FR3138034A1 - Composition comprising at least one particular imidazole type compound, at least one zinc salt, and at least one coloring agent - Google Patents

Abstract

The present invention relates to a cosmetic composition comprising at least one particular imidazole type compound, at least one zinc salt, and at least one coloring agent chosen from direct dyes, pigments and mixtures thereof. The present invention also relates to a process for coloring keratin fibers, in particular human keratin fibers such as hair, in which the cosmetic composition as described above is applied to said fibers. The present invention also relates to the use of the cosmetic composition according to the invention for coloring keratin fibers, in particular human keratin fibers such as hair.

Description

Composition comprising at least one particular imidazole type compound, at least one zinc salt, and at least one coloring agent

The present invention relates to a cosmetic composition comprising at least one particular imidazole type compound, at least one zinc salt, and at least one coloring agent chosen from direct dyes, pigments and mixtures thereof.

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

The present invention also relates to the use of the cosmetic composition according to the invention for coloring keratin fibers, in particular human keratin fibers such as hair.

Hair coloring has been a principle known for a long time, whether for coloring hair or lightening it. This allows anyone to change the color of their hair.

In the processes for coloring keratin fibers, it is particularly known to color keratin fibers using different techniques using direct dyes for non-permanent colorings or precursors of oxidation dyes for permanent colorings.

Non-permanent coloring or direct coloring consists of dyeing keratin fibers with dye compositions containing direct dyes. These dyes are colored and coloring molecules with an affinity for keratin fibers. They are applied to the keratin fibers for a time necessary to obtain the desired coloring, then rinsed.

Some of these dyes can be used in lightening conditions, which makes it possible to obtain visible coloring on dark hair.

However, the use of these dye compositions can present a certain number of disadvantages. Indeed, after application to the keratin fibers, the dyeing power obtained may not be entirely satisfactory, or even low, and lead to a restricted range of colors. The colorings may also not be sufficiently tenacious against external agents such as light, shampoos, perspiration and also be too selective, that is to say the difference in coloring is too great along the length of the hair. the same keratin fiber which is differently sensitized between its tip and its root.

Compositions also tend to change over time, which affects their coloring performance.

Thus, there is a real need to provide a composition for coloring keratin fibers, in particular human keratin fibers such as hair, which does not present the drawbacks mentioned above, that is to say which is capable of to lead to good performance, particularly in terms of color increase, power and chromaticity, while having low selectivity and good tenacity, for a wide range of shades, and which is capable of leading to good dyeing performance , even after a period of storage, while having good qualities of use. These compositions must also respond to consumers' environmental concerns.

The subject of the present invention is therefore a cosmetic composition comprising:
a) one or more imidazole type compounds of general formula (I):
(I)
in which R ¹ and R ² independently represent:
- a hydrogen atom;
- a (C ₁ -C ₆ ) alkyl group optionally substituted by one or more identical or different groups chosen from: –C(O)OR and –NR'R'', with R representing a hydrogen atom or a group ( C ₁ -C ₄ )alkyl and R' and R'' independently representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group;
R ¹ and R ² being able to form with the carbon atom which carries them a (hetero)cycle of 4 to 8 members, preferably of 4 to 6 members; And
R ³ represents:
- a hydrogen atom;
- a (C ₁ -C ₆ ) alkyl group,
b) one or more zinc salts, and
c) one or more coloring agents chosen from direct dyes and/or pigments.

The composition according to the invention makes it possible in particular to obtain colorings having good performance in terms of coloring tenacity, in particular with shampoos.

The combination of zinc salts and imidazole type compounds according to the invention allows the immobilization of coloring agents, such as direct dyes and pigments, and thus improves its hold on the surface of keratin fibers.

The composition according to the invention also makes it possible to achieve the above objectives, in particular in terms of color increase, coloring power, chromaticity, selectivity, as well as good qualities of use, in particular a easy application all along the fiber.

The present invention also relates to a process for coloring keratin fibers, in particular human keratin fibers such as hair, comprising the application to said fibers of a cosmetic composition as defined above.

The present invention further relates to the use of the cosmetic composition according to the invention for coloring keratin fibers, in particular human keratin fibers such as hair.

The present invention also relates to the use of a coordination polymer capable of being obtained from one or more zinc salts, as defined above, and one or more imidazole type compounds of formula (I) as defined below to immobilize one or more coloring agents on keratin fibers, in particular hair.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the example which follows.

In what follows, and unless otherwise indicated, the limits of a domain of values are included in this domain, in particular in the expressions “between” and “ranging from… to…”.

Furthermore, the expression “at least one” used in this description is equivalent to the expression “one or more”.

a) Imidazole-type compounds
The composition according to the present invention comprises one or more imidazole type compounds of general formula (I):
(I)
in which R ¹ and R ² independently represent:
- a hydrogen atom;
- a (C ₁ -C ₆ ) alkyl group optionally substituted by one or more identical or different groups chosen from: –C(O)OR and –NR'R'', with R representing a hydrogen atom or a group ( C ₁ -C ₄ )alkyl and R' and R'' independently representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group;
R ¹ and R ² being able to form with the carbon atom which carries them a (hetero)cycle of 4 to 8 members, preferably of 4 to 6 members; And
R ³ represents:
- a hydrogen atom;
- a (C ₁ -C ₆ ) alkyl group.

For the purposes of the present invention, we mean:
▪ by “(hetero)cycle”, a cycle or heterocycle,
▪ by "cycle", a carbocycle, mono or polycyclic, condensed or not, saturated or unsaturated, in particular aromatic, comprising from 6 to 22 carbon atoms, said cycle being able to be substituted by one or more identical or different groups, in particular chosen from : (C ₁ -C ₆ )alkyl, (C ₁ -C ₆ )alkoxy, (C ₁ -C ₆ )hydroxyalkyl, hydroxyl (–OH) or carboxyl (–COOH),
▪ by "heterocycle", a mono or polycyclic group, condensed or not, saturated or unsaturated, in particular aromatic, comprising from 5 to 22 members and containing from 1 to 3 heteroatoms chosen from the atom of nitrogen, oxygen or sulfur, said heterocycle being able to be substituted by one or more groups, identical or different, in particular chosen from: (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₆ ) hydroxyalkyl, hydroxyl ( –OH) or carboxyl (–COOH).

Preferably, R ¹ and R ² form with the carbon atom which carries them a (hetero)cycle of 4 to 8 members, preferably from 4 to 6 members, more preferably R ¹ and R ² form with the carbon atom which carry them a cycle of 4 to 6 links.

Preferably, R ³ represents a hydrogen atom.

