DE102011085416A1 - Composition, useful for color changing of keratin fibers, and for color enhancement of oxidative color change in human hair , comprises a coloring compound comprising oxidation dye precursors and/or precursors of nature-analogous dyes - Google Patents

Abstract

Composition comprises at least one coloring compound comprising oxidation dye precursors and/or precursors of nature-analogous dyes, in a carrier, where the agent further contains at least one mixture of cellulose and at least one anionic polysaccharide. An independent claim is included for kit-of-parts comprising at least two separately prefabricated containers, where the first container contains an agent as dye preparation, and the second container contains an oxidizing agent composition comprising at least one chemical oxidizing agent, preferably hydrogen peroxide.

Description

The invention relates to an agent for oxidative color change of keratinic fibers, which contains in a cosmetic carrier in addition to a coloring compound, a specific combination of two polysaccharides. The agents according to the invention are particularly suitable for color intensification in oxidative dyeing on human hair.

Changing the shape and color of the hair is an important area of modern cosmetics. This allows the hair's appearance to be adapted to current fashion trends as well as to the individual wishes of the individual. In addition to the desired dyeing and shaping performance, these agents should cause the least possible damage to the hair. To provide color-changing cosmetic agents, in particular for the skin or keratin-containing fibers such as human hair, the skilled person knows various dyeing systems depending on the requirements of the dyeing.

For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components which under the influence of oxidants or of atmospheric oxygen form the actual dyes with one another. The oxidation stains are characterized by excellent, long lasting staining results. For temporary dyeings usually dyeing or tinting agents are used which contain so-called substantive dyes as a coloring component. These are dye molecules that attach directly to the substrate and do not require an oxidative process to form the paint. Finally, another dyeing process has received great attention, in the precursors of the natural hair dye melanin on the substrate, eg. As hair, are applied, which then form naturally oxidized dyes in the context of oxidative processes in the hair.

Although commercial hair dyes already meet high demands on fastness properties, in particular wash resistance, perspiration fastness and light fastness, as well as on dyeing performances, especially with regard to color intensity, luminosity of the color and uniformity of the coloration on different fiber types, there is still the desire to further improve these properties.

The object of the present invention is therefore to provide cosmetic agents for the color change of keratinic fibers, which further improve the properties described above, which in particular bring about an improved intensity of the dyeing and whose dyeings have improved fastness properties.

In an unpredictable manner, it has now been found that color-modifying agents which, in addition to a color-modifying component, contain at least one polysaccharide combination consisting of a cellulose and an anionic polysaccharide, solve the above-mentioned technical problem in a particular way.

A first subject of the invention is therefore an agent for the color change of keratinic fibers, in particular human hair, which contains in a cosmetic carrier at least one coloring compound,
selected from oxidation dye precursors and / or precursors of natural-analogous dyes, contains,
and which is characterized in that the agent additionally contains at least one mixture of cellulose and at least one anionic polysaccharide.

Under keratinic fibers or keratin fibers are furs, wool, feathers and especially human hair to understand. Although the compositions according to the invention are primarily suitable for dyeing keratin fibers, in principle there is nothing to prevent their use in other fields as well.

The agents according to the invention contain the active ingredients in a cosmetic carrier. This cosmetic carrier is watery, alcoholic or watery-alcoholic. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, propellant-free foams, foam aerosols or other preparations which are suitable for use on the hair. For the purposes of the present invention, aqueous-alcoholic carriers are water-containing compositions containing 3 to 70% by weight of a C ₁ -C ₄ -alcohol, based on the total weight of the application mixture, in particular ethanol or isopropanol. A watery Carrier according to the invention contains at least 30 wt .-%, in particular at least 50 wt .-% water, based on the total weight of the application mixture.

As the first essential ingredient, the agent according to the invention contains at least one mixture of cellulose and at least one anionic polysaccharide.

Cellulose is composed of β-1,4-glycosidically linked D-glucopyranose units. In the solid state, crystalline regions alternate with those of low order (amorphous regions) in cellulose. Natural and manufacturing impurities, such as in particular the presence of carboxy groups, are typically in the range of about 1%. Therefore, according to the invention, cellulose itself is not considered to be an anionic polysaccharide.

Cellulose which can be used according to the invention has a degree of polymerization (DP), ie a length of glucopyranose units, of from about 10 to about 8,000. However, it has been found that in particular celluloses with a low degree of polymerization exert a positive effect on the dyeing properties of the compositions.

In particular so-called microcrystalline cellulose shows advantageous effects. Microcrystalline cellulose is obtained by partial alkaline or acidic hydrolysis of celluloses in which only the amorphous regions of the semi-crystalline cellulose are attacked and completely dissolved. This results first microfine cellulose, which is disaggregated in aqueous suspension under mechanical force in microcrystalline cellulose.

The degree of polymerization remaining after hydrolysis (also leveling off degree of polymerization = LODP) of the microcrystalline cellulose is in the range of about 30-400.

Preferred celluloses are therefore microcrystalline celluloses and have a degree of polymerization of from 30 to 400.

An embodiment of the present invention is therefore characterized in that the agent contains microcrystalline cellulose as cellulose.

According to the invention, anionic polysaccharides are polysaccharides in whose framework or in their side chains regular sugar monomers with anionic groups, in particular carboxylate, sulfate or phosphate, are contained. Examples of carboxylate-containing monomers are carboxyalkyl ethers of sugars and sugar acids (uronic acids).

Anionic polysaccharides preferred according to the invention are carboxyalkylcelluloses, xanthan, alginic acid, carrageenan, tragacanth, karaya gum, gum arabic, gellan, pectin, agaropectin and / or one of their physiologically tolerated salts. Physiologically acceptable salts are in particular the ammonium salts and the salts of alkali metals, especially sodium and potassium, alkaline earth metals, in particular magnesium and Calcuim, and zinc.

