DESCRIPTION

COMPOSITION FOR COLORING KERATIN FIBERS

TECHNICAL FIELD

The present invention relates to a composition, in particular a cosmetic composition for coloring keratin fibers such as hair.

BACKGROUND ART

It is known to dye keratin fibers, in particular human hair, with dyeing compositions containing oxidative coloring precursors, generally called oxidative bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidative bases are generally combined with couplers. These bases and these couplers are colorless or weakly colored compounds which, combined with oxidizing products, can give rise to colored compounds through an oxidative condensation process.

This type of coloring by oxidation makes it possible to obtain colors with very high visibility, and the ability to cover white hair in a wide variety of shades, but it results in damage to the keratin fibers due to the use of oxidizing agents and alkaline agents (in particular by repeated application or by combination with other hair treatments).

On the other hand, it is also known to dye keratin fibers, in particular human hair, with dyeing compositions containing direct dyes. Conventional direct dyes are in particular the following: benzene nitrates, anthraquinones, nitropyridines, azos, xanthines, acridines, azines, and triarylmethane-type or natural colorings. Hair coloring using direct dyes has advantages over hair coloring using oxidative dyes: it rarely gives rise to allergy issues, it causes less damage to the hair, and it gives vivid color visibility, but has a disadvantage of less color lastingness to shampoos.

For example, FR2980704A1, FR2980700A1, FR 2922445A1, FR 2922446A1, US2009/070945A1, US2011/296631 Al, WO2018/137587, US2020/368005A1, and EP1604647A1 disclose compositions for dyeing hair.

DISCLOSURE OF INVENTION

An objective of the present invention is to provide a new composition for coloring keratin fibers, such as hair, which can provide keratin fibers with improved color intensity and lastingness.

The above objective of the present invention can be achieved by a composition comprising:

(a) at least one polylysine, and

(b) at least one coloring agent selected from dyes and pigments, where the dyes are selected from oxidative dyes and direct dyes other than irridoid dyes, wherein the (a) polylysine has a weight-average molecular weight in the range of 4,500 g/mol to 25,000 g/mol and is covalently bound to neither the dyes nor polyorganosiloxane, and the composition has a pH value ranging from 8 to 12.

The composition may comprise the (b) at least one coloring agent selected from oxidative dyes, and, the composition comprises at least one additional alkaline agent.

When the composition comprises the (b) at least one coloring agent selected from oxidative dyes and at least one additional alkaline agent, the alkaline agent(s) may be present in an amount of 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, and even more preferably 4% by weight or more; and/or 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 8% by weight or less, relative to the total weight of the composition.

In another embodiment, the composition comprises the (b) at least one dye selected from direct dyes, and, the composition comprises at least one additional alkaline agent in an amount of less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight, and even more preferably less than 0.05% by weight, relative to the total weight of the composition.

The (a) polylysine may be epsilon-poly lysine.

The (a) polylysine may have a weight-average molecular weight in the range of 4,500 g/mol to 20,000 g/mol.

The (a) polylysine(s) may be present in the composition in an amount of 0.05% to 10% by weight, preferably 0.1% to 5% by weight, more preferably 0.2% to 3% by weight, and even more preferably 0.3% to 2% by weight, relative to the total weight of the composition.

The (a) polylysine may be in the free form.

The dye may be selected those in the free form.

The composition may comprise at least one acid in an amount of less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight, even more preferably less than 0.3% by weight, and in particular less than 0.1% by weight, relative to the total weight of the composition.

The composition may be for coloring keratin fibers with improved color intensity and color lastingness.

The present invention also relates to a cosmetic process for coloring keratin fibers, preferably hair, comprising a step of applying onto the keratin fibers the composition according to the present invention.

The present invention also relates to a use of the (a) polylysine to enhance color intensity and color lastingness of the keratin fibers colored with (b) at least one coloring agent selected from dyes and pigments, where the dyes are selected from oxidative dyes and direct dyes other than irridoid dyes and the (a) polylysine has a weight-average molecular weight in the range of 4,500 g/mol to 25,000 g/mol.

BEST MODE FOR CARRYING OUT THE INVENTION

After diligent research, the inventors have surprisingly found that the composition according to the present invention can enhance the color intensity and lastingness of the colored keratin fiber.

Thus, the present invention relates to a composition, preferably a composition for coloring keratin fibers, comprising:

(a) at least one polylysine, and

(b) at least one coloring agent selected from dyes and pigments, where the dyes are selected from oxidative dyes and direct dyes other than irridoid dyes, wherein the (a) polylysine has a weight-average molecular weight in the range of 4,500 g/mol to 25,000 g/mol and is covalently bound to neither the dyes nor polyorganosiloxane, and the composition has a pH value ranging from 8 to 12.

Another aspect of the present invention is a process for coloring keratin fibers by applying to the keratin fibers the composition according to the present invention above.

In the present specification, upper limits and lower limits of numerical ranges can be combined arbitrarily. For example, any combinations of upper limits and lower limits of a numerical range of a content of each ingredients is available and is within a scope of the disclosure of the present specification.

Hereafter, the composition and the process according to the present invention will each be described in a detailed manner.

[Composition]

The composition according to the present invention comprises:

(a) at least one polylysine, and

(b) at least one coloring agent selected from dyes and pigments, where the dyes are selected from oxidative dyes and direct dyes other than irridoid dyes, wherein the (a) polylysine has a weight-average molecular weight in the range of 4,500 g/mol to 25,000 g/mol and is covalently bound to neither the dyes nor polyorganosiloxane, and the composition has a pH value ranging from 8 to 12.

The composition according to the present invention is intended for coloring keratin fibers. The term “keratin fibers” means fibers of human or animal origin, such as head hair, bodily hair, the eyelashes, the eyebrows, wool, angora, cashmere or fur. According to the present invention, the keratin fibers are preferably human keratin fibers, more preferentially the hair.

In particular, the composition according to the present invention is for coloring keratin fibers with improved color intensity and color lastingness.

The composition according to the present invention has a pH value of from 8 to 12, preferably from 8.5 to 12, and more preferably from 9 to 12, and even more preferably from 9 to 11. In another preferred embodiment, the composition according to the present invention has a pH value of 9.5 or more, for example, has a pH value of from 9.5 to 12.

The composition according to the present invention comprises (a) at least one polylysine and (b) at least one coloring agent selected from dyes and pigments, where dyes are selected from oxidative dyes and direct dyes other than irridoid dyes. These components will each be described in a detailed manner.

(Polylysine) The composition according to the present invention comprises (a) at least one polylysine. Two or more types of polylysines may be used in combination. Thus, a single type of polylysine or a combination of different types of polylysines may be used.

Polylysines correspond to the condensation of several amino acids lysine. Polylysine can be a natural homopolymer of L-lysine that can be produced by bacterial fermentation.

Polylysines are typically used as a natural preservative in food products. Polylysine is a polyelectrolyte which is soluble in polar solvents such as water.

Polylysine can be, for example, epsilon-polylysine (or referred as “e-polylysine”), which is a condensation of amino groups at the £-position and carboxyl groups of lysines, or alphapolylysine (or referred as “a-polylysine”), which is a condensation of amino groups at the exposition and carboxyl groups of lysines. Polylysine is commercially available in various forms, such as poly D-lysine and poly L-lysine. The polylysine is generally a condensate of L-lysines, i.e., poly L-lysine.

The poly-lysine has a weight-average molecular weight in the range of 4,500 g/mol to 25,000 g/mol. Preferably, the poly-lysine has a weight-average molecular weight in the range of 4,500 g/mol to 20,000 g/mol. Weight-average molecular weight for the purposes of this invention can be determined by general technology in the art, for example, size exclusion chromatography (GPC).

As an example of polylysine, mention may be made of:

- Epsilon-poly-L-lysine of JNC CORPORATION which is a 25% solution of Epsilon-poly-L- lysine having a weight-average molecular weight of around 4,700 g/mol in aqueous solution;

- Epsilon-poly-L-lysine of TCR CANADA which is Epsilon-poly-L-lysine having a weightaverage molecular weight of around 18,000 g/mol.

According to one particular embodiment, the polylysine may be a modified polylysine, for example, a polylysine with a fatty chain as described in application FR 2889448, a polylysine with a guanidine or biguanidine function as described in application FR 2851465, a thiolated polylysine as described in the application FR2853533.

The polylysine may be in the form of organic or inorganic salts. The addition salts with an acid are, for example, the hydrochloric or hydrobromic acid, sulfuric acid, citric acid, succinic acid, tartaric acid, lactic acid, para-toluenesulphonic acid, phosphoric acid, or acetic acid salts; or fatty acid salts, such as linoleic acid, oleic acid, palmitic acid, stearic acid, behenic acid, and 18-methylicosanoic acid. The addition salts with a base are, for example, a sodium salt, a calcium salt, or a hydroxyalkylamine salt, for example, N-methylglucamine, aminopropane diol or triethanolamine.

In some preferred embodiments of the present invention, the polylysine of the present invention is present in a form of a single molecule in the composition, or is not covalently bound to other compounds. In one embodiment of the present invention, the polylysine is not covalently bound to dye compounds. In one embodiment of the present invention, the polylysine is not covalently bound to polyorganosiloxane compounds. The term “polyorganosiloxane” is well-known in the art to mean compounds having Si-0 main chain and organic functional groups attached to the main chain. In another embodiment of the present invention, the polylysine is in the free form. The term “free form” here indicates that the polylysine is not covalently bound to any other compounds.

The polylysine(s) may be present in the composition according to the present invention in an amount of 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and even more preferably 0.3% by weight or more; and/or may be 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less, and even more preferably 2% by weight or less, relative to the total weight of the composition.

The polylysine(s) may be present in the composition according to the present invention in an amount of 0.05% to 10% by weight, preferably 0.1% to 5% by weight, more preferably 0.2% to 3% by weight, and even more preferably 0.3% to 2% by weight, relative to the total weight of the composition.

(Coloring Agent)

The composition according to the present invention comprises (b) at least one coloring agent. Two or more types of coloring agents may be used in combination. Thus, a single type of coloring agent or a combination of different types of coloring agents may be used.

The coloring agent of the present invention is selected from dyes, pigments, and mixtures thereof.

•Dyes

The dyes of the present invention are selected from oxidative dyes and direct dyes other than irridoid dyes.

In one embodiment of the present invention, the composition comprises at least one oxidative dye and at least one direct dye in combination.

The dye of the present invention is not covalently bound to the (a) polylysine. Therefore, the dye can be selected from oxidative dyes and direct dyes other than dyes covalently bonded to the polylysine. This can mean that the composition according to the present invention does not comprises dyes covalently bound to the polylysine.

In another embodiment of the present invention, the dye is in the free form. The term “free form” here indicates that the dye is not covalently bound to any other compounds.

The dye of the present invention is not an irridoid dye. Therefore, the dye is selected from oxidative dyes and direct dyes other than irridoid dyes. This can mean that the composition according to the present invention does not comprises any irridoid dyes.

Dyes are different from “pigments” in that dyes are soluble in the cosmetic medium while pigments are particles, which are not soluble in the cosmetic medium.

- Oxidative Dye The oxidative dyes may be selected from oxidation bases and couplers.

The oxidation base can be selected from those conventionally known in oxidation dyeing, preferably from the group consisting of ortho- and para-phenylenediamines, double bases, ortho- and para-aminophenols, heterocyclic bases, and the acid addition salts thereof.

There may be mentioned in particular:

- (I) the para-phenylenediamines of the following formula (I) and their addition salts with an acid: in which:

Ri represents a hydrogen atom, a C1-C4 alkyl radical, a monohydroxy(Ci-C4 alkyl) radical, a polyhydroxy-(C2-C4 alkyl) radical, a (Ci-C4)alkoxy(Ci-C4)alkyl radical, a C1-C4 alkyl radical substituted with a nitrogen-containing group, a phenyl radical, or a 4 ’-aminophenyl radical; R-2 represents a hydrogen atom, a C1-C4 alkyl radical, a monohydroxy(Ci-C4 alkyl) radical, a polyhydroxy(C2-C4 alkyl) radical, a (Ci-C4)alkoxy(Ci-C4)alkyl radical, or a C1-C4 alkyl radical substituted with a nitrogen-containing group;

Ri and R2 may also form with the nitrogen atom carrying them a 5- or 6-membered nitrogencontaining heterocycle optionally substituted with one or more alkyl, hydroxyl, or ureido groups;

R3 represents a hydrogen atom, a halogen atom such as a chlorine atom, a C1-C4 alkyl radical, a sulpho radical, a carboxyl radical, a monohydroxy(Ci-C4 alkyl) radical, a hydroxy(Ci-C4 alkoxy) radical, an acetylamino(Ci-C4 alkoxy) radical, a mesylamino(Ci-C4 alkoxy) radical, or a carbamoylamino(Ci-C4 alkoxy) radical; and

R4 represents a hydrogen or halogen atom or a C1-C4 alkyl radical.

Among the nitrogen-containing groups of formula (I) above, there may be mentioned in particular the amino, mono(Ci-C4)alkylamino, (Ci-C4)dialkylamino, (Ci-C4)trialkylamino, monohydroxy(Ci-C4)alkylamino, di(monohydroxy(Ci-C4)alkyI)amino, imidazolinium, and ammonium radicals.