Preferably, R ¹ and R ² form with the carbon atoms which carry them a (hetero)cycle of 4 to 8 members, in particular of 4 to 6 members, and R ³ represents a hydrogen atom.

More preferably, the compound of formula (I) is that in which R ¹ and R ² form with the carbon atoms which carry them a 6-membered aromatic ring and R ³ represents a hydrogen atom. This formula corresponds to benzimidazole.

Preferably, the total content of the imidazole type compound(s) of formula (I) ranges from 2 to 20%, more preferably from 10 to 20% by weight, more preferably still from 12 to 18% by weight, relative to the weight total composition.

In a particular embodiment, the total benzimidazole content preferably ranges from 2 to 20%, more preferably from 10 to 20% by weight, more preferably still from 12 to 18% by weight, relative to the total weight of the composition.

b) Zinc salts
The composition according to the invention further comprises one or more zinc salts.

The zinc salt(s) may be organic or inorganic zinc salts.

For the purposes of the present invention, the term zinc salts means hydrated or non-hydrated forms.

The zinc salt(s) which can be used in the present invention can be chosen from Zn(NO ₃ ) ₂ (zinc nitrate), ZnCl ₂ (zinc chloride), ZnBr ₂ (zinc bromide), ZnI ₂ (zinc iodide) , Zn(C1O ₄ ) ₂ (zinc perchlorate), ZnSO ₄ (zinc sulfate), Zn ₃ (PO ₄ ) ₂ (zinc phosphate), Zn(CH ₃ COO) (zinc acetate), Zn ₃ (C ₆ H ₅ O ₇ ) ₂ (zinc citrate), Zn(CH ₂ C(CH ₃ )CO ₂ ) ₂ (zinc methacrylate), Zn(CH ₂ CHCO ₂ ) ₂ (zinc acrylate), Zn(OCH ₂ CH ₂ CH ₃ ) ₂ (zinc propoxide), Zn(C ₁₀ H ₁₄ O ₇ ) (zinc acetylacetonate), Zn(C ₇ H ₁₂ NO ₃ S) ₂ (zinc acetylmethionate), Zn(C ₄ H ₆ NO ₄ ) ₂ (zinc aspartate), ZnCO ₃ (zinc carbonate), Zn ₅ (CH ₃ O ₆ ) ₂ (zinc carbonate hydroxide), zinc coceth sulfate (Zinc coceth sulfate), C ₁₂ H ₂₂ O ₁₄ Zn (zinc gluconate), C ₄ H ₈ N ₂ O ₄ Zn (zinc glycinate), C ₆₀ H ₉₀ O ₈ Zn (zinc glycyrrhetinate), Zinc hydrolyzed collagen, Zn(C ₃ H ₅ O ₃ ) ₂ ( zinc lactate), C ₂₄ H ₄₆ O ₄ Zn (zinc laurate), C ₂₈ H ₅₄ O ₄ Zn (zinc myristate), ZnO (zinc oxide), C ₃₂ H ₆₂ O ₄ Zn (zinc palmitate) , Zinc PCA (Zinc salt of pyrrolidone carboxylic acid), Zn(C ₆ H ₅ O ₄ S) ₂ (zinc phenolsulfonate), Zn(C ₅ H ₄ NOS) ₂ (zinc pyrithione), C ₃₆ H ₆₆ O ₆ Zn (zinc ricinoleate), C ₁₄ H ₁₀ O ₆ Zn (zinc salicylate), C ₃₆ H ₇₀ O ₄ Zn (zinc stearate), ZnS (zinc sulfide), C ₂₂ H ₃₈ O ₄ Zn (zinc undecylenate), ZINC DNA (zinc salt of deoxyribonucleic acid), and mixtures thereof.

Preferably, the zinc salt(s) are inorganic zinc salts. In other words, the zinc salt(s) are preferably chosen from zinc mineral acid salts.

More preferably, the zinc salt(s) are chosen from zinc chloride, zinc nitrate, and mixtures thereof.

Preferably, the total content of the zinc salt(s) b) ranges from 0.5 to 10% by weight, more preferably from 1 to 8% by weight, more preferably still from 3 to 5% by weight, relative to the weight total composition.

In a preferred embodiment of the invention, the content of the zinc salt(s) b) chosen from zinc mineral acid salts ranges from 0.5 to 10% by weight, more preferably from 1 to 8% by weight. weight, more preferably still from 3 to 5% by weight, relative to the total weight of the composition.

In a particular embodiment of the invention, the total zinc chloride content ranges from 0.5 to 10% by weight, more preferably from 1 to 8% by weight, more preferably still from 3 to 5% by weight, relative to the total weight of the composition.

In another particular embodiment of the invention, the total zinc nitrate content ranges from 0.5 to 10% by weight, more preferably from 1 to 8% by weight, even more preferably from 3 to 5% by weight. , relative to the total weight of the composition.

Preferably, the molar ratio between the total content of zinc salts and the total content of imidazole type compounds of general formula (I) ranges from 1/1 to 1/4.

In a particular embodiment of the invention, the molar ratio between the total zinc salt content and the total benzimidazole content ranges from 1/1 to 1/4.

In a particular embodiment of the invention, the molar ratio between the total content of zinc mineral acid salts and the total content of benzimidazole ranges from 1/1 to 1/4.

In another particular embodiment of the invention, the molar ratio between the total content of zinc salts chosen from zinc chloride, zinc nitrate, and their mixtures and the total content of imidazole type compounds of general formula (I) goes from 1/1 to 1/4.

In a preferred embodiment of the invention, the molar ratio between the total content of zinc salts chosen from zinc chloride, zinc nitrate, and mixtures thereof and the total content of benzimidazole ranges from 1/1 to 1 /4.

c) Coloring agents
The composition according to the present invention further comprises one or more coloring agents c) chosen from direct dyes and/or pigments.

By “coloring agent” we mean an oxidation dye, a direct dye or a pigment.

By “direct dye” we mean a natural and/or synthetic dye, including in the form of extract(s), different from oxidation dyes. These are colored compounds which will diffuse superficially on the fiber. They can be ionic or non-ionic, i.e. anionic, cationic, neutral or non-ionic.

Preferably, the total content of the coloring agent(s) c) ranges from 0.001% to 15% by weight, more preferably from 0.005% to 10% by weight, relative to the total weight of the composition.

Direct dyes
The coloring agent(s) c) used in the composition according to the invention can be chosen from direct dyes.