Particularly preferred anionic polysaccharides are carboxyalkylcelluloses and their physiologically acceptable salts. Very particular preference is given to using sodium carboxymethylcellulose as the anionic polysaccharide.

A further embodiment of the present invention is therefore characterized in that the agent as anionic polysaccharide comprises at least one compound selected from carboxyalkylcelluloses, alginic acid, carrageenan, tragacanth, karaya gum, gum arabic, pectin, agaropectin and / or one of its physiologically acceptable salts, preferably selected from sodium carboxymethylcellulose.

For particularly advantageous effects of the invention cellulose and anionic polysaccharide are used in a certain weight ratio to each other. Preferred here is a weight ratio of cellulose and anionic polysaccharide of 1 to 1 to 15 to 1, preferably 2 to 1 to 10 to 1 and particularly preferably 3 to 1 to 8 to 1.

A further embodiment of the present invention is therefore characterized in that the agent comprises a mixture of cellulose and anionic polysaccharide in a weight ratio of 1: 1 to 15: 1, preferably 2: 1 to 10: 1, and more preferably 3: 1 to 8: 1 1, contains.

Particularly preferred agents according to the invention comprise a mixture of microcrystalline cellulose and sodium carboxymethylcellulose (cellulose gum), preferably in a weight ratio of 3: 1 to 10: 1.

An inventively preferred mixture is the raw material called Avicel ^® PC 611 (FMC), which is sold as a mixture of microcrystalline cellulose and sodium carboxymethylcellulose with a content of sodium carboxymethylcellulose from 11 to 19%.

Agents preferred according to the invention are characterized in that the agent comprises the mixture of cellulose and at least one anionic polysaccharide in a proportion by weight of from 0.1 to 10.0% by weight, preferably from 0.2 to 5.0% by weight and in particular from 0.5 to 2.5 wt .-%, each based on the total weight of the composition contains.

The compositions according to the invention furthermore contain a coloring compound selected from oxidation dye precursors and / or precursors of naturally-analogous dyes.

In a preferred embodiment, agents according to the invention contain as coloring components at least one oxidation dye precursor.

The oxidation dye precursors are preferably used in an amount of 0.005 to 25 wt .-%, preferably from 0.05 to 20 wt .-% and particularly preferably from 0.1 to 15 wt .-%, each based on the ready-to-use oxidation colorant.

In a preferred embodiment, the compositions of the invention contain at least one developer type and / or type of coupler oxidation dye precursor. Preferably, the colorants of the present invention contain at least one developer type oxidation dye precursor and at least one coupler type oxidation dye precursor.

The developer and coupler components are usually used in free form. In the case of substances having amino groups, however, it may be preferable to use them in salt form, in particular in the form of the hydrochlorides and hydrobromides or the sulfates.

Inventive developer components are selected from p-phenylenediamine, binuclear developer components, p-aminophenol, o-aminophenol, heterocyclic developer components and / or the derivatives of the above classes of substances. The developer components are preferably used in an amount of 0.05 to 10 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use oxidation colorant.

Preferred p-phenylenediamines are selected from one or more compounds of the group formed from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl -p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl -p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) aniline, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (2-hydroxyethyl ) amino-2-methylaniline, 4-N, N-bis (2-hydroxyethyl) amino-2-chloroaniline, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl) -p- phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (2-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p- phenylenediamine, N-ethyl-N-2-hydroxyethyl-p-phenylenediamine, N- (2,3-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine , 2- (2-hydroxyethyloxy) -p-phenylene diamine, 2-methoxymethyl-p-phenylenediamine, 2- (2-acetylaminoethyloxy) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3 - (1H-imidazol-1-yl) propyl] amine, 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts. Particularly preferred p-phenylenediamine derivatives according to the invention are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl) -p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine, 2-methoxymethyl-p Phenylenediamine and the physiologically acceptable salts of these compounds.

It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups. In particular, preferred binuclear developer components are selected from at least one of the following compounds: N, N'-bis (2-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3- diamino-propan-2-ol, N, N'-bis (2-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) tetramethylenediamine , N, N'-bis (2-hydroxyethyl) -N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis [4- (methylamino) phenyl] tetramethylenediamine, N, N ' -Diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) - 1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis- (2 ', 5'- di-aminophenyl) -1,4,7,10-tetraoxadecane and their physiologically acceptable salts. Particularly preferred binuclear developer components are selected from N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hydroxy) hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane, 1,10- Bis- (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane or one of the physiologically acceptable salts of these compounds.

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particularly preferred p-aminophenols are p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2 - [(2-hydroxyethyl) aminomethyl] phenol, 4-amino-2- (1,2-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6- dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically acceptable salts. Particularly preferred compounds are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (1,2-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol or one of the physiologically acceptable salts of these compounds.

Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component may be selected from heterocyclic developer components, such as pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives or their physiologically acceptable salts. Preferred pyrimidine derivatives are the compounds 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine , 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine. Preferred pyrazole derivatives are the compounds selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4 '-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino 1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-t-butyl-1-methylpyrazole, 4,5-diamino-1-t butyl-3-methylpyrazole, 4,5-diamino-1- (2-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2-aminoethyl) amino-1,3-dimethylpyrazole, and their physiologically acceptable salts.

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of pyrazolo [1,5-a] pyrimidine and its tautomeric forms, provided that a tautomeric equilibrium exists. The pyrazolo [1,5-a] pyrimidines are in particular selected from pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7- diamine, pyrazolo [1,5-a] pyrimidine-3,5-diamine, 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine, 3-aminopyrazolo [1,5-a] pyrimidine 7-ol, 3-aminopyrazolo [1,5-a] pyrimidin-5-ol, 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-aminopyrazolo [1, 5-a] pyrimidin-3-ylamino) ethanol, 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-aminopyrazolo [ 1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol; 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 3-amino-7-dimethylamino-2, 5-dimethylpyrazolo [1,5-a] pyrimidine and its physiologically acceptable salts and their tautomeric forms when tautomeric equilibrium is present.

Particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl) -p- phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole-1) yl) propyl] amine, N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diaminopropan-2-ol, bis (2-hydroxy-5 -aminophenyl) methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane, 1,10-bis- (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (1,2-dihydroxyethyl ) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, as well as the physiologically acceptable salts of these compounds.

Coupler components do not form a significant color within the framework of the oxidative dyeing alone, but always require the presence of developer components. Therefore, it is preferred according to the invention that at least one developer component is additionally used when using at least one coupler component.

Coupler components according to the invention are preferably selected from m-aminophenol, m-diaminobenzene, o-diaminobenzene, o-aminophenol, naphthalene derivatives having at least one hydroxyl group, di- or trihydroxybenzene, pyridine, pyrimidine, monohydroxy- or monoaminoindole, monohydroxy- or monoaminoindoline, pyrazolone , Benzomorpholine, quinoxaline and / or the derivatives of the preceding classes of substances. The coupler components are preferably used in an amount of 0.005 to 10 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use colorant.

The inventively preferred m-aminophenols or derivatives thereof are selected from at least one compound selected from the group consisting of m-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2- chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5- Amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3-diethylaminophenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-methylaminobenzene, 3-ethylamino 4-methylphenol, 2,4-dichloro-3-aminophenol and the physiologically acceptable salts of the abovementioned compounds.

The inventively preferred m-diaminobenzenes or their derivatives are selected from at least one compound from the group formed from m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy ) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene , 2 - ({3 - [(2-Hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl } amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4 - (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene and the physiologically acceptable salts of said compounds.

The inventively preferred o-diaminobenzenes or derivatives thereof are selected from at least one compound selected from the group consisting of 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of said compounds.

Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1 , 2,4-trihydroxybenzene.

The inventively preferred pyridine derivatives are selected from at least one compound of the group formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino 6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2 , 6-dimethoxypyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiologically acceptable salts of the aforementioned compounds ,

Preferred naphthalene derivatives having at least one hydroxy group are selected from at least one compound of the group formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1.3 Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.

The inventively preferred indole derivatives are selected from at least one compound of the group which is formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable salts of the aforementioned compounds.

The inventively preferred indoline derivatives are selected from at least one compound of the group which is formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable salts of the aforementioned compounds.

Preferred pyrimidine derivatives are selected from at least one compound of the group formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2 -Amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine and the physiologically acceptable salts of the aforementioned compounds.

Particularly preferred coupler components according to the invention are selected from 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol , 5- (2-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenyl) propane, 2,6-bis (2 ' -hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] - 2-methoxy-5-methylphenyl} amino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene , 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydro xy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the abovementioned compounds.

In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can stand.

Developer-type and coupler-type oxidation dye precursors are particularly preferably used in certain combinations. However, other dye precursors can also be combined with the oxidation dye precursors mentioned as combination and / or their physiologically tolerated salts. Preferred agents therefore contain, as the oxidation dye product, at least one of the combinations selected from p-toluenediamine / resorcinol; p-toluenediamine / 2-methylresorcinol; p-toluenediamine / 5-amino-2-methyl phenol; p-toluenediamine / 3-aminophenol; p-toluenediamine / 2- (2,4-diaminophenoxy) ethanol; p-toluenediamine / 1,3-bis (2,4-diaminophenoxy) propane; p-toluenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; p-toluenediamine / 2-amino-3-hydroxypyridine; p-toluenediamine / 1-naphthol; 2- (2-hydroxyethyl) -p-phenylenediamine / resorcinol; 2- (2-hydroxyethyl) -p-phenylenediamine / 2-methylresorcinol; 2- (2-hydroxyethyl) -p-phenylenediamine / 5-amino-2-methyl phenol; 2- (2-hydroxyethyl) -p-phenylenediamine /-aminophenol 3; 2- (2-hydroxyethyl) -p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol; 2- (2-hydroxyethyl) -p-phenylenediamine / 1,3-bis (2,4-diaminophenoxy) propane; 2- (2-hydroxyethyl) -p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; 2- (2-hydroxyethyl) -p-phenylenediamine / 2-amino-3-hydroxypyridine; 2- (2-hydroxyethyl) -p-phenylenediamine / 1-naphthol; 2-methoxymethyl-p-phenylenediamine / resorcinol; 2-methoxymethyl-p-phenylenediamine / 2-methylresorcinol; 2-methoxymethyl-p-phenylenediamine / 5-amino-2-methyl phenol; 2-methoxymethyl-p-phenylene diamine / 3-aminophenol; 2-methoxymethyl-p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol; 2-methoxymethyl-p-phenylene diamine / 1,3-bis (2,4-diaminophenoxy) propane; 2-methoxymethyl-p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; 2-methoxymethyl-p-phenylenediamine / 2-amino-3-hydroxypyridine; 2-methoxymethyl-p-phenylenediamine / 1-naphthol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / resorcinol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 2-methylresorcinol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 5-amino-2-methyl phenol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 3-aminophenol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 2- (2,4-diaminophenoxy) ethanol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 1,3-bis (2,4-diaminophenoxy) propane; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 2-amino-3-hydroxypyridine; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 1-naphthol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / resorcinol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-methylresorcinol; 4,5-diamino-1- (2-hydroxyethyl) pyrazol / 5-amino-2-methyl phenol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 3-aminophenol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2- (2,4-diaminophenoxy) ethanol; 4,5- Diamino-1- (2-hydroxyethyl) pyrazole / 1,3-bis (2,4-diaminophenoxy); 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-amino-3-hydroxypyridine; and 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1-naphthol.

In a further embodiment of the present invention, at least one dye precursor of naturally-analogous dyes is added as the coloring component.