Among the para-phenylenediamines of formula (I) above, mention may be more particularly made of para-phenylenediamine, para-tolylenediamine, 2-chloro-paraphenylenediamine, 2,3- dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para- phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethylpara- phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl- paraphenylenediamine, 4-amino-N,N-diethyl-3 -methylaniline, N,N-bis(P-hydroxyethyl)-para- phenylenediamine, 4-N,N-bis(P-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis( - hydroxyethyl)amino-2-chloroaniline, 2-P-hydroxyethyl-para-phenylenediamine, 2-fluoro- paraphenylenediamine, 2-isopropyl-para-phenylenediamine, N-(P-hydroxypropyl)- paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3- methylpara-phenylenediamine, N,N-(ethyl-p-hydroxyethyl)-para-phenylenediamine, N-(P,y- dihydroxypropyl)-para-phenylenediamine, N-(4’-aminophenyl)-para-phenylenediamine, N- phenyl-para-phenylenediamine, 2-P-hydroxyethyloxy-para-phenylenediamine, 2-P- acetylamino-ethyloxy-para-phenylenediamine, N-(0-methoxyethyl)-para-phenylenediamine, 2-methyl-l-N-p-hydroxyethyl-para-phenylenediamine, N-(4-aminophenyl)-3-hydroxy- pyrrolidine, 2-[{2-[(4-aminophenyl)amino]ethyl}(2-hydroxyethyl)amino]-eth anol, and their addition salts with an acid.

Among the para-phenylenediamines of formula (I) above, most particularly preferred are para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-0- hydroxyethyl-para-phenylenediamine, 2-0-hydroxyethyloxy-para-phenylenediamine, 2,6- dimethyl-para-phenylenediamine, 2, 6-diethyl -para-phenylenediamine, 2,3 -dimethyl-para- phenylenediamine, N,N-bis(0-hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine, and their addition salts with an acid.

- (II) According to the present invention, “double bases” are understood to mean compounds containing at least two aromatic rings on which amino and/or hydroxyl groups are carried.

Among the double bases which can be used as oxidation bases in the dyeing compositions in accordance with the present invention, mention may be made in particular of compounds corresponding to the following formula (II), and their addition salts with an acid: in which:

- Zi and Z2, which are identical or different, represent a hydroxyl or -NH2 radical which may be substituted with a C1-C4 alkyl radical or with a linking arm Y;

- the linking arm Y represents a linear or branched alkylene chain comprising from 1 to 14 carbon atoms, which may be interrupted by or which may end with one or more nitrogencontaining groups and/or one or more heteroatoms such as oxygen, sulphur, or nitrogen atoms, and optionally substituted with one or more hydroxyl or Ci-Ce alkoxy radicals;

- R5 and Re represent a hydrogen or halogen atom, a C1-C4 alkyl radical, a monohydroxy(Ci- C4 alkyl) radical, a polyhydroxy(C2-C4 alkyl) radical, an amino(Ci-C4 alkyl) radical, or a linking arm Y;

- R , RS, R9, Rio, Rih and R12, which are identical or different, represent a hydrogen atom, a linking arm Y, or a C1-C4 alkyl radical; it being understood that the compounds of formula (II) contain only one linking arm Y per molecule.

Among the nitrogen-containing groups of formula (II) above, mention may be made in particular of the amino, mono(Ci-C4)alkylamino, (Ci-C4)dialkylamino, (Ci-C4)trialkylamino, monohydroxy(Ci-C4)alkylamino, imidazolinium, and ammonium radicals.

Among the double bases of formulae (II) above, mention may be more particularly made of N,N’-bis(0-hydroxyethyl)-N,N’-bis(4’-aminophenyl)-l,3- diaminopropanol, N,N’-bis(0- hydroxyethyl)-N,N’-bis(4’-aminophenyl)ethylenediamine, N,N’-bis(4-aminophenyl)- tetramethylenediamine, N,N’ -bis(0-hydroxyethyl)-N,N’ -bis(4- aminophenyl)tetramethylenediamine, N,N’-bis(4-methylaminophenyl)tetramethylenediamine, N,N’-bis(ethyl)-N,N’-bis(4’-amino-3’-methylphenyl)et hylene-diamine, 1 ,8-bis(2,5- diaminophenoxy)-3,5-dioxaoctane, and their addition salts with an acid.

Among these double bases of formula (II), N,N’-bis(P-hydroxyethyl)-N,N’-bis(4’- aminophenyl)-l,3-diaminopropanol, l,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, or one of their addition salts with an acid are particularly preferred.

- (Ill) The para-aminophenols corresponding to the following formula (III), and their addition salts with an acid: in which:

- R13 represents a hydrogen atom, or a halogen atom such as fluorine, a C1-C4 alkyl, monohydroxy(Ci-C4 alkyl), (Ci-C4)alkoxy(Ci-C4)-alkyl, amino(Ci-C4 alkyl), or hydroxy(Ci- C4)alkylamino-(Ci-C4 alkyl) radical,

- R14 represents a hydrogen atom, or a halogen atom such as fluorine, a C1-C4 alkyl, monohydroxy(Ci-C4 alkyl), polyhydroxy(C2-C4 alkyl), amino(Ci-C4 alkyl), cyano(Ci-C4 alkyl), or (Ci-C4)alkoxy(Ci-C4)alkyl radical.

Among the para-aminophenols of formula (III) above, mention may be more particularly made of para-aminophenol, 4-amino-3 -methylphenol, 4-amino-3 -fluorophenol, 4-amino-3- hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino- 2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(P- hydroxyethylaminomethyl)phenol, and their addition salts with an acid.

- (IV) The ortho-aminophenols which can be used as oxidation bases in the context of the present invention are chosen in particular from 2-aminophenol, 2-amino-l-hydroxy-5- methylbenzene, 2-amino-l-hydroxy-6-methylbenzene, 5-acetamido-2-aminophenol, and their addition salts with an acid.

- (V) Among the heterocyclic bases which can be used as oxidation bases in the dyeing compositions in accordance with the present invention, mention may be more particularly made of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their addition salts with an acid.

Among the pyridine derivatives, mention may be more particularly made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6- methoxypyridine, 2-(P-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4- diaminopyridine, and their addition salts with an acid.

Among the pyrimidine derivatives, mention may be more particularly made of the compounds described, for example, in patents DE 2 359 399; JP 88-169571; and JP 91-10659, or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6- triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6- diaminopyrimidine, 2,5,6-triamino-pyrimidine, and the pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which there may be mentioned pyrazolo[l ,5-a]-pyrimidine-3,7-diamine; 2,5-dimethyl-pyrazolo[l ,5-a]-pyrimidine- 3,7-diamine; pyrazolo[l ,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[l ,5-a]pyrimidine- 3,5-diamine; 3-aminopyrazolo[l,5-a]pyrimidin-7-ol; 3-amino-pyrazolo[l,5-a]pyrimidin-5-ol; 2-(3-amino-pyrazolo-[l,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[l,5- a]pyrimidin-3 -ylamino)ethanol, 2- [(3 -amino-pyrazolo [ 1 ,5 -a]pyrimidin-7-yl)-(2-hydroxy- ethyl)amino] -ethanol, 2-[(7-aminopyrazolo[l ,5-a]-pyrimidin-3-yl)-(2- hydroxyethyl)amino]ethanol, 5,6-dimethylpyrazolo-[l ,5-a]pyrimidine-3,7-diamine, 2,6- dimethylpyrazolo-[l,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethyl-pyrazolo[l,5- a]pyrimidine-3 ,7-diamine, 3 -amino-5-methyl-7-imidazolylpropyl-aminopyrazolo [ 1 , 5 - a] - pyrimidine, their addition salts and their tautomeric forms, when a tautomeric equilibrium exists, and their addition salts with an acid.

Among the pyrazole derivatives, mention may more particularly be made of the compounds described in patents DE 3 843 892 and DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749, and DE 195 43 988 such as 4,5-diamino-l-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-l -(4’-chlorobenzyl)-pyrazole, 4,5-diamino-l ,3- dimethylpyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, 4,5-diamino-l-methyl-3- phenylpyrazole, 4-amino- 1 ,3-dimethyl-5-hydrazino-pyrazole, 1 -benzyl-4,5-diamino-3- methyl-pyrazole, 4,5-diamino-3-tert-butyl- 1 -methylpyrazole, 4,5-diamino- 1 -tertbutyl-3- methylpyrazole, 4,5-diamino-l -(P-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-l-(P- hydroxyethyl)pyrazole, 4,5-diamino- 1 -ethyl-3 -methylpyrazole, 4,5-diamino- 1 -ethyl-3-(4’- methoxyphenyl)pyrazole, 4,5-diamino- 1 -ethyl-3 -hydroxy-methylpyrazole, 4,5-diamino-3- hydroxymethyl-1 -methylpyrazole, 4,5 -diamino-3 -hydroxymethyl- 1 -isopropyl-pyrazole, 4,5- diamino-3 -methyl- 1 -isopropyl-pyrazole, 4-amino-5 -(2 ’ -aminoethyl)amino- 1,3- dimethylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5-triamino-pyrazole, 3, 5 -diamino- 1- methyl-4-methylaminopyrazole, 3 ,5-diamino-4-(P-hydroxy-ethyl)amino- 1 -methylpyrazole, and their addition salts with an acid.

Among the heterocyclic bases which can be used as oxidation bases, mention may more particularly be made of diaminopyrazolopyrazolones and especially 2,3-diamino-6,7-dihydro- lH5El-[pyrazolol,2,a]pyrazol-l-one and the addition salts of these diaminopyrazolopyrazolones with an acid.

The coupler may be an oxidation coupler which can be selected from those conventionally known in oxidation dyeing, preferably from the group consisting of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthols, heterocyclic couplers, and the acid addition salts thereof.

The heterocyclic couplers may be selected from the group consisting of indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1,3- benzodioxoles, quinolines, and their addition salts with an acid.

These couplers are more particularly chosen from 2,4-diamino- 1 -(P- hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 5-N-(P-hydroxyethyl)amino-2- methylphenol, 3 -aminophenol, 2-chloro-3-amino-6-methylphenol, 1,3 -dihydroxybenzene (or resorcinol), l,3-dihydroxy-2-methylbenzene, 4-chloro- 1,3 -dihydroxybenzene, 2-amino-4-(p- hydroxyethylamino)- 1 -methoxybenzene, 1 ,3 -diaminobenzene, 2-methyl-5 - hydroxyethylaminophenol, 4-amino-2 -hydroxytoluene, 1 ,3 -bis(2,4-diaminophenoxy)- propane, sesamol, 2,4-diaminophenoxyethanol, l-amino-2-methoxy-4,5-methylene- dioxybenzene, a-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6- hydroxy-indoline, 2,6-dihydroxy-4-methylpyridine, l-H-3-methylpyrazol-5-one, l-phenyl-3- methylpyrazol-5-one, 2-amino-3 -hydroxypyridine, 3,6-dimethyl-pyrazolo[3,2-c]-l ,2,4- triazole, 2,6-dimethylpyrazolo[l,5-b]-l,2,4-triazole, and their addition salts with an acid.

In general, the addition acid salts of the oxidation bases and couplers are chosen in particular from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates, and acetates.

- Direct dye

A direct dye means a colored substance which does not require the use of an oxidizing agent in order to develop its color.

The term "direct dye" means natural and/or synthetic dyes, which are soluble in the cosmetic medium, other than oxidation dyes which absorb color in the visible spectrum, i.e. which appear to be visually colored; they are dyes which will diffuse superficially on the keratin fibres.

The direct dyes may be selected from natural direct dyes and synthetic direct dyes.

The expression "natural direct dye" is understood to mean any dye or dye precursor that is naturally occurring and is produced by extraction (and optionally by purification) from a plant matrix or an animal such as an insect, optionally in the presence of natural compounds such as ash or ammonia.

As natural direct dyes, mention may be made of quinone dyes (such as lawsone and juglone), alizarin, purpurin, laccaic acid, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigoids such as indigo, sorghum, isatin, betanin, curcuminoids (such as curcumin), spinulosin, various types of chlorophyll and chlorophyllin, hematoxylin, hematein, brazilein, brazilin, safflower dyes (such as carthamin), flavonoids (such as rutin, quercetin, catechin, epicatechin, morin, apigenidin, and sandalwood), anthocyans (such as apigeninidin and apigenin), carotenoids, tannins, orceins, santalins and cochineal carmine.

It is also possible to use extracts or decoctions containing natural direct dye(s), in particular henna-based extracts, curcuma longa extract, sorghum leaf-sheath extract, haematoxylon campechianum extract, green tea extract, pine bark extract, cocoa extract, and logwood extract.

It is preferable that the natural direct dye be chosen from the group consisting of curcuminoids, santalins, chlorophyllin, haematoxylin, haematein, brazilein, brazilin, sorghum, laccaic acid, lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigoids, isatin, spinulosin, apigenin, orcein, betanin, flavonoids, anthocyans, and extracts or decoctions containing these compounds.

Alternatively, the natural direct dyes may be preferably chosen from, for example, hydroxylated quinones, indigoids, hydroxyflavones, santalins A and B, isatin and its derivatives, and brasilin and its hydroxylated derivatives.

The hydroxylated quinones are preferably benzoquinones, naphthoquinones, and mono- or polyhydroxylated anthraquinones which are optionally substituted with groups such as alkyl, alkoxy, alkenyl, chloro, phenyl, hydroxyalkyl and carboxyl.

The naphthoquinones are preferably lawsone, juglone, flaviolin, naphthazarin, naphthopurpurin, lapachol, plumbagin, chloroplumbagin, droserone, shikonin, 2 -hydroxy-3 - methyl- 1 ,4-naphthoquinone, 3 ,5-dihydroxy- 1 ,4-naphthoquinone, 2,5-dihydroxy- 1 ,4- naphthoquinone, 2-methoxy-5-hydroxy-l,4-naphthoquinone and 3-methoxy-5-hydroxy-l,4- naphthoquinone.

The benzoquinones are preferably spinulosin, atromentin, aurentioglyocladin, 2,5-dihydroxy- 6-methylbenzoquinone, 2-hydroxy-3-methyl-6-methoxybenzoquinone, 2, 5-dihydroxy-3,6- diphenylbenzoquinone, 2,3-dimethyl-5-hydroxy-6-methoxybenzoquinone and 2,5-dihydroxy- 6-isopropylbenzoquinone.