The synthetic direct dyes that can be used are for example chosen from those conventionally used in direct coloring, and among which we can cite all the aromatic and/or non-aromatic dyes in common use such as nitrated benzene, azo, hydrazono, nitrated direct dyes ( hetero)arylic, tri(hetero)arylmethane, (poly)methinic, carbonyl, azinic, porphyrinic, metalloporphyrinic, quinonic and in particular anthraquinonic, indoamine, phthalocyanic and their mixtures.

Among the nitrated benzene direct dyes, mention may be made of: 1,4-diamino-2-nitrobenzene, 1-amino-2 nitro-4-b-hydroxyethylaminobenzene; 1-amino-2 nitro-4-bis(β-hydroxyethyl)-aminobenzene; 1,4-bis(b-hydroxyethylamino)-2-nitrobenzene; 1-b-hydroxyethylamino-2-nitro-4-bis-(β-hydroxyethylamino)-benzene; 1-b-hydroxyethylamino-2-nitro-4-aminobenzene; 1-β-hydroxyethylamino-2-nitro-4-(ethyl)(b-hydroxyethyl)-aminobenzene; 1-amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene; 1-amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene; 1,2-diamino-4-nitrobenzene; 1-amino-2-β-hydroxyethylamino-5-nitrobenzene; 1,2-bis-(β-hydroxyethylamino)-4-nitrobenzene; 1-amino-2-tris-(hydroxymethyl)-methylamino-5-nitrobenzene; 1-Hydroxy-2-amino-5-nitrobenzene; 1-Hydroxy-2-amino-4-nitrobenzene; 1-Hydroxy-3-nitro-4-aminobenzene; 1-Hydroxy-2-amino-4,6-dinitrobenzene; 1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene; 1-Methoxy-2-β-hydroxyethylamino-5-nitrobenzene; 1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene; 1-β,γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene; 1-β-hydroxyethylamino-4-β,γ-dihydroxypropyloxy-2-nitrobenzene; 1-β,γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene; 1-β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene; 1-β-hydroxyethylamino-3-methyl-2-nitrobenzene; 1-β-aminoethylamino-5-methoxy-2-nitrobenzene; 1-Hydroxy-2-chloro-6-ethylamino-4-nitrobenzene; 1-Hydroxy-2-chloro-6-amino-4-nitrobenzene; 1-Hydroxy-6-bis-(β-hydroxyethyl)-amino-3-nitrobenzene; 1-β-hydroxyethylamino-2-nitrobenzene; 1-Hydroxy-4-β-hydroxyethylamino-3-nitrobenzene.

Among the azo direct dyes, we can cite: Basic Red 51, Basic Orange 31, Disperse Red 17, Acid Yellow 9, Acid Black 1, Basic Red 22, Basic Red 76, Basic Yellow 57, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 35, Acid Yellow 23, Acid Orange 24, Disperse Black 9, Basic Brown 16, Basic Brown 17.

Hydrazono direct dyes include: Basic Yellow 87.

Among the direct aryl nitrate dyes, we can cite: HC Blue 2, HC Yellow 2, HC Red 3, 4-hydroxypropylamino-3-nitrophenol, N,N’-bis-(2-hydroxyethyl)-2-nitro-phenylenediamine.

Among the triarylmethane direct dyes, we can cite: Basic Violet 1, Basic Violet 2 (New Fuchsin), 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), Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50; Carminic Acid.

Quinonic direct dyes include: Disperse Red 15, Solvent Violet 13, Acid Violet 43, Disperse Violet 1, Disperse Violet 4, Disperse Blue 1, Disperse Violet 8, Disperse Blue 3, Disperse Red 11, Acid Blue 62, Disperse Blue 7, Basic Blue 22, Disperse Violet 15, Basic Blue 99, as well as the following compounds: 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone, 1-aminopropylamino-4-methylaminoanthraquinone, 1-aminopropylamino-anthraquinone, 5-β-hydroxyethyl-1,4-diaminoanthraquinone, 2-aminoethylamino-anthraquinone, 1,4-bis-(β,γ-dihydroxypropylamino)-anthraquinone, Acid Blue 25, Acid Blue 43, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Mordant Red 3, Acid Black 48, HC Blue 16.

Among the direct azinic dyes, we can cite: Basic Blue 17, Basic Red 2.

Among the direct indoamine dyes, we can cite: 2-β-hydroxyethylamino-5-[bis-(β-4'-hydroxyethyl)amino]anilino-1,4-benzoquinone, 2-β-hydroxyethylamino-5-(2' -methoxy-4'-amino)anilino-1,4-benzoquinone, 3-N(2'-chloro-4'-hydroxy)phenyl-acetylamino-6-methoxy-1,4-benzoquinone imine, 3-N(3 '-chloro-4'-methylamino)phenyl-ureido-6-methyl-1,4-benzoquinone imine, 3-[4'-N-(ethyl,carbamylmethyl)-amino]-phenyl-ureido-6-methyl-1 ,4-benzoquinone imine.

Natural direct dyes are for example chosen from lawsone, juglone, indigo, leuco indigo, indirubin, isatin, hennotannic acid, alizarin, carthamine, morin, purpurin, carminic acid, kermesic acid, laccaic acid, purpurogalline, protocatechaldehyde, curcumin, spinulosin, apigenidin, orceins, carotenoids, betanin, chlorophylls, chlorophyllins or monascus.

Among the useful orthodiphenols according to the invention, mention may be made of: catechin, quercetin, brazilin, hematein, hematoxylin, chlorogenic acid, caffeic acid, gallic acid, L DOPA, cyanidin, (-)-Epicatechin, (-)-Epigallocatechin, (-) )-Epigallocatechin 3-gallate (EGCG), Isoquercetin, Pomiferin, esculetin, 6,7-Dihydroxy-3-(3-hydroxy-2,4-dimethoxyphenyl)coumarin, Santalin A and B, mangiferin, butein, Maritimetine, Sulfuretin, Robtein, betanidine, Pericampylinone A., Theaflavin, Proanthocyanidin A2, Proanthocyanidin B2, Proanthocyanidin C1, Procyanidins DP 4-8, Purpurogalline, 5,6-Dihydroxy-2-methyl-1,4-naphthoquinone, Alizarin, Wedelolactone and natural extracts containing them.

Preferably, triarylmethane direct dyes are used, and more preferably, Basic Violet 2 (New Fuchsin).

Preferably, the coloring agent(s) chosen from direct dyes represent from 0.001% to 15% by weight, more preferably from 0.005% to 10% by weight, relative to the total weight of the composition.

Pigments
The coloring agent(s) c) used in the composition according to the invention can also be chosen from pigments.

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

These are solid particles, white or colored, naturally insoluble in the hydrophilic and lipophilic liquid phases usually used in cosmetics or made insoluble by formulation in the form of lacquer, where appropriate. More particularly, pigments are poorly or not soluble in hydroalcoholic media.