The dyestuff precursors of naturally-analogous dyes are preferably indoles and indolines which have at least two groups selected from hydroxy and / or amino groups, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In another embodiment, the colorants contain at least one indole and / or indoline derivative. Compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent. The dye precursors of naturally-analogous dyes are each preferably used in an amount of from 0.001 to 5% by weight, in particular from 0.1 to 3.5% by weight, based on the total weight of the agents.

Preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid, and more preferably 5,6-dihydroxyindoline. Preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole , 5,6-Dihydroxyindole-2-carboxylic acid and in particular 5,6-dihydroxyindole.

In order to achieve a balanced and subtle nuance formation, it may be advantageous according to the invention if the agents according to the invention additionally contain further coloring components.

Furthermore, the compositions according to the invention may contain, as additional coloring component for shading, at least one substantive dye. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. The substantive dyes are each preferably used in an amount of 0.001 to 5 wt .-%, based on the total agent. The total amount of substantive dyes is preferably at most 3% by weight. Direct dyes are known as anionic, cationic and nonionic substantive dyes.

Preferred anionic substantive dyes are those under the international designations or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1, Acid Black 52, bromophenol blue and tetrabromophenol blue known compounds.

Preferred cationic substantive dyes are cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, aromatic systems substituted with a quaternary nitrogen group such as Basic Yellow 57, Basic Red 76, Basic Blue 99 , Basic Blue 347, Basic Brown 16 and Basic Brown 17, cationic anthraquinone dyes such as HC Blue 16 (Bluequat B), as well as substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, in particular Basic Yellow 87, Basic Orange 31 and Basic Red 51. The cationic substantive dyes sold under the trademark Arianor are also particularly preferred cationic substantive dyes in accordance with the invention.

Suitable nonionic substantive dyes are in particular nonionic nitro and quinone dyes and neutral azo dyes. Preferred nonionic substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2 -nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 6-nitro-1,2,3 , 4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, Picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

It is not necessary for oxidation dye precursors, direct dyes, or naturally-analogous dyes to each be uniform compounds. Rather, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing or for other reasons, eg. As toxicological, must be excluded.

The agents according to the invention are preferably formulated as flowable preparations. The means should be formulated so that the agent can be well applied and distributed well on the one hand, on the other hand, however, is sufficiently viscous that the agent remains at the site of action during the exposure time and does not run.

It has therefore proved to be advantageous according to the invention, when agents contain at least one thickener. With regard to these thickeners, there are no fundamental restrictions. Both organic and purely inorganic thickening agents can be used. Preferably, the thickener is an anionic, synthetic polymer. Preferred anionic polymers are acrylic acid and / or methacrylic acid polymers or copolymers which are preferably present in the compositions according to the invention in an amount of from 0.1 to 10% by weight, particularly preferably from 1 to 5% by weight, based in each case on the weight of the agent, are included. Further preferably, the thickener is a cationic synthetic polymer. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C ₁ -C ₄ -hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable. Such polymers can also be used as copolymers with nonionic monomer units, preferably acrylamide, methacrylamide, acrylic acid-C ₁ -C ₄ -alkyl ester and methacrylic acid-C ₁ -C ₄ -alkyl ester. Nonionic, fully synthetic polymers, such as polyvinyl alcohol or polyvinylpyrrolidinone, are also useful as thickeners of the invention. Further preferably, other naturally occurring, optionally modified thickeners are used, such as dextrins, cellulose derivatives, such as methylcellulose, and hydroxyalkylcelluloses. As inorganic thickeners, phyllosilicates (polymeric, crystalline sodium disilicates) have proven to be particularly suitable in the context of the invention. In particular clays, preferably magnesium aluminum silicates, such as, for example, bentonite, especially smectites, such as montmorillonite or hectorite, which may optionally also be suitably modified, and synthetic sheet silicates are preferred.

Particularly advantageous thickening agents are those which, in addition to the thickening power, additionally contribute to the desired properties of the agents, such as care properties. It was found that especially amphoteric polymers have this property to a particular degree. In a preferred embodiment, however, the compositions according to the invention additionally contain at least one amphoteric polymer. In this case, the amphoteric polymer can be constructed by polymerization of ethylenic monomers, which can be used both from different, cationic group-carrying monomers and various monomers carrying anionic groups and optionally also nonionic monomers. Preferred cationic monomers are dialkyldiallylammonium compounds, quaternary alkyl-vinyl-imidazolium compounds and (meth) acrylic acid esters or (meth) acrylic acid amides having trialkylammonioalkyl radicals. Preferred anionic monomers are physiologically acceptable salts of acrylic acid or methacrylic acid. Suitable nonionic monomers which may additionally be used are vinylcaprolactam, vinylpyrrolidinone, vinylimidazole, acrylamide and methacrylamide.

in der R1 und R2 unabhängig voneinander für Wasserstoff oder eine Methylgruppe stehen, R3, R4 und R5 unabhängig voneinander für Alkylgruppen mit 1 bis 4 Kohlenstoff-Atomen stehen, Y eine NH-Gruppe oder ein Sauerstoffatom, p eine ganze Zahl von 2 bis 5 und A^– ein physiologisch verträgliches Anion einer organischen oder anorganischen Säure ist,
und von mindestens einem anionischen Monomer, ausgewählt aus Acrylsäure und/oder Methacrylsäure und/oder einem deren physiologisch verträglichen Salze.A preferred embodiment of the first subject of the invention is characterized in that the agent additionally contains at least one amphoteric polymer which is derived from at least one cationic monomer having quaternary ammonium groups of the general formula (I),

in which R 1 and R 2 independently of one another represent hydrogen or a methyl group, R 3, R 4 and R 5 independently of one another represent alkyl groups having 1 to 4 carbon atoms, Y denotes an NH group or an oxygen atom, p denotes an integer from 2 to 5 and A ^{- is} a physiologically acceptable anion of an organic or inorganic acid,
and at least one anionic monomer selected from acrylic acid and / or methacrylic acid and / or a physiologically acceptable salt thereof.