The anthraquinones are preferably alizarin, quinizarin, purpurin, carminic acid, chrysophanol, kermesic acid, rhein, aloe emodin, pseudopurpurin, quinizarincarboxylic acid, frangula emodin, 2-methylquinizarin, 1 -hydroxy anthraquinone and 2-hydroxyanthraquinone.

The indigoids are preferably indigo, indirubin, isoindigo and Tyrian purple.

The hydroxyflavones are preferably quercetin and morin.

The expression "synthetic direct dye" is understood to mean any dye or dye precursor that is produced by chemical synthesis.

The direct dye can be selected from the group consisting of acidic (anionic) direct dyes, basic (cationic) direct dyes, and neutral (nonionic) direct dyes.

Non-limiting examples of synthetic dyes include (nonionic) neutral, anionic (acidic), and cationic (basic) dyes such as azo, methine, carbonyl, azine, nitro(hetero)aryl types or tri(hetero)arylmethane direct dyes, porphyrins and phthalocyanines, alone or as mixtures.

More particularly, the azo dyes comprise an -N=N- functional group, the two nitrogen atoms of which are not simultaneously involved in a ring. However, it is not ruled out for one of the two nitrogen atoms of the -N=N- sequence to be involved in a ring.

The dyes of the family of the methines are more particularly compounds comprising at least one sequence chosen from >C=C< and -N=C<, the two atoms of which are not simultaneously involved in a ring. However, it is specified that one of the nitrogen or carbon atoms of the sequences can be involved in a ring. More particularly, the dyes of this family result from compounds of the following types: true methine (comprising one or more of the above-mentioned -C=C- sequences); azomethine (comprising at least one or more -C=N- sequences) with, for example, the azacarbocyanines and their isomers, the diazacarbocyanines and their isomers, the tetraazacarbocyanines; mono- and diarylmethane; indoamines (or diphenylamines); indophenols; indoanilines.

As regards to the dyes of the family of the carbonyls, mention may be made, for example, of synthetic dyes chosen from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, indanthrone, flavone, (iso)violanthrone, isoindolinone, benzimidazolone, iso- quinolinone, anthrapyridone, pyrazoloquinazoline, perinone, quinacridone, quinophthalone, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole or coumarin dyes.

As regards to the dyes of the family of the cyclic azines, mention may in particular be made of azine, xanthene, thioxanthene, fluorindine, acridine, (di)oxazine, (di)thiazine or pyronine dyes.

The nitro(hetero)aromatic dyes are more particularly nitrobenzene or nitropyridine direct dyes.

As regards to the dyes of porphyrin or phthalocyanine type, use may be made of cationic or noncationic compounds optionally comprising one or more metals or metal ions, such as, for example, alkali and alkaline earth metals, zinc and silicon.

Mention may be made, as examples of synthetic direct dyes which are particularly suitable, of nitrobenzene dyes, azo, azomethine or methine direct dyes, azacarbocyanines, such as tetraazacarbocyanines (tetraazapentamethines), quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes, or azine, xanthene, triarylmethane, indoamine, phthalocyanine and porphyrin direct dyes, alone or as mixtures. More preferably still, these synthetic direct dyes are chosen from nitrobenzene dyes, azo, azomethine or methine direct dyes and tetraazacarbocyanines (tetraazapentamethines); alone or as mixtures.

Mention may be made, among the azo, azomethine, methine or tetraazapentamethine direct dyes which can be used according to the present invention, of the cationic dyes described in Patent Applications WO 95/15144, WO 95/01772 and EP 714 954; FR 2 189 006, FR 2 285 851, FR-2 140 205, EP 1 378 544 and EP 1 674 073.

Thus, mention may in particular be made of the cationic direct dyes corresponding to the following formulae: in which:

D represents a nitrogen atom or the -CH group,

Ri and R2, which are identical or different, represent a hydrogen atom; a C1-C4 alkyl radical which can be substituted by a -CN, -OH or -NH2 radical or can form, with a carbon atom of the benzene ring, an optionally oxygen-comprising or nitrogen-comprising heterocycle which can be substituted by one or more C1-C4 alkyl radicals; or a 4'-aminophenyl radical, R3 and R’3, which are identical or different, represent a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano radical, a C1-C4 alkyl radical, a C1-C4 alkoxy radical or an acetyloxy radical,

X" represents an anion, preferably chosen from chloride, methyl sulphate and acetate, A represents a group chosen from the following structures: in which R4 represents a C1-C4 alkyl radical which can be substituted by a hydroxyl radical; in which:

Rs represents a hydrogen atom, a C1-C4 alkoxy radical or a halogen atom, such as bromine, chlorine, iodine or fluorine,

Re represents a hydrogen atom or a C1-C4 alkyl radical or forms with a carbon atom in the benzene ring, a heterocycle which optionally comprises oxygen and/or is optionally substituted by one or more Ci -C4 alkyl groups,

R7 represents a hydrogen atom or a halogen atom, such as bromine, chlorine, iodine or fluorine,

Di and D2, which are identical or different, represent a nitrogen atom or the -CH group, m - 0 or 1 ,

X’ represents a cosmetically acceptable anion preferably chosen from chloride, methyl sulphate and acetate,

E represents a group chosen from the following structures: in which R’ represents a C1-C4 alkyl radical; when m = 0 and when Di represents a nitrogen atom, then E can also denote a group with the following structure: in which R’ represents a C1-C4 alkyl radical.

The following cationic direct dyes are also particularly suitable to the invention:

X' represents an anion preferably chosen from chloride, iodide, methyl sulphate, ethyl sulphate, or acetate.

As examples of the cationic direct dyes, mention may be made of 4-nitro-o- phenylenediamine, 2-nitro-p-phenylenediamine, N,N'-bis-(2-hydroxyethyl)-2-nitro-p- phenylenediamine, 4-nitrophenylaminoethylurea, and 2-amino-6-chloro-4-nitrophenol, 2,6- diamino-3 -((pyridine-3 -yl)-azo)pyridine.

The synthetic direct dye may be selected from fluorescent dyes. Two or more types of fluorescent dyes may be used in combination.

The fluorescent dyes according to the present invention contain one or more colored and fluorescent chromophores.

The use of some fluorescent dyes may make it possible to obtain, on dark hair, colors which are more visible than with conventional hydrophilic or hydrophobic direct dyes.

Furthermore, these fluorescent dyes, when applied to dark hair, may also make it possible to lighten the hair without damaging it.

As used herein, the term "fluorescent dyes" is understood to mean fluorescent compounds and optical brighteners. In at least one embodiment, the fluorescent dye is soluble in the medium of the composition.

Fluorescent dyes are fluorescent compounds which absorb visible radiation, for example, wavelengths ranging from 400 to 800 run, and which are capable of re-emitting light in the visible region at a higher wavelength.

According to one embodiment, the fluorescent dyes useful for the present invention re-emit orange-colored fluorescent light. They exhibit, for instance, a maximum re-emission wavelength ranging from 500 to 700 nm.

Non-limiting examples of fluorescent dyes include compounds known in the art, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, Release 2004, 7th edition, "Fluorescent Dyes" chapter.

The optical brighteners of the present disclosure, also known under the name "brighteners", or "fluorescent brighteners", or "fluorescent brightening agents" or "FWA", or "fluorescent whitening agents", or "whiteners", or "fluorescent whiteners", are colorless transparent compounds as they do not absorb in visible light but only in ultraviolet light (wavelengths ranging from 200 to 400 nanometers) and convert the energy absorbed into fluorescent light of higher wavelength emitted in the visible part of the spectrum, generally in the blue and/or green, that is to say in wavelengths ranging from 400 to 550 nanometers. Optical brighteners are known in the art, for example, they are described in Ullmann's Encyclopedia of Industrial Chemistry (2002), "Optical Brighteners" and Kirk-Othmer Encyclopedia of Chemical Technology (1995): "Fluorescent Whitening Agents".

Soluble fluorescent compounds that may especially be mentioned include those belonging to the following families: naphthalimides, coumarins, xanthenes and in particular xanthenodiquinolizines and azaxanthenes; naphtholactams; azlactones; oxazines; thiazines; dioxazines; azo compounds; azomethines; methines; pyrazines; stilbenes; ketopyrroles; and pyrenes.

In terms of ionic nature, the direct dye may be selected from the group consisting of acidic direct dyes, basic direct dyes and neutral direct dyes, which covers all possible types of direct dyes, such as so-called nitro dyes and HC dyes. Acidic direct dyes have an anionic moiety in their chemical structure. Basic direct dyes have a cationic moiety in their chemical structure. Neutral direct dyes are nonionic.

According to an embodiment, it is preferable that the direct dye comprises at least one acidic direct dye.

The anionic direct dyes are commonly known as "acidic direct dyes" for their affinity with alkaline substances (see, for example, "Industrial Dyes, Chemistry, Properties, Application", Klaus Hunger Ed. Wiley-VCH Verlag GmbH & Co KGaA, Weinheim 2003). Anionic or acid dyes are known in the literature (see, for example, " Ullman ’s Encyclopedia of Industrial Chemistry", Azo Dyes, 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007. a03 245, point 3.2; ibid, Textile Auxiliaries, 2002 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007. a26 227 and "Ashford's Dictionary of Industrial Chemicals", Second Edition, p. 14-p. 39, 2001).

The term "anionic direct dyes" means any direct dye comprising in its structure at least one sulfonate group SO?" and/or at least one carboxylate group C(O)O' and/or at least one phosphonate group P(=O)O'O' and optionally one or more anionic groups G' with G', which may be identical or different, representing an anionic group chosen from alkoxide O', thioalkoxide S', phosphonate, carboxylate and thiocarboxylate: C(Q)Q” with Q and Q’, which may be identical or different, representing an oxygen or sulfur atom; preferably, G' represents a carboxylate, i.e. Q and Q’ represent an oxygen atom.

The preferred anionic dyes of the formula of the present invention are chosen from acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, anionic styryl dyes, and indigoids and acidic natural dyes; each of these dyes containing at least one sulfonate, phosphonate or carboxylate group bearing a cationic counterion X ⁺ , where X ⁺ represents an organic or mineral cationic counter ion preferably chosen from alkali and alkaline-earth metals, such as Na ⁺ and K ⁺

Preferred acid dyes may be chosen from: a) the diaryl anionic azo dyes of formula (II) or (IP):

in which formulae (II) and (IP):

• R.7, RS, RS>, RIO, R'7, R'S, R'9 and R'w, which may be identical or different, represent a hydrogen atom or a group chosen from: alkyl; alkoxy, alkylthio; hydroxyl, mercapto; nitro;

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

(O)2S(O’)-, X ⁺ as defined previously;

(O)CO‘-, X ⁺ as defined previously ;

(O)P(O ₂ ’)-, 2X ⁺ as defined previously ;

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

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

(di)(alkyl)amino; aryl(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O')-, X ⁺ and iv) alkoxy with X ⁺ ; optionally substituted heteroaryl; preferably a benzothiazolyl group; cycloalkyl; especially cyclohexyl,

Ar-N=N- with Ar representing an optionally substituted aryl group, preferably a phenyl optionally substituted with one or more alkyl, (O)2S(O‘)-, X ⁺ or phenylamino groups; or alternatively two contiguous groups R? with Rs or Rs with R9 or R9 with Rio together form a fused benzo group A’; and R’7 with R’s or R’s with R’9 or R’9 with R’10 together form a fused benzo group B’; with A’ and B’ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O‘)-, X ⁺ ; iv) hydroxyl; 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 X ⁺ , R°, X, X’, X” and Ar as defined previously;

• W represents a sigma bond o, an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(R _a )(Rb)- with Ra and Rb, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively R _a and Rb form, together with the carbon atom that bears them, a spiro cycloalkyl; preferably W represents a sulfur atom or Ra and Rb together form a cyclohexyl; it being understood that formulae (II) and (If) comprise at least one sulfonate (O)2S(O’)-, X ⁺ or phosphonate (O)P(O2‘) 2X ⁺ or carboxylate (O)C(O‘)-, X ⁺ radical on one of the rings A, A', B, B' or C with X ⁺ as defined previously;

As examples of dyes of formula (II), mention may be made of Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Food Red 17, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, 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, Pigment Red 57; and as examples of dyes of formula (IP), mention may be made of Acid Red 111, Acid Red 134, and Acid Yellow 38; b) the anthraquinone dyes of formulae (III) and (III'): in which formulae (III) and (IIP):

• R22, R23, R24, R25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from: alkyl; hydroxyl, mercapto; alkoxy, alkylthio; aryloxy or arylthio optionally substituted, preferably substituted with one or more groups chosen from alkyl and (O)2S(O')-, X ⁺ with X ⁺ as defined previously; aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (O)2S(O‘)-, X ⁺ with X ⁺ as defined previously;

(di)(alkyl)amino;

(di)(hydroxyalkyl)amino;

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

• Z’ represents a hydrogen atom or a group NR28R29 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from: alkyl; polyhydroxyalkyl such as hydroxyethyl; aryl optionally substituted with one or more groups, particularly i) alkyl such as methyl, w-dodecyl, -butyl; ii) (O)2S(O')-, X ⁺ with X ⁺ as defined previously; iii) R°- C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R°, X, X’ and X” as defined previously, preferably R° represents an alkyl group; cycloakyl; especially cyclohexyl;

• Z represents a group chosen from hydroxyl and NR’2sR’29 with R’28 and R’29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously; it being understood that formulae (III) and (IIP) comprise at least one sulfonate group (O)2S(O )-, X ⁺ with X ⁺ as defined previously;

As examples of dyes of formula (III), mention may be made of Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, HC Blue 16, which is a cationic anthraquinone dye, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; and EXT Violet 2, and as examples of dyes of formula (IIP), mention may be made of Acid Black 48; and c) the quinoline-based dyes of formula (IV): in which formula (IV):

• Rei represents a hydrogen or halogen atom or an alkyl group;

• R62, R63 and R64, which may be identical or different, represent a hydrogen atom or a group (O)2S(O’)-, X ⁺ with X ⁺ as defined previously;