The pigments which can be used are in particular chosen from organic and/or mineral pigments known in the art, in particular those which are described in the encyclopedia of chemical technology by Kirk-Othmer and in the encyclopedia of industrial chemistry by Ullmann. Mention may in particular be made as pigments of organic and inorganic pigments such as those defined and described in Ullmann's Encyclopedia of Industrial Chemistry "Pigment organics", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a20 371 and ibid, “Pigments, Inorganic, 1. General” 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim10.1002/14356007.a20_243.pub3

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

The pigments can for example be chosen from mineral pigments, organic pigments, lacquers, pigments with special effects such as pearls or flakes, and their mixtures.

The pigment may be a mineral pigment. By “mineral pigment” we mean any pigment which meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Mention may be made, among the mineral pigments useful in the present invention, of iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

The pigment may be an organic pigment. By “organic pigment”, we mean any pigment which meets the definition of the Ullmann encyclopedia in the organic pigment chapter. The organic pigment may in particular be chosen from the compounds nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, of metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

In particular, the white or colored organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, blue pigments codified in Color Index under references Cl 42090, 69800, 69825, 73000, 74100, 74160, yellow pigments coded in the Color Index under references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 470 05, green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, orange pigments codified in the Color Index under the references CI 11725, 15510, 45370, 71105, red pigments codified in the Color Index under the references CI 12085, 12120 , 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73 360, 73915, 75470, pigments obtained by oxidative polymerization of indole derivatives , phenolics as described in patent FR 2 679 771.

According to a particular embodiment of the invention, pigment pastes of organic pigments are used as pigment(s), such as the products sold by the company HOECHST under the name:
- COSMENYL YELLOW IOG: Pigment YELLOW 3 (Cl 11710);
- COSMENYL YELLOW G: Pigment YELLOW 1 (Cl 11680);
- ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);
- COSMENYL RED R: Pigment RED 4 (Cl 12085);
- CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);
- VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);
- COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);
- VERT COSMENYL GG: Pigment GREEN 7 (Cl 74260);
- COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

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

By “lacquer”, we mean dyes adsorbed on insoluble particles, the whole thus obtained remaining insoluble during use. The inorganic substrates on which the dyes are adsorbed are for example alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum. Among the organic dyes, we can cite cochineal carmine.

As examples of lacquers, we can cite the products known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410). ), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 7 (CI 15 850:1), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).

The pigment(s) may also be special effect pigments.

By “special effect pigments” we mean pigments which generally create a colored appearance (characterized by a certain nuance, a certain vividness and a certain clarity) which is non-uniform and changes depending on the observation conditions (light , temperature, observation angles, etc.). They are therefore opposed to colored pigments which provide a classic uniform opaque, semi-transparent or transparent shade.

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

As examples of pigments with special effects, we can cite pearlescent pigments such as titanium mica covered with an iron oxide, mica covered with an iron oxide, mica covered with bismuth oxychloride, titanium mica covered with chromium oxide, titanium mica covered with an organic dye in particular of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. It may also be mica particles on the surface of which at least two successive layers of metal oxides and/or organic coloring materials are superimposed.

Mother-of-pearl can more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or copper color or reflection.

As an illustration of the mother-of-pearl that can be used in the context of the present invention, mention may in particular be made of gold-colored mother-of-pearl, notably marketed by the company ENGELHARD under the name Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504. (Chromalite) and Monarch gold 233X (Cloisonne); bronze mother-of-pearls marketed in particular by the company MERCK under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona), by the company Eckart under the name Prestige Bronze and by the company ENGELHARD under the name Super bronze (Cloisonne ) ; orange pearls marketed in particular by the company ENGELHARD under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company MERCK under the name Passion orange (Colorona) and Matte orange (17449) (Microna); brown colored mother-of-pearl sold in particular by the company ENGELHARD under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); mother-of-pearl with a copper reflection, notably marketed by the company ENGELHARD under the name Copper 340A (Timica) and by the company Eckart under the name Prestige Copper; mother-of-pearl with a red reflection, notably marketed by the MERCK company under the name Sienna fine (17386) (Colorona); mother-of-pearl with a yellow reflection, notably marketed by the company ENGELHARD under the name Yellow (4502) (Chromalite); red pearls with a gold reflection, notably marketed by the company ENGELHARD under the name Sunstone G012 (Gemtone); black mother-of-pearl with a gold reflection, notably marketed by the company ENGELHARD under the name Nu antique bronze 240 AB (Timica), blue mother-of-pearl, notably marketed by the company MERCK under the name Matte blue (17433) (Microna), Dark Blue (117324) (Colorona), white mother-of-pearl with silver reflection marketed in particular by the MERCK company under the name Xirona Silver and pinkish-golden-green orange mother-of-pearl in particular marketed by the MERCK company under the name Indian summer (Xirona) and their mixtures.

In addition to nacres on a mica support, we can consider multilayer pigments based on synthetic substrates such as alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

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

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

The size of the pigment(s) used in the composition according to the present invention generally ranges from 10 nm to 200 μm, preferably from 20 nm to 80 μm, and more preferably from 30 nm to 50 μm.

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

By “dispersing agent” is meant a compound which makes it possible to protect the dispersed particles against their agglomeration or flocculation. This dispersing agent can be a surfactant, an oligomer, a polyphenol or a polymer or a mixture of several of them, carrying one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can cling physically or chemically to the surface of pigments. These dispersing agents also have at least one compatible or soluble functional group in the continuous medium. Said agent can be charged, it can be anionic, cationic, zwitterionic or neutral.

According to a particular embodiment of the invention, the dispersing agents used are chosen from esters of 12-hydroxystearic acid more particularly and of C8 to C20 fatty acids and of polyols such as glycerol, diglycerin, such that poly(12-hydroxystearic) acid stearate with a molecular weight of approximately 750 g/mol such as that sold under the name Solsperse 21 000 by the company Avecia, polygyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel or polyhydroxystearic acid such as that sold under the reference Arlacel P100 by the company Uniqema, polyphenols such as tannic acid and their mixtures.

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

In a preferred embodiment, the composition according to the invention may optionally also comprise one or more polyphenols.

In a particularly preferred embodiment, the composition comprises one or more coloring agents chosen from pigments and one or more polyphenols as dispersing agents.

When the composition comprises polyphenols, their total content preferably ranges from 1 to 10% by weight, more preferably from 2 to 8% by weight, even more preferably from 3 to 7% by weight, relative to the total weight of the composition. .