In this formula, particularly preferably in formula (I), the group Y is NH. p preferably represents the number 3. R 1 and R 2 are preferably hydrogen. R3, R4 and R5 are preferably methyl. A ^- is preferably chloride.

Particularly preferred amphoteric polymers are sold under the INCI name "Acrylamidopropyltrimonium Chloride / Acrylates Copolymer".

The amphoteric polymers are preferably present in a total amount of 0.01 to 5 wt .-%, preferably 0.05 to 3 wt .-% and most preferably from 0.1 to 2 wt .-%, based on the total amount of ready-to-use agent.

Usually, the compositions according to the invention additionally comprise as surface-active substance an emulsifier or a surfactant, surface-active substances being referred to as surfactants or as emulsifiers, depending on the field of application. In particular, anionic and nonionic surfactants and emulsifiers are preferred.

A further embodiment of the present invention is therefore characterized in that the agent additionally contains at least one nonionic and / or anionic surfactant.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. Preferred anionic surfactants are alkyl sulfates, alkyl ether sulfates, each having from 10 to 18 carbon atoms in the alkyl group, and polyalkoxylated ether carboxylic acids having from 6 to 20 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and carboxyalkyl ether derivatives of alkyl polyglucosides.

A further embodiment of the first subject of the invention is characterized in that the agent contains as additional anionic surfactant at least one carboxymethyl ether derivative of an alkylpolyglucoside of the formula R'O- (Z) _n , in which R 'is a C ₁₀ -C ₂₀ -alkyl chain, Z is a sugar residue having 5 or 6 carbon atoms and n is a number from 1 to 15.

An example of preferred carboxymethyl ether derivatives of an alkyl polyglucoside is sold under the trade names Plantapon LGC Sorb (INCI name: Lauryl Glucose Carboxylate, Lauryl Glucoside).

The anionic surfactants are used in preferably in a total amount of 0.1 to 30 wt .-%, preferably 1 to 25 wt .-% and most preferably from 1 to 15 wt .-%, based on the total amount of the ready-to-use agent ,

Surface-active compounds of the nonionic surfactant type have also proven particularly advantageous. Such compounds are, for example, adducts of polyethylene oxide with fatty alcohols, wherein addition products of polyethylene oxide to fatty alcohols are particularly preferred which have an average degree of ethoxylation of 10 to 45, in particular from 12 to 30, such as steareth-20, coceth-15, oleth-20 or also Ceteareth-30, as well as Alkylpolyglucoside according to the general formula RO- (Z) _n , wherein R is alkyl, Z is for sugar and n is the number of sugar units.

A further embodiment of the first subject of the invention is characterized in that the agent as additional nonionic surfactant at least one alkyl polyglucoside of the formula R''O- (Z ') _m , wherein R''is a C ₁₀ -C ₂₀ alkyl chain, Z' is a sugar residue with 5 or 6 carbon atoms and m is a number from 1 to 15.

Examples of such compounds bear the INCI names Decyl Glucoside, Lauryl Glucoside, Cetearyl Glucoside and Coco Glucoside.

Agents preferred according to the invention contain as nonionic surfactant the adduct of coconut fatty alcohol with (poly) glucose, which is known by the INCI name Coco-Glucoside. Such a product is sold, inter alia, under the trade name Lamesoft PO 65 (INCI name: Coco-Glucoside, Glyceryl Oleate, Aqua).

The nonionic surfactants are used in preferably in a total amount of 0.1 to 30 wt .-%, preferably 1 to 20 wt .-% and most preferably from 1 to 10 wt .-%, based on the total amount of the ready-to-use agent ,

In the case of oxidative dyeings, the development of the color can in principle be done with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired.

A further embodiment of the invention is therefore an agent which additionally contains an oxidizing agent selected from hydrogen peroxide and its solid addition products of organic and inorganic compounds. Suitable solid addition products according to the invention are in particular the addition products of urea, melamine, polyvinylpyrrolidinone and sodium borate in question.

Hydrogen peroxide is preferably used as oxidizing agent. The amount of hydrogen peroxide in the ready-to-use agent is preferably from 0.5 to 12% by weight, preferably from 0.8 to 6% by weight, in each case based on the ready-to-use agent.

In an application of additional oxidizing agents, the actual colorant is expediently immediately before use by mixing a preparation according to the invention comprising in a cosmetic carrier at least one coloring compound selected from oxidation dye precursors and / or precursors of natural-analogous dyes, and a preparation containing the additional oxidizing agent, in particular hydrogen peroxide. The agent according to the invention may contain a mixture of cellulose and at least one anionic polysaccharide in the preparation with the coloring compounds and / or in the oxidizing agent preparation. The preparation with the coloring compounds preferably contains a mixture of cellulose and at least one anionic polysaccharide.

Furthermore, it has proven to be advantageous if the agents, if appropriate also preparation containing coloring compounds, and / or the oxidizing agent preparations of oxidative colorants contain at least one stabilizer or complexing agent. Common and preferred chelating agents in the context of the present invention are, for example, polycarboxylic acids, nitrogen-containing monocarboxylic or polycarboxylic acids, especially ethylenediaminetetraacetic acid (EDTA), ethylenediamine disuccinic acid (EDDS) and nitrilotriacetic acid (NTA), geminal diphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP ), Aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and cyclodextrins, alkali stannates (sodium stannate), alkali pyrophosphates (tetrasodium pyrophosphate, disodium pyrophosphate), alkali metal phosphates ( Sodium phosphate), and phosphoric acid. According to the invention, the agents preferably contain complexing agents of from 0.01 to 3% by weight, preferably from 0.05 to 1% by weight, based in each case on the total weight of the composition according to the invention.