• or alternatively Rei with R62, or Rei with R454, together form a benzo group optionally substituted with one or more groups (O)2S(O')-, X ⁺ with X ⁺ as defined previously;

• G represents an oxygen or sulfur atom or a group NRe with Re representing a hydrogen atom or an alkyl group; particularly G represents an oxygen atom; it being understood that formula (IV) comprises at least one sulfonate group (O)2S(O’)-, X ⁺ with X ⁺ as defined previously;

As examples of dyes of formula (IV), mention may be made of Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5: d) triarylmethane dyes of formula (Va) or (V'a) the triarylmethane direct dye(s) according to the present invention are catonic dyes of formulae (Va) and (V'a) below:

and also the organic or mineral acid or base addition salts thereof, the geometrical isomers, optical isomers and tautomers thereof, and the mesomeric forms thereof, and the solvates thereof such as hydrates: in which formulae (Va) and (Va) below:

Ri, R2, R3 and R4, which may be identical or different, represent a hydrogen atom or one of the following groups: (Ci-C6)alkyl which is optionally substituted, preferably with a hydroxyl group; aryl such as phenyl, aryl(Ci-C4)alkyl such as benzyl, heteroaryl, heteroaryl(Ci-C4)alkyl, or else two groups Ri, and R2, and/or R3 and R4, borne by the same nitrogen atom form, together with the nitrogen atom which bears them, an optionally substituted heterocycloalkyl group such as morpholino, piperazino or piperidino, preferably Ri, R2, R3 and R4, which may be identical or different, represent a hydrogen atom or a (Ci- C4)alkyl group;

Rs, Re, R7, Rs, R9, Rio, R11, R12, R13, R14, R15, and Rie, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from i) hydroxyl, ii) thiol, iii) amino iv) (di)(Ci-C4)(alkyl)amino, v) (di)arylamino such as (di)phenylamino, vi) nitro, vii) acylamino (-NR-C(O)R') in which the R radical is a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the R’ radical is a C1-C2 alkyl radical; viii) carbamoyl ((R)2N-C(O)-) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group; ix) carboxylic acid or ester, (-O-C(O)R') or (-C(O)OR'), in which the R' radical is a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical is a C1-C2 alkyl radical; x) alkyl which is optionally substituted, in particular with a hydroxyl group; xi) alkylsulfonylamino (RSO2-NR-) in which the R radical represents a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical represents a C1-C4 alkyl radical, a phenyl radical; xii) aminosulfonyl ((R)2N-SO2-) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group; xiii) (Ci-C4)alkoxy; and xiv) (Ci-C4)alkylthio; or else two radicals borne by two contiguous carbon atoms R5 and Re and/or R7 and Rs and/or R9 and Rio and/or Rn and R12 and/or R13 and R14 and/or R15 and Ri6 form, together with the carbon atoms which bear them, an aryl or heteroaryl, preferably benzo, 6-membered fused ring, said ring possibly also being optionally substituted, preferably an unsubstituted benzo ring;

Q’ represents an anionic counterion as defined previously, for achieving electron neutrality of the molecule, preferably chosen from halides such as chloride or bromide, and phosphate; when the cationic dye comprises one or more anionic substituents such as COOR or SO3R with R denoting a hydrogen or a cation, it is understood that there are then more cationic substituents than anionic substituents, such that the overall resulting charge of the triarylmethane structure is cationic, counterbalanced by Q'.

Even more preferably the direct dye(s) a) of the present invention are chosen from formulae (Va) and (V'a) such as from HC Blue 15, which is a neutral triarylmethane direct dye,

According to one preferred embodiment, the direct dye(s) a) is (are) chosen from the triarylmethane dyes of formula (Va) or (V'a), in which, taken alone or separately,

Ri, R2, R3 and R4 represent a hydrogen atom or a (Ci-C4)alkyl group such as methyl or ethyl;

Rs, R6, R7, Rs, R9, Rio, R11, R12, R13, R14, R15, and Ri6 represent a hydrogen atom, a halogen atom, such as chlorine, or a (Ci-C4)alkyl group such as methyl or ethyl, an amino group, a (di)(Ci-C4)(alkyl)amino group and, preferably, at least one of the R9, Rio, R11 or R12 groups represents a hydrogen atom, a halogen atom (Cl), or an amino group, or a (Ci- C4)(alkyl)amino or (di)(Ci-C4)(alkyl)amino group, preferably in the para position with respect to the phenyl group.

Preferably, the direct dye(s) of triaylmethane structure are chosen from Basic Violet 1 , Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 14, Basic Blue 1, Basic Blue 7, Basic Blue 26, Basic Green 1, Basic Blue 77 (also called HC Blue 15), and mixtures thereof.

It is preferable that the acidic direct dye be selected from the group consisting of Yellow 5, Orange 4, EXT. Violet 2, Acid Black 1 and Acid Violet 43 (CI 60730).

According to an embodiment, it is preferable that the direct dye comprise at least one basic direct dye.

The basic direct dyes, which can be used in the present invention, can include, but are not limited to, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17, Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 11, Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, and Basic Yellow 57.

According to an embodiment, it is preferable that the direct dye comprise at least one neutral (nonionic) direct dye.

The neutral (nonionic) direct dyes, which can be used in the present invention, can include, but are not limited to, nitro dyes, such as 4-amino-3 -nitrophenol, 2-amino-5-nitrophenol, 2- nitro-5 -glyceryl methylaniline, 3 -methylamino-4-nitrophenoxy ethanol, 4- hydroxypropylamino-3 -nitrophenol, HC dyes such as HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 9, Yellow 10, HC Red 1, HC Red 3, HC Red 7, HC Red 10, HC Red 7, HC Red 11, HC Blue 2, HC Blue 12, HC Blue 14, HC Orange 1, HC Orange 2, HC Violet 1, HC Violet 2, and disperse dyes.

The examples of the disperse dyes may include, but are not limited to, Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Blue 7, Disperse Brown 4, Disperse Orange 3, Disperse Red 11, Disperse Red 15, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, and Disperse Violet 15.

In one preferred embodiment of the present invention, the direct dye is selected from neutral synthetic direct dyes such as neutral anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane direct dyes.

• Pigments

In one embodiment, the coloring agent may be selected from pigments.

The term "pigments" should be understood as meaning white or colored, inorganic or organic particles of any shape which are insoluble and are intended to color or dye the keratin fibers.

The pigments can be white or colored, inorganic and/or organic.

Among the inorganic pigments that may be used, non-limiting mention may be made of titanium dioxide, optionally surface treated, zirconium or cerium oxide, as well as zinc, (black, yellow or red) iron or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, or metal powders, such as aluminum powder or copper powder. The pigments can also be chosen from nanopigments formed of metal oxides, such as titanium dioxide, zinc oxide, iron oxide, zirconium oxide, and cerium oxide, and mixtures thereof.

The term "nanopigments" is understood to mean pigments having a mean particle size ranging from 1 nm to 500 nm, such as particle sizes ranging from 10 nm to 100 nm.

Among the organic pigments that may be used, non-limiting mention may be made of carbon black, pigments of D&C type and lakes, such as lakes based on cochineal carmine and on barium, strontium, calcium or aluminum. For example, Red 33 (Disodium 5-amino-4- hydroxy-3-(phenylazo)-naphthalene-2,7-disulfonate) and Red 202 (Calcium bis[2-(3-carboxy- 2-hydroxynephthylazo)-5-methylbenzenesulfonate) may be used as the pigment of D&C type.

The organic pigment may also be a diketopyrrolopyrroles (DPP) such as the ones described in EP-A-542669, EP-A-787730, EP-A-787731 and WO-A- 96/08537.

The organic pigment may be selected from bio-pigments such as BioChromaDerm® or BioChromaEyes® provided from Biotic Phocea in France.

Preferably, the pigment may be chosen from metal oxides such as titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, and chromium oxide; manganese violet; Prussian blue; ultramarine blue; chromium hydrate; ferric blue; aluminum powder; copper powder; carbon black; pigments of D&C type; lakes; pearlescent pigments; and mixtures thereof.

The term "pearlescent pigments" should be understood as meaning iridescent particles of any shape, such as particles produced by certain shellfish in their shells or else synthesized. The pearlescent agents can be chosen from white pearlescent agents, such as mica covered with titanium dioxide or with bismuth oxychloride; colored pearlescent agents, such as titanium oxide-coated mica covered with iron oxide, titanium oxide-coated mica covered with ferric blue or chromium oxide, or titanium oxide-coated mica covered with an organic pigment of the above-mentioned type; and pearlescent agents based on bismuth oxychloride.

The coloring agent(s) may be present in the composition according to the present invention in an amount of 0.005% by weight or more, preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and even more preferably 0.08% by weight or more; and/or may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 3% by weight or less, relative to the total weight of the composition.

The coloring agent(s) may be present in the composition according to the present invention in an amount of 0.005% to 15% by weight, preferably 0.01% to 10% by weight, more preferably 0.05% to 5% by weight, and even more preferably 0.08% to 3% by weight, relative to the total weight of the composition.

(Alkaline Agent)

In one embodiment of the present invention, the composition comprises at least one additional alkaline agent in addition to the (a) polylysine. Two or more types of alkaline agents may be used in combination. Thus, a single type of alkaline agent or a combination of different types of alkaline agents may be used.

The alkaline agent may be an inorganic alkaline agent. It may be possible that the inorganic alkaline agent be selected from the group consisting of ammonia; ammonium salts; alkaline metal hydroxides; alkaline earth metal hydroxides; alkaline metal phosphates and monohydrogenophosphates such as sodium phosphate or sodium monohydrogenophosphate.

As examples of the inorganic alkaline metal hydroxides, mention may be made of sodium hydroxide and potassium hydroxide. As examples of the alkaline earth metal hydroxides, mention may be made of calcium hydroxide and magnesium hydroxide.

The ammonium salt can be organic ammonium salt or inorganic ammonium salt. The organic ammonium salt may be selected from, for example, ammonium salts with trimethylamine, triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, lysine, arginine; and ammonium formate, ammonium acetate, and alkylammonium hydroxides such as tetramethylammonium hydroxide, and mixtures thereof. The inorganic ammonium salt may be selected from, for example, ammonium carbonate, ammonium hydroxide, ammonium bicarbonate, ammonium chloride, ammonium nitrate, ammonium sulfate, and ammonium phosphate, and mixtures thereof.

The alkaline agent may be an organic alkaline agent. It is preferable that the organic alkaline agent be selected from the group consisting of monoamines and derivatives thereof; diamines and derivatives thereof; polyamines and derivatives thereof; basic amino acids and derivatives thereof; oligomers of basic amino acids and derivatives thereof; polymers of basic amino acids and derivatives thereof; urea and derivatives thereof; and guanidine and derivatives thereof. As examples of the organic alkaline agents, mention may be made of alkanolamines such as mono-, di- and tri-ethanolamine, and isopropanolamine; urea, guanidine and their derivatives; basic amino acids such as lysine, ornithine or arginine; and diamines such as those described in the structure below: wherein R denotes an alkylene such as propylene optionally substituted by a hydroxyl or a Ci- C4 alkyl radical, and Ri, R2, R3 and R4 independently denote a hydrogen atom, an alkyl radical or a C1-C4 hydroxyalkyl radical, which may be exemplified by 1,3 -propanediamine and derivatives thereof. Arginine, urea and monoethanolamine are preferable.

The alkaline agent can be included so that the pH of the reducing composition can range from 8 to 12, preferably from 8.5 to 12, and more preferably from 9 to 12.

In one embodiment (i) of the present invention, when the composition comprises the (b) at least one coloring agent selected from oxidative dyes, the composition comprises at least one additional alkaline agent.

In the embodiment (i) of the present invention, the additional alkaline agent may be present in the composition in an amount of 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, and even more preferably 4% by weight or more; and/or may be 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 8% by weight or less, relative to the total weight of the composition.

In the embodiment (i) of the present invention, the additional alkaline agent may be present in the composition in an amount of 1 to 20% by weight, preferably 2 to 15% by weight, more preferably 3 to 10% by weight, and even more preferably 4 to 8% by weight, relative to the total weight of the composition.

In another embodiment (ii) of the present invention, when the composition comprises the (b) coloring agent selected from direct dyes, the composition comprise at least one additional alkaline agent in an amount of less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight, and even more preferably less than 0.05% by weight, relative to the total weight of the composition.

In the embodiment (ii), the composition according to the present invention may be free from any alkaline agent.

(Other Ingredients)

The composition of the present invention may also comprise one or more additional ingredients as following.

- Cationic Polymer

The composition according to the present invention may comprise at least one cationic polymer. A single type of cationic polymer may be used, but two or more different types of cationic polymers may be used in combination.

It should be noted that, for the purposes of the present invention, the term “cationic polymer” denotes any polymer containing cationic groups and/or groups that may be ionized into cationic groups.

A type of the cationic polymer is not particularly limited as long as the effect of the present invention is obtaind. Since the effect of the present invention can be produced from the combination of the (a) polylysine and the (b) coloring agent of the present invention, any kind of cationic polymers can be used.

Such polymers may be chosen from those already known per se as improving the cosmetic properties of the hair, i.e., especially those described in patent application EP-A-337 354 and in French patents FR-2 270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519 863.

The cationic polymers that are preferred are chosen from those containing units comprising primary, secondary, tertiary and/or quaternary amine groups, which may either form part of the main polymer chain or may be borne by a side substituent directly attached thereto.

The cationic polymers used generally have a number-average molecular mass of between approximately 500 and approximately 5><10 ⁶ and preferably between approximately 10 ³ and approximately 3 x 10 ⁶ .

Among the cationic polymers that may be mentioned, more particularly are polymers of the polyamine, polyamino amide and polyquatemary ammonium type.

These are known products. They are described in particular in French patents 2 505 348 and 2 542 997. Among the said polymers, mention may be made of the following.