In a preferred embodiment, the composition according to the invention may optionally also comprise tannic acid.

In a particularly preferred embodiment, the composition comprises one or more coloring agents chosen from pigments and tannic acid as dispersing agent.

When the composition comprises tannic acid, its total content preferably ranges from 1 to 10% by weight, more preferably from 2 to 8% by weight, more preferably still from 3 to 7% by weight, relative to the total weight. of the composition.

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

Thus the previously surface-treated pigments useful in the context of the invention are pigments which have totally or partially undergone a surface treatment of a chemical, electronic, electro-chemical, mechano-chemical or mechanical nature, with an organic agent such as those which are described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, p. 53-64 before being dispersed in the composition according to the invention. These organic agents can for example be chosen from amino acids; waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, for example aluminum stearate or laurate; metal alkoxides; polysaccharides, for example chitosan, cellulose and its derivatives; polyethylene; (meth)acrylic polymers, for example polymethylmethacrylates; polymers and copolymers containing acrylate units; the proteins ; alkanoamines; silicone compounds, for example silicones, polydimethylsiloxanes, alkoxysilanes, alkylsilanes, siloxy-silicates; fluorinated organic compounds, for example perfluoroalkyl ethers; fluoro-silicone compounds.

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

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

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

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

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

Preferably, an organic agent linked to the pigments in a covalent manner will be used.

The surface treatment agent can represent from 0.1 to 50% by weight of the total weight of the pigments treated on the surface, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 10% by weight. weight.

Preferably, the surface treatments of the pigments are chosen from the following treatments:
- a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW;
- a Chitosan treatment such as the CTS surface treatment marketed by LCW;
- a Triethoxycaprylylsilane treatment such as the AS surface treatment marketed by LCW;
- a Methicone treatment such as the SI surface treatment marketed by LCW;
- a Dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW;
- a Dimethicone / Trimethylsiloxysilicate treatment such as the Covasil 4.05 surface treatment marketed by LCW;
- a Lauroyl Lysine treatment such as the LL surface treatment marketed by LCW;
- a Lauroyl Lysine Dimethicone treatment such as the LL/SI surface treatment marketed by LCW;
- a Magnesium Myristate treatment such as the MM surface treatment marketed by LCW;
- an Aluminum Dimyristate treatment such as the MI surface treatment marketed by Miyoshi;
- a Perfluoropolymethylisopropyl ether treatment such as the FHC surface treatment marketed by LCW;
- an Isostearyl Sebacate treatment such as the HS surface treatment marketed by Miyoshi;
- a Disodium Stearoyl Glutamate treatment such as the NAI surface treatment marketed by Miyoshi;
- a Dimethicone / Disodium Stearoyl Glutamate treatment such as the SA / NAI surface treatment marketed by Miyoshi;
- a Perfluoroalkyl Phosphate treatment such as the PF surface treatment marketed by Daito;
- an Acrylate Copolymer/Dimethicone and Perfluoroalkyl Phosphate treatment such as the FSA surface treatment marketed by Daito;
- a Polymethylhydrogen siloxane / Perfluoroalkyl Phosphate treatment such as the FS01 surface treatment marketed by Daito;
- a Lauryl Lysine / Aluminum Tristearate treatment such as the LL-StAI surface treatment marketed by Daito;
- an Octyltriethylsilane treatment such as the OTS surface treatment marketed by Daito;
- an Octyltriethylsilane / Perfluoroalkyl Phosphate treatment such as the FOTS surface treatment marketed by Daito;
- an Acrylate/Dimethicone Copolymer treatment such as the ASC surface treatment marketed by Daito;
- an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito;
- a Microcrystalline Cellulose and Carboxymethyl Cellulose treatment such as the AC surface treatment marketed by Daito;
- a Cellulose treatment such as the C2 surface treatment marketed by Daito;
- an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito;
- a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito.

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

The compositions used in the composition according to the present invention may additionally comprise one or more pigments not treated on the surface.

According to a particular embodiment of the invention, the pigment(s) are mineral pigments.

According to another particular mode of the invention, the pigment(s) are chosen from mother-of-pearl.

According to a particular embodiment of the invention, the dispersing agent is present with organic or inorganic pigments in particulate form of submicron size in the composition comprising them.

By "sub-micronic" or in English "sub-micronic", we mean pigments whose particle size has been micronized by micronization method and whose average particle size is less than one micrometer (µm), in particular ranging from 0 .1 to 0.9 µm, and preferably ranging from 0.2 to 0.6 µm.

According to one embodiment, the dispersing agent and the pigment(s) are present in quantity (dispersant: pigment) ranging from 0.5:1 to 2:1, particularly ranging from 0.6:1 to 1.5:1 or better ranging from 0.6:1 to 1.2:1.

According to a particular embodiment, the dispersing agent is suitable for dispersing the pigments and is compatible with a condensation-curable formulation.
By "compatible" is meant, for example, that said dispersing agent is miscible in the oily phase of the composition containing the pigment(s), it does not delay or reduce hardening. The dispersing agent is preferably cationic.

The dispersing agent(s) may therefore have a silicone skeleton, such as silicone polyether and amino-silicone type dispersants. Among the suitable dispersing agents we can cite:
- amino-silicones, ie silicones comprising one or more amino groups, such as those marketed under the names and references: BYK LPX 21879, by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, marketed by Genesee polymers,
- silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik,
- polydimethylsiloxane silicones (PDMS) with carboxylic groups such as X-22162 and X-22370 by Shin-Etsu, silicone epoxy such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695, by Genesee Polymers, or Tego ® RC 1401, Tego ® RC 1403, Tego ® RC 1412, by Evonik.

According to a particular embodiment, the dispersing agent(s) are of the amino-silicone type and are positively charged.

We can also cite dispersing agents having chemical groups capable of reacting with the reagents of the oily phase and thus are capable of improving the 3D network formed from the amino-silicone. For example, silicone epoxy pigment dispersants may react chemically with the pre-polymer amino-silicone amino group(s) to increase the cohesion of the amino-silicone film comprising the pigment(s).

Preferably, the pigment(s) used in the composition of the invention are chosen from mother-of-pearl, carbon blacks such as Black 2, iron oxides in particular red, brown or black and micas coated with oxide. iron, triarylmethane pigments in particular blue and violet such as BLUE 1 LAKE, azo pigments in particular red such as D&C RED 7, alkali or alkaline earth metal salts of lithol red such as the calcium salt of red of lithol B, and their mixtures.

More preferably, the pigment(s) used in the composition are chosen from carbon blacks such as Black 2, iron oxides in particular red, brown or black, and mixtures thereof.

