightened.

The hair keratin fibers can be washed before application of the hair coloring composition according to the invention.

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 to the hair keratin fibers is generally carried out at room temperature (between 15 to 25° C.).

Preferably, after application of the hair coloring composition to the hair keratin fibres, the wait is between 1 minute and 6 hours, in particular between 2 minutes and 2 hours, more particularly between 3 minutes and 1 hour, preferentially between 5 minutes and 30 minutes, for example before a step of washing, rinsing, spinning or drying.

Preferably, a step of washing, rinsing, spinning or drying is implemented after the application of the hair coloring composition to the hair keratin fibres.

Preferably, a rinsing step is implemented after the application of the hair coloring composition to the hair keratin fibres.

The method according to the invention may also comprise a step of applying heat to the hair keratin fibers using a heating tool, for example such as a helmet, a hair dryer, a straightening or loop, a climazon.

The present invention also relates to the use of the hair coloring composition as defined above, for coloring hair keratin fibers such as the hair.

The invention is illustrated in more detail in the following examples, in which the contents are indicated in% by weight of active material (unless otherwise indicated).

Example 1: Process for the synthesis of the (poly)carbodiimide compound

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 the mixture is cooled to room temperature.

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

Example 2

The following hair coloring composition A according to the invention and the comparative hair coloring composition A' are prepared:

Composition HAS HAS' Polycarbodiimide of Example 1 4 - HC Orange n°2 0.5 0.5 Water Qsp 100% Qsp 100%

Protocol

Hair coloring composition A or A' is applied to locks of dry, Caucasian, natural, 100% white hair, at the rate of 2 g of composition per gram of lock.

The locks of hair are then dried with a hair dryer with a comb, then combed and left at room temperature for 24 hours.

Then, the locks of hair thus colored are subjected to several repeated shampoos so as to evaluate the tenacity (the persistence) of the coloring with the shampoos.

Shampoo protocol

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

A standard shampoo (ElsèveColorVive) is applied evenly to the colored locks at a rate of 0.4g of shampoo per gram of locks, gently kneading the locks of hair along its length (6 passes) for 15 seconds, from root to The point.

The locks of hair are then placed in a watch glass and left to rest for 1 minute; then they are rinsed with water by passing the wick between the fingers (15 passages). The locks of hair are then wrung out between two fingers before the next shampoo.

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

Results

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

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

The persistence of the color is defined here as the % of color remaining at the Xth shampoo. It is calculated by making the ratio of the color remaining at the Xth shampoo (∆E _X : difference in color with the uncolored hair) with the initial color (∆E ₀ ).

The persistence of the Xth shampoo Px is calculated according to the following equation:

We obtain the following results (Px):

Number of shampoos Composition A Composition A' 0 100% 100% 5 90% 86% 10 85% 81% 15 81% 76% 20 77% 70%

The hair coloring composition A according to the invention allows an improved color persistence, therefore a better tenacity to shampoos, compared to the comparative hair coloring composition A′.

Claims (12)

Hair coloring composition comprising:
- one or more (poly)carbodiimide compounds, preferably corresponding to the following formula (II):

in which :
-R₁and R₂represent, independently, a hydrocarbon radical optionally interrupted by one or more heteroatom(s),
-X₁and X₂represent, independently, an oxygen atom O, a sulfur atom S or an NH group;
- L₁independently represents a C divalent aliphatic hydrocarbon radical₁-VS₁₈, a C cycloalkylene radical₃-VS₁₅, a C heterocycloalkylene group₃-VS₁₂or an arylene group at C₆-VS₁₄, and mixtures thereof ;
- n and z designate, independently, an integer ranging from 1 to 20, with n+z ≥ 2; and w denotes an integer ranging from 1 to 3;
- E independently represents a group chosen from the following divalent groups: -O-R₃-O-; -S-R₄-S-; -R₅-N(R₆)-R₄-N(R₆)-R₅- in which R₃and R₄independently represent a divalent hydrocarbon radical optionally interrupted by one or more heteroatom(s); R₅independently represents a covalent bond or a divalent saturated hydrocarbon radical, optionally interrupted by one or more heteroatom(s); R₆independently represents a hydrogen atom or a hydrocarbon radical optionally interrupted by one or more heteroatom(s); and
- one or more non-ionic amino direct dyes. Hair coloring composition according to the preceding claim, in which the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:
- X ₁ and X ₂ 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. Hair coloring composition according to one of the preceding claims, in which the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:
- X ₁ and X ₂ 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. Hair coloring composition according to one of the preceding claims, in which the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:
-X₁and X₂represent an oxygen atom;
-R₁and R_2,independently represent the compound of formula R₁₃-[O-CH₂-C(H)(R)₁₄)]_q- in which R₁₃represents a C-alkyl group₁-VS₄or phenyl, preferably C-alkyl₁-VS_4,preferentially a methyl, R₁₄represented 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 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. Hair coloring composition according to one of the preceding claims, in which the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which:
-X₁and X₂represent an oxygen atom;
-R₁and R_2,independently represent the compound of formula R₁₃-[O-CH₂-C(H)(R)₁₄)]_q- in which R₁₃represents a C-alkyl group₁-VS₄or phenyl, preferably C-alkyl₁-VS_4,more preferably a methyl, R₁₄represented 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 1 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, 4,4-dicyclohexylene methane, preferably 4,4-dicyclohexylene methane; and
- E represents an -O-R group₃-O- in which R₃represents a linear or branched C alkylene radical₁-VS₁₈such as methylene, propylene, butylene ethylene, optionally interrupted by one or more heteroatom(s). Hair coloring composition according to one of the preceding claims, in which the (poly)carbodiimide compound is chosen from the compounds of formula (XII):

in which L₁is the 4,4-dicyclohexylene methane, n and z denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10, E represents a group -O-R₃-O- in which R₃represents a butylene radical, and r and s denote an integer ranging from 4 to 30. Hair coloring composition according to one of the preceding claims, in which the total quantity of the (poly)carbodiimide compound or compounds ranges from 0.01 to 40% by weight, preferentially from 0.1 to 30% by weight, better still from 0.5 to 25% by weight, better still from 1 to 10% by weight relative to the total weight of the hair coloring composition. Hair dye composition according to one of the preceding claims, in which the nonionic amine direct dyes are chosen from nitro amine benzene dyes, better still from the following nitro amine benzene dyes, alone or as a mixture:
- HC Yellow No. 9, with the formula:

- 2-Nitro-5-Glyceryl Methylaniline, of formula:

- HC Orange n°2 with formula:

- 2-hydroxyethylamino-5-nitroanisole of formula:

- the compounds of the following formulas:





as well as their acid or base, organic or inorganic salts and their optical and geometric isomers. Hair coloring composition according to one of the preceding claims, in which the nonionic amino direct dyes are chosen from the following compounds: HC Yellow No. 9, HC Orange No. 2 and 2-NITRO-5-GLYCERYL METHYLANILINE , as well as mixtures thereof. Hair coloring composition according to one of the preceding claims, comprising the nonionic amine direct dye(s), in particular the nitro amine benzene direct dye(s), in a total content ranging from 0.001 to 15% by weight, better still from 0.01 to 10% by weight, preferably from 0.02 to 5% by weight, even better from 0.05 to 2% by weight, preferably from 0.2 to 1% by weight, relative to the total weight of the composition. Process for dyeing hair keratin fibers such as the hair, in which the hair dye composition as defined in one of Claims 1 to 10 is applied to the said fibres. Use of the hair coloring composition as defined in one of Claims 1 to 10, for coloring hair keratin fibers such as the hair.