(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of formula (I), (II), (III) or (IV) below: in which

R.3, which may be identical or different, denote a hydrogen atom or a CH3 radical;

A, which may be identical or different, represent a linear or branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;

R4, Rs and Re, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group containing from 1 to 6 carbon atoms;

Ri and R2, which may be identical or different, represent hydrogen or an alkyl group containing from 1 to 6 carbon atoms, and preferably methyl or ethyl; and X denotes an anion derived from an inorganic or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.

The polymers of family (1) can also contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C1-C4) alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinyl-caprolactam, and vinyl esters.

Thus, among these polymers of family (1), mention may be made of:

- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as the product sold under the name Hercofloc by the company Hercules,

- the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described, for example, in patent application EP-A-080 976 and sold under the name Bina Quat P 100 by the company BASF,

- the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate sold under the name Reten by the company Hercules,

- quaternized or non-quatemized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name “Gafquat” by the company ISP, for instance “Gafquat 734” or “Gafquat 755”, or alternatively the products known as “Copolymer 845, 958 and 937”. These polymers are described in detail in French patents

2 077 143 and 2 393 573,

- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP, and

- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers sold in particular under the name Styleze CC 10 by ISP, and quaternized vinylpyrrolidone/dimethylaminopropyl methacrylamide copolymers such as the product sold under the name “Gafquat HS 100” by the company ISP.

(2) The cellulose ether derivatives comprising quaternary ammonium groups, which are described in French patent 1 492 597, and in particular the polymers sold under the names “JR” (JR 400, JR 125, JR 30M) or “LR” (LR 400, LR 30M) by the company Amerchol. These polymers are also defined in the CTFA dictionary as hydroxyethylcellulose quaternary ammoniums that have reacted with an epoxide substituted with a trimethylammonium group.

(3) Cationic cellulose derivatives such as the copolymers of cellulose or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, described especially in US patent 4 131 576, such as hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted especially with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.

The commercial products corresponding to this definition are more particularly the products sold under the name Celquat L 200 and Celquat H 100 by the company Akzo Nobel.

(4) The cationic guar gums described more particularly in US patents 3 589 578 and

4 031 307, such as guar gums containing trialkylammonium cationic groups. Use is made, for example, of guar gums modified with a salt (e.g., chloride) of 2,3 - epoxypropyltrimethylammonium. Mention may be made of guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyl trimonium chloride, such as those sold especially under the trade names Jaguar C13S, Jaguar CMS, Jaguar C17 and Jaguar C162 by the company Solvay.

(5) Polymers consisting of piperazinyl units and of divalent alkylene or hydroxyalkylene radicals containing straight or branched chains, optionally interrupted by oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, and also the oxidation and/or quatemization products of these polymers. Such polymers are described, in particular, in French patents 2 162 025 and 2 280 361.

(6) Water-soluble polyamino amides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyamino amides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyamino amide; these polyamino amides can be alkylated or, if they contain one or more tertiary amine functions, they can be quatemized. Such polymers are described, in particular, in French patents 2 252 840 and 2 368 508.

(7) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers containing, as a main constituent of the chain, units corresponding to formula (V) or (VI): in which formulae k and t are equal to 0 or 1 , the sum k + 1 being equal to 1 ; R9 denotes a hydrogen atom or a methyl radical; R7 and Rs, independently of each other, denote an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower (C1-C4) amidoalkyl group, or R7 and Rs can denote, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidyl or morpholinyl; R7 and Rs, independently of each other, preferably denote an alkyl group having from 1 to 4 carbon atoms; and Y' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. These polymers are described in particular in French patent 2 080 759 and in its Certificate of Addition 2 190 406.

Among the polymers defined above, mention may more particularly be made of the dimethyldiallylammonium chloride homopolymer sold under the name “Merquat 100” by the company Nalco (and its homologues of low weight-average molecular mass) and the copolymers of diallyldimethylammonium chloride and of acrylamide, sold under the name “Merquat 550”.

(8) The quaternary diammonium polymer containing repeating units corresponding to the formula: in which formula (VII):

Rio, Rn, R12 and R13, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or alternatively Rio, R11, R12 and R13, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second hetero atom other than nitrogen, or alternatively Rio, R11, R12 and R13 represent a linear or branched Ci-Ce alkyl radical substituted with a nitrile, ester, acyl or amide group or a group -CO-O-R14- D or -CO-NH-R14-D where R14 is an alkylene and D is a quaternary ammonium group;

Ai and Bi represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

X* denotes an anion derived from an inorganic or organic acid;

Ai, Rio and R12 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if Ai denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, Bi can also denote the group -(CH2) _n -CO-D-OC-(CH2) _n - in which D denotes: i) a glycol residue of formula: -O-Z-O-, where Z denotes a linear or branched hydrocarbonbased radical or a group corresponding to one of the following formulae: -(CH2-CH2-O)X-CH ₂ -CH2-; and

-[CH2-CH(CH ₃ )-O] _y -CH2-CH(CH3)- where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; ii) a bis-secondary diamine residue such as a piperazine derivative; iii) a bis-primary diamine residue of formula -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon-based radical, or alternatively the divalent radical -CH2-CH2-S-S-CH2- CH2-; or iv) a ureylene group of formula -NH-CO-NH-.

Preferably, X' is an anion such as chloride or bromide.

These polymers generally have a number-average molecular mass of between 1000 and 100 000.

It is more particularly possible to use polymers that consist of repeating units corresponding to the following formula in which

Rio, R11, R12 and R13, which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms approximately, n and p are integers ranging from 2 to 20 approximately, and X’ is an anion derived from a mineral or organic acid.

One particularly preferred compound of formula (VIII) is that for which Rio, Rn R12 and R13 represent a methyl group, n=3, p=6 and X=C1, which is called Hexadimethrine chloride according to the INCI (CTFA) nomenclature.

(9) Polyamines such as Polyquart H sold by Cognis, which is given under the reference name “Polyethylene glycol (15) tallow polyamine” in the CTFA dictionary.

(10) Crosslinked methacryloyloxy(Ci-C4)alkyltri(Ci-C4)alkylammonium salt polymers such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quatemized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quatemized with methyl chloride, the homo- or copolymerization being followed by crosslinking with a compound containing olefinic unsaturation, in particular methylenebisacrylamide. A crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of the said copolymer in mineral oil can be used more particularly. This dispersion is sold under the name “Salcare® SC 92” by the company BASF. A crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester can also be used. These dispersions are sold under the names “Salcare® SC 95” and “Salcare® SC 96” by the company Allied Colloids.

(11) Cationic Polyaminoacids

As the cationic polymer, it may be possible to use cationic polyaminoacids, which may be cationic homopolymers or copolymers, with a plurality of amino groups and carboxyl groups. The amino group may be a primary, secondary, tertiary or quaternary amino group. The amino group may be present in a polymer backbone or a pendent group, if present, of the cationic polyaminoacids. The carboxyl group may be present in a pendent group, if present, of the cationic polyaminoacids.

As examples of the cationic polyaminoacids, mention may be made of cationized collagen, cationized gelatin, steardimonium hydroxypropyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin protein, steardimonium hydroxypropyl hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed soy protein, and the like.

(12) Other cationic polymers which can be used in the context of the present invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives.

It is preferable that the cationic polymer be a polyquatemium polymer or a polymeric quaternary ammonium salt.

Polymeric quaternary ammonium salts are cationic polymers comprising at least one quatemized nitrogen atom. Mention may in particular be made, as polymeric quaternary ammonium salts, of the Polyquatemium products (CTFA name), which contribute mainly to the quality of foam and feeling of the skin after use, in particular the feeling of the skin after use. These polymers can preferably be chosen from the following polymers: Polyquatemium-5, such as the product Merquat 5 sold by Nalco;

Polyquatemium-6, such as the product Salcare SC 30 sold by BASF and the product Merquat 100 sold by Nalco;

Polyquatemium-7, such as the products Merquat S, Merquat 2200, Merquat 7SPR, and Merquat 550 sold by Nalco and the product Salcare SC 10 sold by BASF;

Polyquatemium-10, such as the product Polymer JR400 sold by Amerchol;

Polyquatemium-11, such as the products Gafquat 755, Gafquat 755N and Gafquat 734 sold by ISP;

Polyquatemium-15, such as the product Rohagit KF 720 F sold by Rohm;

Polyquatemium-16, such as the products Luviquat FC905, Luviquat FC370, Luviquat HM552 and Luviquat FC550 sold by BASF;

Polyquatemium-28, such as the product Styleze CC10 sold by ISP;

Polyquatemium-44, such as the product Luviquat Care sold by BASF;

Polyquatemium-46, such as the product Luviquat Hold sold by BASF; and Polyquatemium-47, such as the product Merquat 2001 sold by Nalco.

The cationic polymer (s) may be present in the composition according to the present invention in an amount of 0.001% to 5% by weight, preferably 0.005% to 3% by weight, more preferably 0.01% to 2% by weight, and even more preferably 0.05% to 1% by weight, relative to the total weight of the composition.

- Surfactant

The composition according to the present invention may comprise at least one surfactant. A single type of nonionic surfactant may be used, but two or more different types of nonionic surfactants may be used in combination.

Any surfactant may be used for the present invention. A type of the surfactant is not particularly limited as long as the effect of the present invention is obtaind. Since the effect of the present invention can be produced from the combination of the (a) polylysine and the (b) coloring agent of the present invention, any kind of surfactants can be used.

In one preferred embodiment, the surfactant used for the present invention may be selected from anionic surfactants and nonionic surfactants, and mixtures thereof.

• Nonionic Surfactant

The nonionic surfactant may have an HLB (Hydrophilic Lipophilic Balance) value of from 3.0 to 7.0, preferably from 3.5 to 6.0, and more preferably from 4.0 to 5.0. Alternatively, the nonionic surfactant may have an HLB value of from 11 to 17, preferably from 12 to 16, and more preferably from 13 to 15. If two or more nonionic surfactants are used, the HLB value is determined by the weighted average of the HLB values of all the nonionic surfactants.

The nonionic surfactant may be chosen from:

(1) surfactants chosen from polyglyceryl fatty acid esters, polyoxyalkylenated alkyl glycerides, and polyoxyalkylenated fatty ethers;

(2) mixed esters of fatty acid or of fatty alcohol, of carboxylic acid and of glycerol;

(3) fatty acid esters of sugars and fatty alcohol ethers of sugars; (4) surfactants chosen from fatty esters of sorbitan and oxyalkylenated fatty esters of sorbitan, and oxyalkylenated fatty esters;

(5) block copolymers of ethylene oxide (A) and of propylene oxide (B),

(6) polyoxy ethylenated (1-40 EO) and polyoxypropylenated (1-30 PO) alkyl (C16-C30) ethers,

(7) silicone surfactants, and

(8) mixtures thereof.

The surfactant (1) may be a fluid at a temperature of less than or equal to 45°C.

The surfactant (1) may be in particular: polyglyceryl fatty acid esters of at least one, preferably one, fatty acid comprising at least one saturated or unsaturated, linear or branched C8-C22 hydrocarbon group such as Cs- C22 alkyl or alkenyl group, preferably Cs-Cis alkyl or alkenyl group, and more preferably Cs- C12 alkyl or alkenyl group, and of 2-12 glycerols, preferably 2-10 glycerols and more preferably 2-8 glycerols; polyoxyethylenated (PEGylated) alkyl glycerides such as polyethylene glycol derivatives of a mixture of mono-, di- and tri-glycerides of caprylic and capric acids (preferably 2 to 30 ethylene oxide units, more preferably 2 to 20 ethylene oxide units, and even more preferably 2 to 10 ethylene oxide units), e.g., PEG-6 Caprylic/Capric Glycerides, PEG-7 Caprylic/Capric Glycerides, and PEG-7 glyceryl cocoate; polyoxyethylenated fatty ethers of at least one, preferably one, fatty alcohol comprising at least one saturated or unsaturated, linear or branched C8-C22 hydrocarbon group such as C8-C22 alkyl or alkenyl group, preferably Cs-Cis alkyl or alkenyl group, and more preferably C8-C12 alkyl or alkenyl group, and of 2 to 60 ethylene oxides, preferably from 2 to 30 ethylene oxides, and more preferably from 2 to 10 ethylene oxides; and mixtures thereof.

It is preferable that the polyglyceryl fatty acid ester have a polyglycerol moiety derived from 2 to 10 glycerols, more preferably from 2 to 8 glycerols, and further more preferably 4 to 6 glycerols.

The polyglyceryl fatty acid ester may be chosen from the mono, di and tri esters of saturated or unsaturated acid, preferably saturated acid, including 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and more preferably 8 to 12 carbon atoms, such as caprylic acid, capric acid, lauric acid, oleic acid, stearic acid, isostearic acid, and myristic acid.

The polyoxyalkylenated fatty ethers, preferably polyoxyethylenated fatty ethers, may comprise from 2 to 60 ethylene oxide units, preferably from 2 to 30 ethylene oxide units, and more preferably from 2 to 10 ethylene oxide units. The fatty chain of the ethers may be chosen in particular from lauryl, behenyl, arachidyl, stearyl and cetyl units, and mixtures thereof, such as cetearyl. Examples of ethoxylated fatty ethers which may be mentioned are lauryl alcohol ethers comprising 2, 3, 4, and 5 ethylene oxide units (CTFA names: Laureth-2, Laureth-3, Laureth-4, and Laureth-5), such as the products sold under the names Nikkol BL-2 by the company Nikko Chemicals, Emalex 703 by the company Nihon Emulsion Co., Ltd, Nikkol BL-4 by the company Nikko Chemicals, and EMALEX 705 by the company Nihon Emulsion Co., Ltd. Mention may also be made of, for example, stearyl alcohol ethers comprising 2, 3, 4, 5, and 20 ethylene oxide units (CTFA names: Steareth-2, Steareth-3, Steareth-4, Steareth-5, and Steareth-20), such as the products sold under the names Emalex 602 by the company Nihon Emulsion Co., Ltd., Emalex 603 by the company Nihon Emulsion Co., Ltd, Nikkol BS-4 by the company Nikko Chemicals, and Emalex 605 by the company Nihon Emulsion Co., Ltd.