Preferably, the coloring agent(s) chosen from the pigments represent from 0.001% to 15% by weight, more preferably from 0.005% to 10% by weight, relative to the total weight of the composition.

The composition according to the invention preferably comprises water. Advantageously, the total water content ranges from 25 to 45% by weight, preferably from 30 to 40% by weight, relative to the total weight of the composition.

The composition according to the invention preferably comprises one or more organic solvents.

The organic solvent(s) may be chosen from linear or branched monoalcohols, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, polyols, polyethylene glycols, aromatic alcohols and their mixtures.

Among the monoalcohols, we can notably cite ethanol, propanol, butanol, isopropanol, isobutanol and their mixtures, better still ethanol.

Among the polyethylene glycols, we can in particular cite propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol and pentylene glycol.

Among the polyols, we can in particular cite glycerol and sorbitol.

Among the aromatic alcohols, we can notably cite benzyl alcohol and phenoxyethanol.

Advantageously, the total content of organic solvents ranges from 25 to 45% by weight, preferably from 30 to 40% by weight, relative to the total weight of the composition.

In a particular embodiment, the total ethanol content ranges from 25 to 45% by weight, preferably from 30 to 40% by weight, relative to the total weight of the composition.

In a preferred embodiment, the composition according to the invention comprises water and an organic solvent.

In a particularly preferred embodiment, the composition according to the invention comprises water and ethanol.

Advantageously, the weight ratio between the total water content and the total organic solvent content is 1.

In a preferred embodiment of the invention, the weight ratio between the total water content and the total ethanol content is 1.

Additives
The cosmetic composition according to the present invention may optionally also comprise one or more additional compounds different from the compounds defined above, preferably chosen from anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants, reducers, softeners, anti-foaming agents, moisturizing agents, UV filters, peptizers, solubilizers, perfumes, anionic, cationic, non-ionic, amphoteric polymers or their mixtures, anti-dandruff agents, antiseborrheic agents , vitamins and pro-vitamins including panthenol, plasticizing agents, solubilizing agents other than the solvents of the invention, acidifying agents, mineral or organic thickening agents, in particular polymeric thickening agents, anti-oxidant agents, hydroxy acids, perfumes, preservatives, and mixtures thereof.

Preferably, when the additional compound(s) above are present in the cosmetic composition according to the invention, the additional compound(s) are generally present in a content comprised for each of them between 0.01 and 20% by weight. , relative to the total weight of the composition.

Of course, those skilled in the art will take care to choose this or these possible additional compounds in such a way that the advantageous properties inherently attached to the cosmetic composition of the invention are not, or substantially not, altered by the addition(s). considered.

Process
The present invention also relates to a process for coloring keratin fibers, in particular human keratin fibers such as hair, comprising the application to said keratin fibers of a cosmetic composition as defined above.

The coloring process according to the invention can be carried out on dry or wet keratin fibers, as well as on all types of fibers, light or dark, natural or colored, permed, bleached or straightened.

According to a particular embodiment of the process of the invention, the fibers are washed before application of the cosmetic composition described above.

The application of the cosmetic composition of the invention to the keratin fibers can be carried out by any conventional means, in particular by means of a comb, a brush, a brush or the fingers.

The coloring process, i.e. application of the cosmetic composition, is generally carried out at room temperature (between 15 to 25°C). The coloring process according to the invention generally uses an exposure time of the composition according to the invention, this exposure time varying from 15 seconds to 1 hour, preferably from 1 minute to 15 minutes, such as 5 minutes.

At the end of the coloring process according to the invention, the keratin fibers can be rinsed with water. They can possibly be washed with shampoo, followed by rinsing with water, before being dried or left to dry.

The present invention also relates to the use of the composition according to the invention as described above for the coloring of keratin fibers, in particular human keratin fibers such as hair.

The present invention also relates to the use of a coordination polymer capable of being obtained from one or more zinc salts, as defined above, and one or more imidazole type compounds of formula (I) as defined previously to immobilize one or more coloring agents on keratin fibers, in particular hair.
For the purposes of the present invention, the coordination polymer represents a three-dimensional hybrid network, consisting of metal-ligand bonds.
In particular, the coordination polymer according to the invention is formed from a precursor based on Zn(II) ions with one or more ligand(s) corresponding to the conjugated base of the imidazole type compound of formula (I ) as defined previously, more particularly the coordination polymer according to the invention is formed from a zinc salt Zn (II) and 1 to 4 imidazole type compounds of formula (I) as described previously.

The following examples serve to illustrate the invention without, however, being limiting in nature.

Examples
In the examples which follow, all quantities are indicated as a mass percentage of active ingredient (MA) relative to the total weight of the composition (unless otherwise stated).

1. Example 1

i) Preparation of compositions A to I:
A hydroalcoholic solution was prepared by mixing an equimass ratio of water and absolute ethanol.
For compositions A to D and G to I, a pigment (red iron oxide) was then added with tannic acid. For compositions E and F, a pigment (carbon black) was then added.
For compositions A, B, E, G to I, the zinc chloride was then dissolved in this mixture.
For compositions A, C, E, G to I, benzimidazole (Bim) was then added. For compositions A, E, G to I, the final molar ratio between zinc chloride and benzimidazole (Zn/Bim) is indicated in the tables below.
The details of the compositions are indicated in Tables 1 and 2 below:

Composition A
(invention) Composition B
(comparative) Composition C
(comparative) Composition D
(comparative) Red iron oxide 6 6 6 6 Tannic acid 5 5 5 5 Carbon black - - - - Water/ethanol 50/50 w/w% Qsp 100 Qsp 100 Qsp 100 Qsp 100 Zinc chloride 4 4 - - Benzimidazole 15 - 15 - Zn/Bim ratio 1/4 - - -

Composition E
(invention) Composition F
(comparative) Composition G
(invention) Composition H
(invention) Composition I
(invention) Red iron oxide - - 6 6 6 Tannic acid - - 5 5 5 Carbon black 4 4 - - - Water/ethanol 50/50 w/w% Qsp 100 Qsp 100 Qsp 100 Qsp 100 Qsp 100 Zinc chloride 4 - 4 4 4 Benzimidazole 15 - 11.25 7.5 3.75 Zn/Bim ratio 1/4 - 1/3 1/2 1/1

ii) Protocol:
Each cosmetic composition indicated in the tables above is applied to a strand of 90% white, dry natural hair so as to cover the strand evenly, at a rate of 1 g of composition per gram of strand, for a period of 5 min pose.
The hair strands are then combed and dried with a hairdryer.
The hair is colored evenly and intensely.
Then, the strands of hair thus colored are subjected to a shampoo in order to evaluate the tenacity (the persistence) of the coloring.