The compositions of the invention contain other auxiliaries and additives. The flowable preparations preferably additionally contain, as further surface-active substance, a cationic, amphoteric and / or zwitterionic surfactant.

Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate, sulfonate or sulfate group in the molecule. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

In another preferred embodiment of the present invention, the agent further contains at least one amphoteric surfactant. Particularly preferred amphoteric surfactants are sold under the INCI name Disodium Cocoamphodipropionate with the trade names Miranol C2M SF conc. (Rhodia), Amphoterge K-2 (Lonza) and Monateric CEM-38 (Unichema) and designation Disodium Cocoamphodiacetate with the trade names Dehyton (Cognis), Miranol C2M (Rhodia) and Ampholak XCO 30 (Akzo Nobel).

The zwitterionic and amphoteric surfactants are preferably present in a total amount of 0.1 to 15 wt .-%, preferably 0.5 to 10 wt .-% and most preferably from 1 to 5 wt .-%, based on the total amount of ready-to-use agent.

Also preferred according to the invention are cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. The cationic surfactants are contained in the compositions according to the invention preferably in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

Furthermore, the agents according to the invention may contain further active ingredients, auxiliaries and additives, for example nonionic polymers, cationic polymers, zwitterionic polymers, anionic polymers, structurants such as glucose, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, fiber-structure-improving active ingredients, in particular monosaccharides and oligosaccharides such as glucose, galactose, fructose and fructose, defoamers such as silicones, dyes for staining the agent, anti-dandruff agents, drugs such as amino acids, oligopeptides and protein hydrolysates, polyphenols and (pseudo) ceramides, panthenol, pantothenic acid, pantolactone, allantoin, Pyrrolidinoncarbonsäuren and salts thereof and Bisabolol, vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H, plant extracts, fats and waxes such as beeswax, montan wax and paraffins, swelling and penetrating substances such as glycerol, Prop glycol ethers, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers, pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate, pigments, brightening agents ( such as sodium persulfate, potassium persulfate or ammonium persulfate), propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, and antioxidants.

The choice of these other substances will be made by those skilled in the art according to the desired properties of the agents. With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of the cosmetics, 2nd edition, Hüthig book publishing house, Heidelberg, 1989 , referenced.

For the sake of fiber preservation, it is desirable if the means for changing the color of the hair have a neutral pH as possible. For improved color formation, however, an alkaline pH is advantageous. Another preferred embodiment of the present invention is that the ready-to-use agent has a pH between 6.0 and 12.0, preferably between 7.0 and 11.5, particularly preferably between 8.0 and 11.0. For the purposes of the present invention, the pH values are pH values which were measured at a temperature of 22 ° C. Usually, the pH is adjusted with pH adjusters. In order to adjust the pH, those skilled in the art are familiar with common acidifying and alkalizing agents. The alkalizing agents which can be used for adjusting the pH are typically selected from inorganic salts, in particular the alkali metals and alkaline earth metals, organic alkalizing agents, in particular amines, basic amino acids and alkanolamines, and ammonia. Acidifying agents which are preferred according to the invention are pleasure acids, such as, for example, citric acid, acetic acid, malic acid or tartaric acid, and also dilute mineral acids. Alkaliating agents preferred according to the invention are selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, 2-aminoethane-1-ol, triethanolamine, ammonia, 1-aminopropane-2 -ol and 2-amino-2-methylpropan-1-ol.

The preparation of the color change agents according to the invention is subject in principle to no restrictions. The agents according to the invention can be formulated as 1-component agents, which are optionally mixed with a second preparation containing, for example, an oxidizing agent immediately before use. However, it has also proven to be preferred in some cases when the product is formulated as a 2-component agent. Within the scope of a preferred embodiment, the means according to the invention are therefore made up in such a way that one of the components essential to the invention is packaged separately. According to the invention, it does not initially matter which of the components according to the invention is packaged separately.

Agents preferred according to the invention are characterized in that the agent is prepared immediately before use by mixing at least two preparations, wherein the at least two preparations are provided in at least two separate prefabricated containers, and wherein a container contains a colorant, which in a cosmetic carrier at least a coloring Compound, in particular an oxidation dye precursor, and additionally contains at least one mixture of cellulose and at least one anionic polysaccharide,
and another container containing an oxidizing agent formulation containing at least one oxidizing agent.

The ready-to-use colorant preferably has a pH of between 5.0 and 12.0, preferably between 6.0 and 11.0.

• (i) ein Container (I) als Farbstoffzubereitung ein Mittel des ersten Erfindungsgegenstands
• (ii) und ein weiterer Container (II) eine Oxidationsmittelzusammensetzung, enthaltend mindestens ein chemisches Oxidationsmittel, insbesondere Wasserstoffperoxid, enthält.

Another object of the present invention is therefore a multi-component packaging unit (kit-of-parts), comprising at least two separately assembled containers, wherein

• (I) a container (I) as a dye preparation a means of the first subject of the invention
• (ii) and another container (II) containing an oxidizing agent composition containing at least one chemical oxidizing agent, in particular hydrogen peroxide.

The preparations of the multicomponent packaging unit are contained in separately packaged containers. For the purposes of the present invention, container is understood to mean an envelope which is present in the form of an optionally reclosable bottle, a tube, a can, a sachet, a sachet or similar wrappings. The wrapping material according to the invention are no limits. However, these are preferably casings made of glass or plastic.

It may be advantageous according to the invention if the multicomponent packaging unit according to the invention contains at least one further hair treatment agent in a separate container, in particular a conditioning agent. In addition, the packaging unit application aids, such as combs, brushes or brushes, personal protective clothing, especially disposable gloves, and optionally include instructions for use. With regard to further preferred embodiments of the multi-component packaging unit (kit-of-parts), what has been said about the agents according to the invention applies mutatis mutandis.