It is also preferred that polyoxyalkylenated fatty ethers be polyethylene glycol ethers of Cs- C24 fatty alcohol or alcohols and polyoxyalkylenated derivatives thereof and polypropylene glycol ethers of C4-C24 fatty alcohol or alcohols such as PPG- 14 butyl ether and PPG- 15 stearyl ether.

The (2) mixed esters of fatty acids, or of fatty alcohol, of carboxylic acid and of glycerol, which can be used as the above nonionic surfactant, may be chosen in particular from the group comprising mixed esters of fatty acid or of fatty alcohol with an alkyl or alkenyl chain containing from 8 to 22 carbon atoms, preferably from 8 to 18 carbon atoms, and more preferably from 8 to 12 carbon atoms, and of a-hydroxy acid and/or of succinic acid, with glycerol. The a-hydroxy acid may be, for example, citric acid, lactic acid, glycolic acid or malic acid, and mixtures thereof.

The alkyl chain of the fatty acids or alcohols from which are derived the mixed esters which can be used in the nanoemulsion of the present invention may be linear or branched, and saturated or unsaturated. They may especially be stearate, isostearate, linoleate, oleate, behenate, arachidonate, palmitate, myristate, laurate, caprate, isostearyl, stearyl, linoleyl, oleyl, behenyl, myristyl, lauryl or capryl chains, and mixtures thereof.

As examples of mixed esters which can be used in the nanoemulsion of the present invention, mention may be made of the mixed ester of glycerol and of the mixture of citric acid, lactic acid, linoleic acid and oleic acid (CTFA name: Glyceryl citrate/lactate/linoleate/oleate) sold by the company Hills under the name Imwitor 375; the mixed ester of succinic acid and of isostearyl alcohol with glycerol (CTFA name: Isostearyl diglyceryl succinate) sold by the company Huis under the name Imwitor 780 K; the mixed ester of citric acid and of stearic acid with glycerol (CTFA name: Glyceryl stearate citrate) sold by the company Hills under the name Imwitor 370; the mixed ester of lactic acid and of stearic acid with glycerol (CTFA name: Glyceryl stearate lactate) sold by the company Danisco under the name Lactodan B30 or Rylo LA30.

The (3) fatty acid esters of sugars, which can be used as the above nonionic surfactant, may be chosen in particular from the group comprising esters or mixtures of esters of C8-C22 fatty acid and of sucrose, of maltose, of glucose or of fructose, and esters or mixtures of esters of C14-C22 fatty acid and of methylglucose.

The C8-C22 or C14-C22 fatty acids forming the fatty unit of the esters which can be used in the present invention comprise a saturated or unsaturated linear alkyl or alkenyl chain containing, respectively, from 8 to 22 or from 14 to 22 carbon atoms. The fatty unit of the esters may be chosen in particular from stearates, behenates, arachidonates, palmitates, myristates, laurates and caprates, and mixtures thereof. Stearates are preferably used.

The (3) fatty alcohol ethers of sugars, which can be used as the above nonionic surfactant, may be solid at a temperature of less than or equal to 45°C and may be chosen in particular from the group comprising ethers or mixtures of ethers of C8-C22 fatty alcohol and of glucose, of maltose, of sucrose or of fructose, and ethers or mixtures of ethers of a C14-C22 fatty alcohol and of methylglucose. These are in particular alkylpolyglucosides. The C8-C22 or C14-C22 faty alcohols forming the faty unit of the ethers which may be used in the nanoemulsion of the present invention comprise a saturated or unsaturated, linear alkyl or alkenyl chain containing, respectively, from 8 to 22 or from 14 to 22 carbon atoms. The fatty unit of the ethers may be chosen in particular from decyl, cetyl, behenyl, arachidyl, stearyl, palmityl, myristyl, lauryl, capryl and hexadecanoyl units, and mixtures thereof, such as cetearyl.

The (4) fatty esters of sorbitan and oxyalkylenated fatty esters of sorbitan which may be used as the above nonionic surfactant may be chosen from the group comprising C16-C22 faty acid esters of sorbitan and oxyethylenated C16-C22 fatty acid esters of sorbitan. They may be formed from at least one faty acid comprising at least one saturated linear alkyl chain containing, respectively, from 16 to 22 carbon atoms, and from sorbitol or from ethoxylated sorbitol. The oxyethylenated esters may generally comprise from 1 to 100 ethylene glycol units and preferably from 2 to 40 ethylene oxide (EO) units.

These esters may be chosen in particular from stearates, behenates, arachidates, palmitates, and mixtures thereof. Stearates and palmitates are preferably used.

The (4) oxyalkylenated faty esters, preferably ethoxylated faty esters, which may be used as the above nonionic surfactant, may be esters formed from 1 to 100 ethylene oxide units, preferably from 2 to 60 ethylene oxide units, and more preferably from 2 to 30 ethylene oxide units, and from at least one faty acid chain containing from 8 to 22 carbon atoms, preferably from 8 to 18 carbon atoms, and more preferably from 8 to 12 carbon atoms. The fatty chain in the esters may be chosen in particular from stearate, behenate, arachidate and palmitate units, and mixtures thereof. Examples of ethoxylated fatty esters which may be mentioned are the ester of stearic acid comprising 40 ethylene oxide units, such as the product sold under the name Myrj 52 (CTFA name: PEG-40 stearate) by the company ICI, as well as the ester of behenic acid comprising 8 ethylene oxide units (CTFA name: PEG-8 behenate), such as the product sold under the name Compritol HD5 ATO by the company Gatefosse.

The (5) block copolymers of ethylene oxide (A) and of propylene oxide (B), which may be used as the above nonionic surfactant, may be chosen in particular from block copolymers of formula (I):

HO(C2H4O) _x (C ₃ H6O) _y (C2H ₄ O) _z H (I) in which x, y and z are integers such that x+z ranges from 2 to 100 and y ranges from 14 to 60, and mixtures thereof, and more particularly from the block copolymers of formula (I) having an HLB value ranging from 8.0 to 14.0.

The (6) polyoxyethylenated (1-40 EO) and polyoxypropylenated (1-30 PO) alkyl (C16-C30) ethers, which may be used as the above nonionic surfactant, may be selected from the group consisting of:

PPG-6 Decyltetradeceth-30; Polyoxyethylene (30) Polyoxypropylene (6) Tetradecyl Ether such as those sold as Nikkol PEN-4630 from Nikko Chemicals Co.,

PPG-6 Decyltetradeceth-12; Polyoxyethylene (12) Polyoxypropylene (6) Tetradecyl Ether such as those sold as Nikkol PEN-4612 from Nikko Chemicals Co.,

PPG-13 Decyltetradeceth-24; Polyoxyethylene (24) Polyoxypropylene (13) Decyltetradecyl Ether such as those sold as UNILUBE 50MT-2200B from NOF Corporation,

PPG-6 Decyltetradeceth-20; Polyoxyethylene (20) Polyoxypropylene (6) Decyltetradecyl Ether such as those sold as Nikkol PEN-4620 from Nikko Chemicals Co.,

PPG-4 Ceteth-1; Polyoxyethylene (1) Polyoxypropylene (4) Cetyl Ether such as those sold as Nikkol PBC-31 from Nikko Chemicals Co.,

PPG-8 Ceteth-1; Polyoxyethylene (1) Polyoxypropylene (8) Cetyl Ether such as those sold as Nikkol PBC-41 from Nikko Chemicals Co.,

PPG-4 Ceteth-10; Polyoxyethylene (10) Polyoxypropylene (4) Cetyl Ether such as those sold as Nikkol PBC-33 from Nikko Chemicals Co.,

PPG-4 Ceteth-20; Polyoxyethylene (20) Polyoxypropylene (4) Cetyl Ether such as those sold as Nikkol PBC-34 from Nikko Chemicals Co.,

PPG-5 Ceteth-20; Polyoxyethylene (20) Polyoxypropylene (5) Cetyl Ether such as those sold as Procetyl AWS from Croda Inc.,

PPG-8 Ceteth-20; Polyoxyethylene (20) Polyoxypropylene (8) Cetyl Ether such as those sold as Nikkol PBC-44 from Nikko Chemicals Co., and

PPG-23 Steareth-34; Polyoxyethylene Polyoxypropylene Stearyl Ether (34 EO) (23 PO) such as those sold as Unisafe 34S-23 from Pola Chemical Industries. They can provide a composition with stability over a long time, even though the temperature of the composition is increased and decreased in a relatively short period of time.

As (7) silicone surfactants, which may be used as the above nonionic surfactant, mention may be made of those disclosed in documents US-A-5364633 and US-A-5411744.

The (7) silicone surfactant as the above nonionic surfactant may preferably be a compound of formula (I): in which:

Ri, R2 and R3, independently of each other, represent a Ci-Ce alkyl radical or a radical - (CH ₂ ) _x -(OCH ₂ CH ₂ ) _y -(OCH ₂ CH ₂ CH ₂ ) _z -OR4, at least one radical Ri, R ₂ or R3 not being an alkyl radical; R4 being a hydrogen, an alkyl radical or an acyl radical;

A is an integer ranging from 0 to 200;

B is an integer ranging from 0 to 50; with the proviso that A and B are not simultaneously equal to zero; x is an integer ranging from 1 to 6; y is an integer ranging from 1 to 30; z is an integer ranging from 0 to 5.

According to one preferred embodiment of the present invention, in the compound of formula (I), the alkyl radical is a methyl radical, x is an integer ranging from 2 to 6 and y is an integer ranging from 4 to 30.

As examples of silicone surfactants of formula (I), mention may be made of the compounds of formula (II): (CH ₃ ) ₃ SiO - [(CH ₃ ) ₂ SiO] _A - (CH ₃ SiO) _B - Si(CH ₃ ) ₃

(ID

(CH ₂ )2-(OCH ₂ CH2) _y -OH in which A is an integer ranging from 20 to 105, B is an integer ranging from 2 to 10 and y is an integer ranging from 10 to 20.

As examples of silicone surfactants of formula (I), mention may also be made of the compounds of formula (III):

H-(OCH ₂ CH ₂ ) _y -(CH2)3-[(CH3)2SiO]A’-(CH2)3-(OCH2CH2) _y -OH (III) in which A’ and y are integers ranging from 10 to 20.

•Anionic Surfactants:

According to the present invention, the type of anionic surfactant is not limited. It is preferable that the anionic surfactant be selected from the group consisting of (Ce-C3o)alkyl sulfates, (Ce-C3o)alkyl ether sulfates, (C6-C3o)alkylamido ether sulfates, alkylaryl polyether sulfates, and monoglyceride sulfates; (C6-C3o)alkylsulfonates, (Ce-C3o)alkylamide sulfonates, (C6-C3o)alkylaryl sulfonates, a-olefm sulfonates, and paraffin sulfonates; (C6-C3o)alkyl phosphates; (C6-C3o)alkyl sulfosuccinates, (Ce-C3o)alkyl ether sulfosuccinates, and (Ce- C3o)alkylamide sulfosuccinates; (Ce-C3o)alkyl sulfoacetates; (Ce-C24)acyl sarcosinates; (Ce- C24)acyl glutamates; (C6-C3o)alkylpolyglycoside carboxylic ethers; (Ce- C3o)alkylpolyglycoside sulfosuccinates; (Ce-C3o)alkyl sulfosuccinamates; (Ce-C24)acyl isethionates; N-(Ce-C24)acyl taurates; C6-C30 fatty acid salts; coconut oil acid salts or hydrogenated coconut oil acid salts; (Cs-C2o)acyl lactylates; (C6-C3o)alkyl-D-galactoside uronic acid salts; polyoxyalkylenated (Ce-C3o)alkyl ether carboxylic acid salts; polyoxyalkylenated (C6-C3o)alkylaryl ether carboxylic acid salts; and polyoxyalkylenated (Ce- C3o)alkylamido ether carboxylic acid salts.

In at least one embodiment, the anionic surfactants are in the form of salts such as salts of alkali metals, for instance sodium; salts of alkaline-earth metals, for instance magnesium; ammonium salts; amine salts; and amino alcohol salts. Depending on the conditions, they may also be in acid form.

It is also preferred that the anionic surfactant be selected from polyoxyalkylenated anionic surfactant, for example, comprising from 2 to 50 alkylene oxide, for instance ethylene oxide, groups.

As the polyoxyalkylenated anionic surfactant, mention can be made of an ester of poly ethoxylated C6-C30 fatty alcohol comprising 2 to 50 ethylene oxide units and a carboxylic acid, a phosphoric acid, or a sulfonic acid, such as Ceteth-10 phosphate.

The surfactant(s) may be present in the composition according to the present invention in an amount of 0.1% to 20% by weight, preferably 0.5% to 15% by weight, more preferably 1% to 10% by weight, and even more preferably 2% to 8% by weight, relative to the total weight of the composition. - Thickening Agent

The composition according to the present invention may comprise at least one thickening agent. A single type of thickening agent may be used, but two or more different types of thickening agent may be used in combination.

A type of the thickening agent is not particularly limited as long as the effect of the present invention is obtaind. Since the effect of the present invention can be produced from the combination of the (a) polylysine and the (b) coloring agent of the present invention, any kind of thickening agents can be used.

It is preferable that the thickening agent be selected from the group consisting of:

(i) associative thickeners;

(ii) crosslinked acrylic acid homopolymers;

(iii) crosslinked copolymers of (meth)acrylic acid and of (Ci-Ce)alkyl acrylate;

(iv) nonionic homopolymers and copolymers comprising ethylenically unsaturated monomers of ester and/or amide type;

(v) ammonium acrylate homopolymers and copolymers of ammonium acrylate and of acrylamide; and

(vi) polysaccharides.