iii) Shampoo protocol:
The shampoo resistance evaluations were conducted according to the following shampoo protocol, 24 hours after application of the compositions according to the application protocol described previously:
The colored hair strands are combed, moistened under water at 35°C before being passed between the fingers 5 times for 5 seconds. The strands of hair are then wrung out between two fingers.
A standard shampoo (Garnier Ultra Doux) is applied evenly to the colored strands at a rate of 0.4 g of standard shampoo per gram of strands, by gently kneading the strands of hair along its length (6 passes) for 15 s, from root to tip.
The hair strands are then placed in a watch glass and allowed to sit for 1 min.
Then, the hair strands are rinsed with water by passing the strands between the fingers (15 passes). The hair strands are then dried between two fingers before the next shampoo.
Once the multiple shampoo tests are done, the hair strands are combed and blow dried.

iv) Results:
The persistence of the color of the highlights was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600D colorimeter (illuminant D65, angle 10°, specular component included).
In this L*a*b* system, L* represents the color intensity, a* indicates the green/red color axis and b* the blue/yellow color axis.
The rise in color dE is calculated according to the following equation:

In this equation, L0*, a0* and B0* are the coordinates of the uncolored wick (BN-90) and L*, a* and b* the coordinates of a colored wick.

The persistence of the coloring is evaluated by the color difference ΔE between the colored strands before shampooing, then after having undergone 1 to 3 shampoos according to the protocol described above. The lower the value of ΔE, the more the color persists after shampooing.
The value of ΔE is calculated according to the following equation:

In this equation, L*a*b* represent the values measured after coloring the hair and after having undergone 1 shampoo, and L0*a0*b0* represent the values measured after coloring the hair but before shampooing.
The lower the ΔE value, the more the color persists after shampooing.

The results are shown in Table 3 below:

Compositions Number of shampoos L* has* b* dE (rise) ΔE Ref BN-90 - 60.14 0.71 15.47 - - Composition A
(invention) 0 33.25 20.78 13.66 33.60 - 1 36.81 21.51 15.77 31.26 4.20 3 42.77 18.68 15.8 24.99 9.98 Composition B
(comparative) 0 32.54 26.43 20.11 38.01 - 1 55.87 16.02 21.15 16.88 25.57 Composition C
(comparative) 0 38.42 19.61 13.49 28.86 - 1 47.89 19.99 20.78 23.45 11.96 Composition D
(comparative) 0 33.08 21.93 15.1 34.39 - 1 48.39 13.35 17.51 17.38 17.71 Composition E
(invention) 0 19.24 0.09 0.09 43.70 - 1 19.41 0.14 0.92 43.25 0.85 3 29.47 0.89 2.27 33.39 10.49 Composition F
(comparative) 0 18.36 -0.07 0.27 44.65 - 1 36.37 0.24 5.05 25.96 18.64 Composition G
(invention) 0 39 25.37 19.24 32.70 - 1 47.25 17.95 17.75 21.65 11.20 3 52.42 15.81 19.42 17.41 16.48 Composition H
(invention) 0 38.24 24.64 17.98 32.54 - 1 45.93 20.04 18.13 24.14 8.96 3 51.31 14.04 17.72 16.15 16.83 Composition I
(invention) 0 36.02 24.39 17.26 33.85 - 1 40.79 21.48 16.47 28.40 5.64 3 47.2 17.6 16.71 21.31 13.09

After 1 shampoo, the ΔE values obtained with the compositions according to the invention (A, E, G, H and I) are lower than those obtained with the comparative compositions (B, C, D and F).

Thus the colored sheathing of keratin fibers using the compositions according to the invention presents an improvement in the retention of color after shampooing.

2. Example 2

i) Preparation of compositions J to M:
A hydroalcoholic solution was prepared by mixing an equimass ratio of water and absolute ethanol.
New fuchsin dye (Basic Violet 2) was then added.
Then, zinc nitrate was then dissolved into this mixture, before the addition of benzimidazole (Bim) or 2-ethylimidazole (Etlm).

The details of the compositions are indicated in Table 4 below:

Composition J
(invention) Composition K
(comparative) Composition L
(invention) Composition M
(comparative) New Fuchsin 0.05 0.05 0.01 0.01 Zinc nitrate, 6H2O 8.71 8.71 0.36 0.36 Benzimidazole 15 - 1.77 - 2-ethylimidazole - 12.2 - 1.44 Water/ethanol 50/50 w/w% Qsp 100 Qsp 100 Qsp 100 Qsp 100 Zn/Bim or Zn/Etlm ratio 1/4 1/4 1/12.5 1/12.5

ii) Protocol:
Each cosmetic composition indicated in the table above is applied to a strand of 90% white, dry natural hair so as to cover the strand evenly, at a rate of 1 g of composition per gram of strand (compositions J and K ) or in a chute at a rate of 20 g of composition per gram of wick (compositions L and M), for an exposure time of 5 min.
The hair strands are then combed and dried with a hairdryer.
The hair is colored evenly and intensely.
Then, the strands of hair thus colored are subjected to a shampoo in order to evaluate the tenacity (the persistence) of the coloring.

iii) Shampoo protocol:
The strands are washed using a standard shampoo (Garnier Ultra Doux) at T = 24 hours following application of the treatment.
The hair strands are then rinsed, combed and dried with a hairdryer.

iv) Results:
The persistence of the color of the highlights was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600D colorimeter (illuminant D65, angle 10°, specular component included).

The calculation of the color rise dE and the persistence of the coloring ΔE is carried out as described in Example 1.
The results are presented in tables 5 and 6 below:

Compositions Number of shampoos L* has* b* dE (rise) ΔE Ref BN-90 - 60.14 0.71 15.47 - - Composition J
(invention) 0 37.1 33.3 -11.11 47.95 - 1 48.44 33.18 -11.35 43.71 11.34 Composition K
(comparative) 0 40.99 21.13 -2.39 33.21 - 1 54.89 9.38 8.08 12.54 21.00

Compositions Number of shampoos L* has* b* dE (rise) Ref BN-90 - 60.14 0.71 15.47 - Composition L
(invention) 0 50.41 22.64 -1.56 29.42 Composition M
(comparative) 0 47.93 18.39 1.93 25.40

Composition K (comparative) has a lower persistence after 1 shampoo than inventive composition J (according to the invention).
Compositions L and M use the ratios of Zn and ligand described in the patent

Furthermore, composition L (according to the invention) makes it possible to obtain a better color build-up compared to the comparative composition M.

The strand of hair of composition J according to the invention and washed with a shampoo has a lower ΔE value compared to the control examples.