The agent according to the invention, if appropriate after mixing with an oxidizing agent preparation, is used in processes for coloring keratinic fibers, in particular human hair and preferably human hair on the living applicant.

Such methods for changing the color of human hair are characterized in that an inventive composition according to the above specifications is applied to the hair, for a contact time of 2 to 45 minutes, preferably 15 to 30 minutes left on the hair, and then the hair is rinsed ,

A preferred embodiment of the method for coloring keratinic fibers is when a composition in a cosmetic carrier containing at least one oxidation dye precursor and additionally at least one mixture of cellulose and at least one anionic polysaccharide, mixed with an oxidizing agent preparation containing hydrogen peroxide to form a homogeneous composition, this is applied to the hair, is left on the hair for an exposure time of 2 to 120 minutes, preferably from 3 to 45 minutes, and then the hair is rinsed out. The application temperatures in the color change of keratinic fibers according to the invention can be in a range between 15 and 45 ° C. After a period of exposure, the hair dye is removed by rinsing the hair to be dyed. The washing with a shampoo can be omitted if a strong surfactant-containing carrier, eg. As a dyeing shampoo was used.

With regard to further preferred embodiments of the method according to the invention, mutatis mutandis the statements made concerning the agents according to the invention apply.

By applying the agents according to the invention for the oxidative dyeing of human hair, a color intensification compared with comparable oxidative colorants is achieved. Likewise, a comparatively reduced washing out of the color from the fibers is observed, so that an increased color intensity is maintained even after many washing operations.

Another subject of the invention is therefore the use of the means of the first subject of the invention for color intensification in the oxidative color change of human hair.

With regard to further preferred embodiments of the uses according to the invention, mutatis mutandis, the statements made with regard to the agents according to the invention apply.

Examples (all quantities in% by weight)

1.1 Coloring Creams (Table 1) raw material V1 E1 Lanette D [1] 9.00 9.00 Lorol techn. [2] 3.10 3.10 FASOS-Na, C12-C14 (2 EO), 27% by weight 11.00 11.00 Plantapon LGC Sorb [3] 5.55 5.55 Ceteareth-12 0.28 0.28 Ceteareth-20 0.50 0.50 isostearic 2.22 2.22 myristic 0.56 0.56 Product W 37194 [5] 2.00 2.00 p-Toluylenediamine 1.15 1.15 2,4,5,6-Tetraaminopyrimidinsulfat 1.10 1.10 2-amino-3-hydroxypyridine 0.41 0.41 resorcinol 0.14 0.14 4-amino-3-nitrophenol 0.011 0.011 2-methyl 0.58 0.58 2,7-diaminonaphthalene 0.034 0.034 Avicel ^® PC 611 [5] - 1.00 ammonium sulfate 0.30 0.30 Sodium sulfite, anhydrous, 96% by weight 0.30 0.30 HEDP, 60% by weight 0.20 0.20 ascorbic acid 0.05 0.05 Potassium hydroxide, 50% by weight 1.63 1.63 Sodium silicate 40/42 0.50 0.50 Ammonia, 25% by weight 7.10 7.10 Perfume qs qs Water, desalted add 100 [1] C ₁₆ -C ₁₈ fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)
[2] C ₁₂ -C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (Cognis)
[3] C ₁₂ -C ₁₄ -Alkylpolyglucoside Carboxylmethyl ether, sodium salt, C ₁₂ -C ₁₄ -alkylpolyglucoside (about 28.5-34%, INCI name: Lauryl Glucose Carboxylate (15-25%), Lauryl Glucose ( 10-20%), Aqua) (BASF)
[4] Sodium acrylate, trimethylammoniopropylacrylamide chloride copolymer (about 20%, INCI name: Acrylamidopropyltrimonium Chloride / Acrylates Copolymer, Aqua) (Bozzetto)
[5] microcrystalline cellulose and sodium carboxymethylcellulose (INCI name: Microcrystalline Cellulose (and) Cellulose Gum) (FMC) 1.2 Developer preparation EW (Table 2) raw material Wt .-% disodiumpyrophosphate 0.30 EDTA, Na ₂ 0.15 Sodium benzoate 0.04 Emulgade F [6] 2.10 Phosphoric acid, 85% by weight 0.04 Hydrogen peroxide, 50% by weight 12,00 Water, demineralized ad 100 [6] INCI name: Cetearyl Alcohol, PEG-40 Castor Oil, Sodium Cetearyl Sulfate (Cognis)

2.1 colorations

The dyeing creams E1 and V1 were mixed before use with the developer solution EW in a weight ratio of 1: 1 and intimately mixed. Per gram of hair (2 types: Kerling International, Backnang (DE), European natural human hair: ENH white and ENH Dunkelblond 7-0) 4 g each of the freshly prepared, ready to use colorant was applied. The exposure time was 30 minutes at 35 ° C for the colorants. Thereafter, the tresses were rinsed with warm water for 30 seconds and air dried.

2.2 Color Intensity - Results

The colorimetric measurements were carried out on 10 cm long strands Euronaturhaar white or Euronaturhaar Dunkelblond (7-0) from Kerling at 4 measuring points per tress. The measuring device used was the Spectralflash SF 450 from Datacolor. The following measurement parameters were used: with gloss / measuring aperture SAV / D65 (daylight) / 10 ° observer. The results of the measurements were quantified using the CIELAB color space.