(i) As used herein, the expression "associative thickener" means an amphiphilic thickener comprising both hydrophilic units and hydrophobic units, for example, at least one C8-C30 fatty chain and at least one hydrophilic unit.

Representative associative thickeners that may be used are associative polymers chosen from:

(aa) nonionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit;

(bb) anionic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit;

(cc) cationic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit; and

(dd) amphoteric amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit, wherein the fatty chain contains from 10 to 30 carbon atoms.

The (aa) nonionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit may, for example, be chosen from:

(l) celluloses modified with groups comprising at least one fatty chain; examples that may be mentioned include: hydroxyethylcelluloses modified with groups comprising at least one fatty chain chosen from alkyl, arylalkyl, and alkylaryl groups, and in which the alkyl groups are, for example, C8-C22, such as the product Natrosol Plus Grade 330 CS(Ci-C6 alkyls) sold by the company Aquaion, and the product Bermocoll EHM 100 sold by the company Berol Nobel, and celluloses modified with polyalkylene glycol alkylphenyl ether groups, such as the product Amercell Polymer HM-1500 (polyethylene glycol (15) nonylphenyl ether) sold by the company Amerchol.

(2) hydroxypropyl guars modified with groups comprising at least one fatty chain, such as the product Esaflor HM 22 (C22 alkyl chain) sold by the company Lamberti, and the products Miracare XC95-3 (C14 alkyl chain) and RE205-1 (C20 alkyl chain) sold by the company Rhodia Chimie.

(3) polyether urethanes comprising at least one fatty chain, such as C10-C30 alkyl or alkenyl groups, for instance the products Elfacos T 210 and Elfacos T 212 sold by the company Akzo or the products Aculyn 44 and Aculyn 46 sold by the company Rohm & Haas.

(4) copolymers of vinylpyrrolidone and of hydrophobic fatty-chain monomers; examples that may be mentioned include: the products Antaron V216 and Ganex V216 (vinylpyrrolidone/hexadecene copolymer) sold by the company I.S.P., and the products Antaron V220 and Ganex V220 (vinylpyrrolidone/eicosene copolymer) sold by the company I.S.P.

(5) copolymers of Ci-Ce alkyl acrylates or methacrylates and of amphiphilic monomers comprising at least one fatty chain, such as the oxyethylenated methyl methacrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208.

(6) copolymers of hydrophilic acrylates or methacrylates and of hydrophobic monomers comprising at least one fatty chain, such as a polyethylene glycol methacrylate/lauryl methacrylate copolymer.

The (bb) anionic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit, may, for example, be chosen from those comprising at least one fattychain allyl ether unit and at least one hydrophilic unit comprising an ethylenic unsaturated anionic monomeric unit, for example, a vinylcarboxylic acid unit and further, for example, be chosen from units derived from acrylic acids, methacrylic acids, and mixtures thereof, wherein the fatty-chain allyl ether unit corresponds to the monomer of formula (I) below:

CH ₂ =C(Ri)CH ₂ OB _n R (I) in which Ri is chosen from H and CH3, B is an ethyleneoxy radical, n is chosen from zero and integers ranging from 1 to 100, R is chosen from hydrocarbon-based radicals chosen from alkyl, arylalkyl, aryl, alkylaryl, and cycloalkyl radicals, containing from 10 to 30 carbon atoms, and further, for example, from 10 to 24 carbon atoms and even further, for example, from 12 to 18 carbon atoms.

In one embodiment, anionic amphiphilic polymers are, for example, polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of lower alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether of formula (I), and from 0% to 1% by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for example, diallyl phthalate, allyl(meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, and methylenebisacrylamide.

The anionic amphiphilic polymers may further be chosen, for example, from those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of a type such as a (C10-C30) alkyl ester of an unsaturated carboxylic acid. The hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to, for example, the monomer of formula (II) below: in which R ¹ is chosen from H, CH3, and C2H5, i.e., acrylic acid, methacrylic acid, and methacrylic acid units. The hydrophobic unit of a type such as a (C10-C30) alkyl ester of an unsaturated carboxylic acid corresponds to, for example, the monomer of formula (III) below: in which R ¹ is chosen from H, CH3, and C2H5 (i.e., acrylate, methacrylate, and methacrylate units) and is, for example, chosen from, for example, H (acrylate units) and CH3 (methacrylate units), and R ² is chosen from C10-C30 alkyl radicals, for example, C12-C22 alkyl radicals.

Examples of (Cio-C3o)alkyl esters of unsaturated carboxylic acids include lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

Among said polymers above, mention may be made, for example, of the products sold by the company Goodrich under the trade names Pemulen TRI, Pemulen TR2, and Carbopol 1382, and further, for example, Pemulen TRI, and the product sold by the company S.E.P.C. under the name Coatex SX.

Among anionic amphiphilic fatty-chain polymers, mention may also be made, for example, of the ethoxylated copolymer of methacrylic acid/methyl acrylate/alkyl dimethyl-meta- isopropenylbenzylisocyanate sold under the name Viscophobe DB 1000 by the company Amerchol.

The (cc) cationic amphiphilic polymers used are, for example, chosen from quatemized cellulose derivatives and polyacrylates comprising amino side groups.

The quatemized cellulose derivatives are, for example, chosen from quatemized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl, and alkylaryl groups comprising at least 8 carbon atoms, and mixtures thereof, and quatemized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl, and alkylaryl groups comprising at least 8 carbon atoms, and mixtures thereof.

Quatemized and non-quatemized polyacrylates comprising amino side groups have, for example, hydrophobic groups, such as Steareth 20 (polyoxy-ethylenated(20) stearyl alcohol) and (Cio-C3o)alkyl PEG-20 itaconate.

The alkyl radicals borne by the above quatemized celluloses and hydroxyethylcelluloses, for example, contain from 8 to 30 carbon atoms.

Examples of quatemized alkylhydroxyethyl-celluloses comprising C8-C30 fatty chains are the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529-18B (C12 alkyl), and Quatrisoft LM-X 529-8 (Ci 8 alkyl) sold by the company Amerchol, and the products Crodacel QM, Crodacel QL (C12 alkyl), and Crodacel QS (Cis alkyl) sold by the company Croda.

Among the (dd) amphoteric amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit, mention may be made, for example, of copolymers of methacrylamidopropyltrimethylammonium chloride/acrylic acid/Cio-Cso alkyl methacrylate, wherein the alkyl radical is, for example, a stearyl radical.

The associative thickener may be an associative polymeric thickener, preferably an associative polyurethane thickener.

The associative polyurethane thickener may be cationic or nonionic.

Among the associative polyurethane thickeners, there may be mention of the associative polyurethane derivatives such as those obtained by polymerization: about 20% to 70% by weight of a carboxylic acid containing an a,P-monoethylenic unsaturation, about 20 to 80% by weight of a nonsurfactant monomer containing an a,P-monoethylenic unsaturation, about 0.5 to 60% by weight of a nonionic mono-urethane which is the product of the reaction of a monohydroxylated surfactant with a monoethylenically unsaturated monoisocyanate.

As the associative polyurethane thickeners, mention can be made of Polyurethane-39 sold under the product name of Luvigel Star® by the company BASF.

(ii) Among the crosslinked acrylic acid homopolymers that may be mentioned are those crosslinked with an allylic alcohol ether of the sugar series. Mention may be made of carbomer, which is a homopolymer of acrylic acid crosslinked with an allyl ether of pentaerythritol, an allyl ether of sucrose, or an allyl ether of propylene, such as the products sold under the names Carbopol 980, 981, 954, 2984, and 5984 by the company Lubrizol or the products sold under the names Synthalen M and Synthalen K by the company 3 VS A.

(iii) The crosslinked copolymers of (meth)acrylic acid and of Ci-Ce alkyl acrylate can be chosen from crosslinked copolymers of methacrylic acid and of ethyl acrylate as an aqueous dispersion comprising 38% active material sold, for example, under the name Viscoatex 538C by the company Coatex, and crosslinked copolymers of acrylic acid and of ethyl acrylate as an aqueous dispersion comprising 28% active material sold under the name Aculyn 33 by the company Rohm & Haas. Crosslinked copolymers of methacrylic acid and of ethyl acrylate include an aqueous dispersion comprising 30% active material sold under the name CARBOPOL AQUA SF-1 by the company NOVEON.

(iv) Among the nonionic homopolymers or copolymers comprising ethylenically unsaturated monomers of ester and/or amide type, mention may be made of the products sold under the names: Cyanamer P250 by the company Cytec (polyacrylamide); PMMA MBX-8C by the company US Cosmetics (methyl methacrylate/ethylene glycol dimethacrylate copolymer); Acryloid B66 by the company Rohm & Haas (butyl methacrylate/methyl methacrylate copolymer); and BPA 500 by the company Kobo (polymethyl methacrylate).

(v) Ammonium acrylate homopolymers that may be mentioned include the product sold under the name Microsap PAS 5193 by the company Hoechst.

Copolymers of ammonium acrylate and of acrylamide include the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst (which are described and prepared in documents FR-2 416 723, U.S. Pat. No. 2,798,053, and U.S. Pat. No. 2,923,692).

(vi) The polysaccharides are, for example, chosen from glucans, modified and unmodified starches (such as those derived, for example, from cereals, for instance wheat, com, or rice, from vegetables, for instance yellow peas, and tubers, for instance potatoes or cassava), amylose, amylopectin, glycogen, dextrans, celluloses, and derivatives thereof (e.g., methylcelluloses, hydroxyalkylcelluloses, hydroxyethylcelluloses, and carboxymethylcelluloses), mannans, xylans, lignins, arabans, galactans, galacturonans, chitins, chitosans, glucuronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acids, and pectins, alginic acid and alginates, arabinogalactans, carrageenans, agars, glycosaminoglucans, gum arabics, gum tragacanths, ghatti gums, karaya gums, carob gums, galactomannans, such as guar gums, and nonionic derivatives thereof (e.g., hydroxypropyl guar), sclerotium gum and xanthan gums, and mixtures thereof.

The thickening agent(s) may be present in the composition according to the present invention in an amount of 0.1% to 20% by weight, preferably 0.5% to 15% by weight, more preferably 1% to 10% by weight, and even more preferably 2% to 8% by weight, relative to the total weight of the composition.

• Cosmetically Acceptable Hydrophilic Organic Solvent

The composition according to the present invention may comprise at least one cosmetically acceptable hydrophilic organic solvent. If two or more of these solvents are used, they may be the same or different.

A type of the hydrophilic organic solvent is not particularly limited as long as the effect of the present invention is obtaind. Since the effect of the present invention can be produced from the combination of the (a) polylysine and the (b) coloring agent of the present invention, any kind of hydrophilic organic solvents can be used.

The cosmetically acceptable hydrophilic organic solvent(s) may include, for example, substantially linear or branched lower mono-alcohols having from 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol, and isobutanol; aromatic alcohols, such as benzyl alcohol and phenylethyl alcohol; polyols or polyol ethers, such as propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerin, propanediol, caprylyl glycol, sorbitol, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol ethers, such as propylene glycol monomethylether, diethylene glycol alkyl ethers, such as diethylene glycol monoethylether or monobutylether; polyethylene glycols, such as PEG-4, PEG-6, and PEG-8, PEG-20, and their derivatives.

The amount of the cosmetically acceptable hydrophilic organic solvent(s) in the composition according to the present invention may range from 0.1% to 20% by weight, preferably from 1% to 15% by weight, and more preferably from 2% to 10% by weight, relative to the total weight of the composition.

• Oil

The composition according to the present invention may comprise at least one oil. The composition may also comprise two or more oils in combination.

Here, “oil” means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg). As the oils, those generally used in cosmetics can be used alone or in combination thereof.

A type of the oil is not particularly limited as long as the effect of the present invention is obtaind. Since the effect of the present invention can be produced from the combination of the (a) polylysine and the (b) coloring agent of the present invention, any kind of oils can be used.

The oils may be volatile or non-volatile. Preferably, the oil is a non-volatile oil.

The non-volatile oil may be selected from:

- hydrocarbon-based oils of animal origin, such as perhydrosqualene,

- hydrocarbon-based oils of plant origin, such as phytostearyl esters, such as phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutamate, triglycerides formed from fatty acid esters of glycerol, in particular in which the fatty acids may have chain lengths ranging from C4 to C36 and especially from Cis to C36, these oils possibly being linear or branched, and saturated or unsaturated; these oils may especially be heptanoic or octanoic triglycerides, shea oil, alfalfa oil, poppy oil, winter squash oil, millet oil, barley oil, quinoa oil, rye oil, candlenut oil, passionflower oil, shea butter, aloe vera oil, sweet almond oil, peach stone oil, groundnut oil, argan oil, avocado oil, baobab oil, borage oil, broccoli oil, calendula oil, camelina oil, canola oil, carrot oil, safflower oil, flax oil, rapeseed oil, cottonseed oil, coconut oil, marrow seed oil, wheatgerm oil, jojoba oil, lily oil, macadamia oil, com oil, meadowfoam oil, monoi oil, hazelnut oil, apricot kernel oil, walnut oil, olive oil, evening primrose oil, palm oil, blackcurrant seed oil, kiwi seed oil, grapeseed oil, pistachio oil, winter squash oil, pumpkin oil, quinoa oil, musk rose oil, sesame oil, soybean oil, sunflower oil, castor oil and watermelon oil, and mixtures thereof, or alternatively caprylic/capric acid triglycerides,

- linear or branched hydrocarbon oils of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, petroleum jelly, mineral oil, polydecenes, polybutenes, hydrogenated polyisobutene such as Parleam, and squalane;

- ether oils containing from 10 to 40 carbon atoms, such as dicaprylyl ether;

- ester oils, for instance oils of formula R1COOR2, in which Ri represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms, preferably 1 to 26 carbon atoms, and R2 represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms, preferably 1 to 26 carbon provided that Ri + R2 > 10. The esters may be chosen especially from fatty acid esters of alcohols, for example, cetyl esters, in particular, cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, isopropyl isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate, 2-ethylhexyl palmitate, alkyl benzoates, in particular C12-C15 alkyl benzoates, polyethylene glycol diheptanoate, propylene glycol 2-diethylhexanoate, and mixtures thereof, hexyl laurate, neopentanoic acid esters, for instance isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldodecyl neopentanoate, isononanoic acid esters, for instance isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, hydroxylated esters, for instance isostearyl lactate and diisostearyl malate

- fluoro oils that are optionally partially hydrocarbon-based and/or silicone-based, for instance fluoro silicone oils, fluoropolyethers and fluorosilicones;

- fatty alcohols that are saturated or unsaturated, linear or branched, and contain 6 to 30 carbon atoms and more particularly from 8 to 30 carbon atoms: mention may be made of cetyl alcohol, stearyl alcohol and a mixture thereof (cetylstearyl alcohol), octyldodecanol, 2- butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or lirioleyl alcohol;

- silicone oils, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane; and phenyl silicone oils such as phenyl trimethicone, and

- mixtures thereof.