Thus the colored sheathing of keratin fibers using the compositions according to the invention presents an improvement in the retention of color after shampooing.

Claims (15)

Cosmetic composition comprising:
a) one or more imidazole type compounds of general formula (I):
(I)
in which R ¹ and R ² independently represent:
- a hydrogen atom;
- a (C ₁ -C ₆ ) alkyl group optionally substituted by one or more identical or different groups chosen from: –C(O)OR and –NR'R'', with R representing a hydrogen atom or a group ( C ₁ -C ₄ )alkyl and R' and R'' independently representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group;
R ¹ and R ² being able to form with the carbon atom which carries them a (hetero)cycle of 4 to 8 members, preferably of 4 to 6 members; And
R ³ represents:
- a hydrogen atom;
- a (C ₁ -C ₆ ) alkyl group,
b) one or more zinc salts, and
c) one or more coloring agents chosen from direct dyes and/or pigments. Composition according to claim 1, characterized in that the imidazole type compound(s) of general formula (I) are those in which R ¹ and R ² form with the carbon atom which carries them a (hetero)cycle of 4 to 8 members, preferably from 4 to 6 members and R ³ represents a hydrogen atom, more preferably the imidazole type compound of formula (I) is benzimidazole. Composition according to any one of the preceding claims, characterized in that the total content of the imidazole type compound(s) of formula (I) ranges from 2 to 20% by weight, preferably from 10 to 20% by weight, more preferably another 12 to 18% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that the zinc salt(s) b) are chosen from organic zinc salts, inorganic zinc salts and mixtures thereof, preferably from zinc mineral acid salts. , more preferably from Zn(NO ₃ ) ₂ (zinc nitrate), ZnCl ₂ (zinc chloride), ZnBr ₂ (zinc bromide), ZnI ₂ (zinc iodide), Zn(C1O ₄ ) ₂ (zinc perchlorate ), ZnSO ₄ (zinc sulfate), Zn ₃ (PO ₄ ) ₂ (zinc phosphate), Zn(CH ₃ COO) (zinc acetate), Zn ₃ (C ₆ H ₅ O ₇ ) ₂ (zinc citrate ), Zn(CH ₂ C(CH ₃ )CO ₂ ) ₂ (zinc methacrylate), Zn(CH ₂ CHCO ₂ ) ₂ (zinc acrylate), Zn(OCH ₂ CH ₂ CH ₃ ) ₂ (zinc propoxide) , Zn(C ₁₀ H ₁₄ O ₇ ) (zinc acetylacetonate), Zn(C ₇ H ₁₂ NO ₃ S) ₂ (zinc acetylmethionate), Zn(C ₄ H ₆ NO ₄ ) ₂ (zinc aspartate), ZnCO ₃ (zinc carbonate), Zn ₅ (CH ₃ O ₆ ) ₂ (zinc carbonate hydroxide), zinc coceth sulfate (Zinc coceth sulfate), C ₁₂ H ₂₂ O ₁₄ Zn (zinc gluconate), C ₄ H ₈ N ₂ O ₄ Zn (zinc glycinate), C ₆₀ H ₉₀ O ₈ Zn (zinc glycyrrhetinate), Zinc hydrolyzed collagen, Zn(C ₃ H ₅ O ₃ ) ₂ (zinc lactate), C ₂₄ H ₄₆ O ₄ Zn (zinc laurate), C ₂₈ H ₅₄ O ₄ Zn (zinc myristate), ZnO (zinc oxide), C ₃₂ H ₆₂ O ₄ Zn (zinc palmitate), Zinc PCA (Zinc salt of acid pyrrolidone-carboxylic acid), Zn(C ₆ H ₅ O ₄ S) ₂ (zinc phenolsulfonate), Zn(C ₅ H ₄ NOS) ₂ (zinc pyrithione), C ₃₆ H ₆₆ O ₆ Zn (zinc ricinoleate), C ₁₄ H ₁₀ O ₆ Zn (zinc salicylate), C ₃₆ H ₇₀ O ₄ Zn (zinc stearate), ZnS (zinc sulfide), C ₂₂ H ₃₈ O ₄ Zn (zinc undecylenate), ZINC DNA (salt of zinc of deoxyribonucleic acid) and their mixtures, more preferably still among Zn(NO ₃ ) ₂ (zinc nitrate), ZnCl ₂ (zinc chloride), and their mixtures. Composition according to any one of the preceding claims, characterized in that the total content of the zinc salt(s) b) ranges from 0.5 to 10% by weight, preferably from 1 to 8% by weight, more preferably from 3 at 5% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that the molar ratio between the total content of zinc salts b) and the total content of imidazole type compounds of general formula (I) ranges from 1/1 to 1/ 4. Composition according to any one of the preceding claims, characterized in that the coloring agent(s) chosen from the pigments are chosen from mother-of-pearl, carbon blacks such as Black 2, iron oxides in particular red, brown or black and micas coated with iron oxide, triarylmethane pigments in particular blue and violet such as BLUE 1 LAKE, azo pigments in particular red such as D&C RED 7, alkali or alkaline earth metal salts of lithol red such as the calcium salt of lithol red B, and their mixtures, preferably among carbon blacks such as Black 2, iron oxides in particular red, brown or black, and their mixtures. Composition according to any one of the preceding claims, characterized in that the coloring agent(s) chosen from direct dyes are chosen from triarylmethane direct dyes, preferably the direct dye is Basic Violet 2 (New Fuchsin). Composition according to any one of the preceding claims, characterized in that the total content of coloring agents c) ranges from 0.001% to 15% by weight, more preferably from 0.005% to 10% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that it further comprises water, preferably in a total content ranging from 25 to 45% by weight, preferably from 30 to 40% by weight, per relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that it further comprises one or more organic solvents, preferably chosen from linear or branched monoalcohols, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, polyols, polyethylene glycol, aromatic alcohols and their mixtures. Composition according to the preceding claim, characterized in that the total content of organic solvents ranges from 25 to 45% by weight, preferably from 30 to 40% by weight, relative to the total weight of the composition. Composition according to any one of the preceding claims, characterized in that it further comprises tannic acid, preferably in a total content preferably ranging from 1 to 10% by weight, more preferably from 2 to 8% by weight , more preferably still from 3 to 7% by weight, relative to the total weight of the composition. Process for coloring keratin fibers, in particular human keratin fibers such as hair, comprising the application to said keratin fibers of a cosmetic composition as defined according to any one of the preceding claims. Use of a composition according to any one of claims 1 to 13 for coloring keratin fibers, in particular human keratin fibers such as hair.