The following color differences were determined (Table 3): No. hair type dye L a b ΔE (untreated / colored) 1.0 ENH knows untreated 70.50 2.55 21.11 - 1.1 ENH knows V1 + EW 18.88 10.61 5.41 54.55 1.2 ENH knows E1 + EW 21.92 12.29 6.97 51.52 2.0 ENH 7-0 untreated 30.82 6.59 12.42 - 2.1 ENH 7-0 V1 + EW 19.15 6.64 3.15 14.90 2.2 ENH 7-0 E1 + EW 20.85 8.07 4.33 12.93

A larger ΔE value means a greater color difference between the untreated and the colored strand. The coloring of the agent E1 according to the invention has, on different hair types, in each case a greater color difference and thus a more intense coloring (experiments 1.1 and 2.1) than the corresponding comparative experiment (experiments 1.2 and 2.2). The use of the colorants according to the invention therefore leads to a significant improvement in the color intensity (ΔE value) of the dyeing.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited non-patent literature

• Kh. Schrader, Basics and Formulations of Cosmetics, 2nd Edition, Hüthig Buch Verlag, Heidelberg, 1989 [0091]

Claims (10)

Agent for the color change of keratinic fibers, in particular human hair, containing in a cosmetic carrier at least one coloring compound selected from oxidation dye precursors and / or precursors of natural analog dyes, characterized in that the composition additionally contains at least one mixture of cellulose and at least one anionic polysaccharide. Composition according to claim 1, characterized in that the agent contains microcrystalline cellulose as cellulose. Agent according to one of claims 1 to 2, characterized in that the agent as anionic polysaccharide at least one compound selected from carboxyalkycellulose, alginic acid, carrageenan, tragacanth, karaya gum, gum arabic, pectin, agaropectin and / or one of these physiologically acceptable salts , preferably selected from sodium carboxymethylcellulose. Composition according to one of claims 1 to 3, characterized in that the agent is a mixture of cellulose and anionic polysaccharide in a weight ratio of 1 to 1 to 15 to 1, preferably 2 to 1 to 10 to 1 and particularly preferably 3 to 1 to 8 to 1, contains. Agent according to one of claims 1 to 4, characterized in that the agent comprises the mixture of cellulose and at least one anionic polysaccharide in a weight fraction of 0.1 to 10.0 wt .-%, preferably from 0.2 to 5.0 wt .-% and in particular from 0.5 to 2.5 wt .-%, each based on the total weight of the composition contains. Agent according to one of claims 1 to 5, characterized in that the agent contains as coloring compound at least oxidation dye products as developer / coupler combinations which are selected from p-toluenediamine / resorcinol; p-toluenediamine / 2-methylresorcinol; p-toluylenediamine / 5-amino-2-methyl phenol; p-toluenediamine / 3-Aminophenol; p-toluenediamine / 2- (2,4-diaminophenoxy) ethanol; p-toluenediamine / 1,3-bis (2,4-diaminophenoxy) propane; p-toluenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; p-toluenediamine / 2-amino-3-hydroxypyridine; p-toluenediamine / 1-naphthol; 2- (2-hydroxyethyl) -p-phenylenediamine / resorcinol; 2- (2-hydroxyethyl) -p-phenylenediamine / 2-methylresorcinol; 2- (2-hydroxyethyl) -p-phenylenediamine / 5-amino-2-methyl phenol; 2- (2-hydroxyethyl) -p-phenylenediamine / 3-aminophenol; 2- (2-hydroxyethyl) -p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol; 2- (2-hydroxyethyl) -p-phenylenediamine / 1,3-bis (2,4-diaminophenoxy) propane; 2- (2-hydroxyethyl) -p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; 2- (2-hydroxyethyl) -p-phenylenediamine / 2-amino-3-hydroxypyridine; 2- (2-hydroxyethyl) -p-phenylenediamine / 1-naphthol; 2-methoxymethyl-p-phenylenediamine / resorcinol; 2-methoxymethyl-p-phenylenediamine / 2-methylresorcinol; 2-methoxymethyl-p-phenylenediamine / 5-amino-2-methyl phenol; 2-methoxymethyl-p-phenylene diamine / 3-aminophenol; 2-methoxymethyl-p-phenylenediamine / 2- (2,4-diaminophenoxy) ethanol; 2-methoxymethyl-p-phenylene diamine / 1,3-bis (2,4-diaminophenoxy) propane; 2-methoxymethyl-p-phenylenediamine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; 2-methoxymethyl-p-phenylenediamine / 2-amino-3-hydroxypyridine; 2-methoxymethyl-p-phenylenediamine / 1-naphthol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / resorcinol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 2-methylresorcinol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 5-amino-2-methyl phenol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 3-aminophenol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 2- (2,4-diaminophenoxy) ethanol; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 1,3-bis (2,4-diaminophenoxy) propane; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 2-amino-3-hydroxypyridine; N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine / 1-naphthol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / resorcinol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-methylresorcinol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 5-amino-2-methyl phenol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 3-aminophenol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2- (2,4-diaminophenoxy) ethanol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1,3-bis (2,4-diaminophenoxy) propane; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-amino-3-hydroxypyridine and 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 1-naphthol and / or one of the physiologically acceptable salts of previous connections. Composition according to one of claims 1 to 6, characterized in that the agent additionally contains at least one amphoteric polymer which is derived from at least one cationic monomer having quaternary ammonium groups of the general formula (I),

in which R 1 and R 2 independently of one another represent hydrogen or a methyl group, R 3, R 4 and R 5 independently of one another represent alkyl groups having 1 to 4 carbon atoms, Y denotes an NH group or an oxygen atom, p denotes an integer from 2 to 5 and A ^{- is} a physiologically acceptable anion of an organic or inorganic acid, and of at least one anionic monomer selected from acrylic acid and / or methacrylic acid and / or a physiologically acceptable salt thereof. Agent according to one of claims 1 to 7, characterized in that the agent additionally contains at least one nonionic and / or anionic surfactant. Kit of parts containing at least two separately assembled containers, wherein (i) a container (I) as a dye preparation contains an agent according to one of claims 1 to 8, (ii) and another container (II) containing an oxidizing agent composition containing at least one chemical oxidizing agent, in particular hydrogen peroxide. Use of a composition according to any one of claims 1 to 8 for color intensification in the oxidative color change of human hair.