The oil may be present in a content ranging from 2% to 40% by weight, preferably from 5% to 35% by weight, and more preferably from 10% to 30% by weight relative to the total weight of the composition.

- Additional Active Ingredient

The composition according to the present invention may comprise at least one additional cosmetically active ingredient e. The term “active ingredient” used herein means an organic compound having any cosmetic or dermatological effects on a keratinous substance, such as skin and hair. Well-known cosmetic active ingredients in the cosmetic field can be used as the optional active ingredients. Preferably, the additional cosmetic ingredients are active ingredients for caring for or conditioning keratinous substances, such as skin and hair.

The additional active ingredients may include, but are not limited to, derivatives of vitamins, such as derivatives of vitamin A (retinol), vitamin C (ascorbic acid), vitamin B3 (niacin) and the like, mucopolysaccharides and derivatives thereof, such as hyaluronic acid and chondroitin and derivatives thereof, and ceramide compounds, such as natural or synthetic ceramides and/or glycoceramides and/or pseudoceramides and/or neoceramides, for example, 2-oleamido-l,3-octadecanedioL

The additional active ingredient(s) may be present in the composition according to the present invention in an amount of 0.01% to 10% by weight, preferably 0.05% to 5% by weight, more preferably 0.1% to 3% by weight, and even more preferably 0.2% to 1% by weight, relative to the total weight of the composition.

- Water

The composition according to the present invention typically comprises water.

The amount of water in the composition may be 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and even more preferably 45% by weight or more; and/or may be 95% by weight or less, preferably 90% by weight or less, and more preferably 85% by weight or less, relative to the total weight of the composition.

- Adjuvants The additional adjuvant(s) may be included in the composition, which may be selected from the group consisting of; anionic, nonionic or amphoteric polymers; penetrating agents; agents for combating hair loss; anti-dandruff agents, suspending agents; chelating or sequestering agents, such as EDTA, pyrophosphate; buffer; opacifying agents; fragrances; pH adjusting agents of acidic agent(s); anti-oxidant or preserving agents, such as chlorhexidine digluconate, sodium metabisulfite, and phenoxyethanol; stabilizers; and mixtures thereof.

The adjuvants may be present in the second composition of the present invention in an amount preferably ranging from 0.001% to 20% by weight, preferably from 0.01% to 10% by weight, more preferably from 0.1% to 5% by weight, and even more preferably from 0.2% to 2% by weight, relative to the total weight of the composition.

In some specific embodiments of the preset invention, the composition comprises at least one acid in an amount of less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight, even more preferably less than 0.3% by weight, and in particular less than 0.1% by weight, relative to the total weight of the composition.

In some specific embodiments of the present invention, the composition comprises the acid in an amount so that the ratio of the amine group number of the (a) polylysine to the acid group number of the acid is 3 time or more, preferably 4 times or more, more preferable 5 times or more, and in particular 10 times or more. In other words, in the composition according to the present invention, the amine group number of the (a) polylysine is 3 times greater, preferably 4 times greater, more preferable 5 times greater, and in particular 10 times greater than that of acid number of the acid, if it is included.

The at least one acid, if present, may be chosen from a fatty carboxylic acid, a fatty ether carboxylic acid, a fatty ether phosphoric acid, a fatty phosphoric acid and mixtures thereof. The at least one acid (b) may contain one or two or more acid groups (a polyacid).

The composition according to the present invention may take various forms, such as, a solution, a gel, a lotion, a serum, a suspension, a dispersion, a fluid, a milk, a paste, a cream, a foam, an emulsion (O/W or W/O form), multiple (e.g., W/O/W, polyol/O/W, and O/W/O) emulsions, and the like. In one specific embodiment, the composition according to the present invention is in the form of an emulsion of the O/W or W/O form.

The composition according to the present invention can be prepared by mixing the above essential and optional ingredients in accordance with any of the processes which are well known to those skilled in the art.

[Cosmetic Process and Use]

The present invention also relates to a cosmetic process for coloring keratin fibers, preferably hair, comprising the step of: applying onto the keratin fibers the composition according to the present invention.

The applying step can be performed by any conventional means such as an applicator, e.g., hands, a spray, a brush and a comb.

When the composition according to the present invention comprises at least one oxidative dye, the process according to the present invention further comprises additional step to mix the composition with at least one developer comprising at least one oxidizing agent to prepare ready-to-use composition prior to the application.

The oxidizing agent may be chosen from hydrogen peroxide, peroxygenated salts, and compounds capable of producing hydrogen peroxide by hydrolysis. For example, the oxidizing agent can be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates and ferricyanides and persalts such as perborates and persulphates. At least one oxidase enzyme chosen, for example, from laccases, peroxidases and 2-electron oxidoreductases such as uricase may also be used as the oxidizing agent, where appropriate in the presence of the respective donor or co-factor thereof.

In one embodiment, the oxidizing agent is hydrogen peroxide, and the developer is an aqueous hydrogen peroxide solution.

In the developer in the form of an aqueous hydrogen peroxide solution, the concentration of the hydrogen peroxide stabilizer may range from 0.0001% to 5% by weight such as from 0.01% to 2% by weight, relative to the total weight of the developer.

The mixing ratio of the composition according to the present invention and the developer is not limited. The mixing ratio may be 1 :3 to 3 : 1 , preferably 1 :2 to 2: 1 , and more preferably 1 : 1 , as the weight ratio thereof.

It is preferable that the process according to the present invention further comprise a step of washing, with or without drying, keratin fibers before and/or after the step of applying the composition onto the keratin fibers.

The keratin fibers to which the composition has been applied can be left for an appropriate time which is required to treat the keratin fibers. The time length for the treatment is not limited, but it may be from 1 minute to 1 hour, preferably 5 minutes to 50 minutes, and more preferably 10 minutes to 40 minutes.

The keratin fibers may be treated at room temperature. Alternatively, the keratin fibers can be heated at 25°C to 65°C, preferably 30°C to 60°C, more preferably 35°C to 55°C, and even more preferably 40°C to 50°C, before and/or during and/or after the step of applying the composition onto the keratin fibers. Preferably, the keratin fibers are treated without heating, before and/or during and/or after the step of applying the composition onto the keratin fibers.

The present invention also relates to a cosmetic process or use of the (a) polylysine to enhance color intensity and color lastingness of the keratin fibers, such as hair, colored with the composition comprising the (b) at least one coloring agent selected from dyes and pigments, where the dyes are selected from oxidative dyes and direct dyes other than irridoid dyes, and the (a) polylysine has a weight-average molecular weight in the range of 4,500 g/mol to 25,000 g/mol.

For the above ingredients (a), (b), the composition, and the alkaline agent, those explained above can be used.

EXAMPLES The present invention will be described in a more detailed manner by way of examples. However, these examples should not be construed as limiting the scope of the present invention.

[Preparation]

(Examples)

Compositions according to Examples 1 to 6 and Comparative Examples 1 to 3 were prepared by mixing the ingredients listed in Tables 1 and 2 in accordance following protocols. The formulations of the compositions and their pH values are summarized in the tables. Epsilon- poly-L-lysines (Mw: around 4,700 g/mol, basic grade) were obtained from JNC corporation. Epsilon-poly-L-lysine (Mw: around 18,000 g/mol, basic grade) was obtained from TCR Canada. The numerical values for the amounts of the ingredients shown in the tables are all based on “% by weight” as active raw materials.

- Preparation protocol for Examples 1 to 4 and Comparative Examples 1 and 2

In 40% of the total amount of deionized water and other solvent, chelating agent was dissolved under 80°C to prepare an aqueous phase. In parallel, in another beaker, oils and surfactants were melted under 80°C to prepare an oil phase. Once those components were well melted and that the aqueous phase was well homogeneous, the content of the oil phase was poured into the water phase and the emulsification was carried out during 10 minutes under stirring. After the mixture cooled down until reaching 50°C, anti-oxidant agents and the oxidative dyes, i.e. p-phenylenediamine, resorcinol, 2,4-diaminophenoxyethanol HCL, p- aminophenol, and/or N,N-bis (2-hydroxyethyl)-p-phenylenediamine sulfate, previously dissolved in hot deionized water, were added to the mixture. After cooled down to 30°C, fragrance and epsilon-poly-L-lysine, were added. Then the alkaline agents were added and mixed with the rest of water. The mixture was let under stirring until the temperature reaches room temperature.

- Preparation protocol for Examples 5 and 6 and Comparative Example 3

The thickening agent was dissolved in hot deionized water at 60°C for 10 minutes and then polymer was added under stirring and dissolved for 10 minutes to prepare a water phase. In another beaker, oils and surfactants were dissolved at 75 °C. When this phase was well melted, it was added into the water phase previously prepared and the emulsification was performed during 10 minutes under stirring. After, the mixture cooled down until reaching 40°C, the preservatives, fragrance and a direct dye (HC blue 16) were added with the rest of water. The mixture was let under stirring until the temperature reaches room temperature.

Table 2 -(active matter %) (Developer) A developer composition was prepared by the following protocol. Chelating agents and preservatives were dissolved in hot deionized water at 80 °C to prepare a water phase. In another beaker, oils and surfactants were mixed under 80 °C to prepare an oil phase. When the 2 phases were well homogeneous, the oil phase was added in the water phase and emulsified during 10 minutes. When the mixture reached room temperature, the hydrogen peroxide and pH adjuster were added with the rest of deionized water.

The formulation of the developer composition is summarized in Table 3 below. The numerical values for the amounts of the ingredients shown in Table 3 are all based on “% by weight” as active raw materials.

Table 3 -(active matter %)

[Evaluation]

(Color Intensity)

A 100% Chinese white hair swatch (1 g, 20 cm) was prepared by conventionally bleaching 100% Chinese hair swatch. The obtained 100% Chinese white hair swatch was washed with a conventional shampoo, rinsed with running tap water at 40°C, and then dried. The compositions according to each of Examples 1 to 5 and Comparative Examples 1 and 2 were mixed with the developer composition in a mixing weight ratio of 1 : 1 before an application.

3 g of each of the mixed compositions or compositions according to Examples 5 and 6 and Comparative Example 3 was applied to 100% Chinese white hair swatch with a spatula at room temperature. After 15 minutes, the swatches were turned on the other side and left for another 15 minutes. Finally, swatches were rinsed with tap water at 40°C, washed with conventional shampoo and rinsed again with tap water at 40°C before they were dried. The difference in color of the colored swatch before and after the coloring process was measured by measuring the colorimetric values (L*, a*, b*, lightness I green-red I blue-yellow) using a Konica Minolta Spectrophotometer CM-3600A. AE* values (between the swatch before and after the treatment of the coloring process under AL*a*b system) were calculated. The larger AE* is, the better the color intensity is.

(Color Lastingness)

Each of the colored Chinese 100% white hair swatches was rinsed with tap water at 40 °C by 40 fingers through, and then the it washed with a conventional shampoo composition by 20 fingers through. The swatches were then rinsed by 30 fingers through under tap water at 40°C and dried gently while being combed. This process is repeated 6 more times to simulate one week of consumer habit. The difference in color of the colored swatch before and after shampooing for 1 cycle and 7 cycles were measured by measuring the colorimetric values (L* (lightness), a* (green-red), b* (blue-yellow), and h (hue angle)) using a Konica Minolta Spectrophotometer CM-3600A. AE* values (between the color of the colored swatch and the color of the shampooed swatch under AL*a*b system) were calculated. The smaller AE* indicates, the better the color lastingness is. The examples and results are summarized in Table 4.

Comparing Examples 1, 3, and 4 and Comparative Example 1, although these compositions comprise the same oxidative dye, Examples 1, 3, and 4 which include the polylysine showed larger AE* before/after coloration and smaller AE* before/ after one or seven shampoos than Comparative Example 1.

Also, comparing Example 2 and Comparative Example 2, although these compositions comprise the same oxidative dye system, Example 2 which includes the polylysine showed larger AE* before/after coloration and smaller AE* before/after one or seven shampoos than Comparative Example 2.

In addition, comparing Examples 5 and 6 and Comparative Example 3, although these compositions comprise the same direct dye system, Examples 5 and 6, which include the polylysine, showed larger or comparable AE* before/after coloration and smaller AE* before/after one or seven shampoos than Comparative Example 3.

Furthermore, comparing Examples 5 and 6, although these examples showed smaller AE* before/after one or seven shampoos than Comparative Example 3 and thus showed superior coloring uptake effect and long-lastingness of coloring than Comparative Example 3, Example 6, which comprises a combination of the polylysine and an alkaline agent, showed much smaller AE* before/after one or seven shampoos than Example 5, which includes polylysine and does not include any other alkaline agents. Therefore, it can be said that, although Examples 5 and 6 exhibit the inventive effect of the present invention, Example 6 could exhibit better lastingness than Example 5.

Therefore, it can be concluded that the compositions according to the present invention can provide an improvement in color intensity and long-lastingness of coloring on the keratin fibers.