EP2906192A1

EP2906192A1 - Hair dye agent comprising aminopyrimidine derivatives

Info

Publication number: EP2906192A1
Application number: EP13774109.6A
Authority: EP
Inventors: Antje Gebert; Helmut Giesa; Annika Koenen
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2012-10-10
Filing date: 2013-10-01
Publication date: 2015-08-19
Also published as: US20150209257A1; US9364407B2; WO2014056758A1; DE102012218460A1

Abstract

The present application relates to agents for dyeing keratin fibers, in particular human hair, the agent containing, in a cosmetic carrier, a) at least one compound of formula (I) and/or a physiologically compatible salt of this compound, in which R¹ is a C₁-C₄ alkyl group, R² is a hydrogen atom, a C₁-C₈ alkyl group, a C₂-C₆ alkenyl group, a C₁-C₆ hydroxyalkyl group, a C₂-C₆ polyhydroxyalkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ alkylamino group, a Di-C₁-C₆ alkylamino group, a C₁-C₆ polyalkoxy group, a C₁-C₆ alkylamido-(C₁-C₆-) alkyl group, wherein the amide function can be substituted by one or two groups X, or is an aryl group, Y is an NH₂ or an OH group, b) at least one coupler component selected from the group made up of 3-amino-2-methylamino-6-methoxypyridine, 3-amino-6-methylphenol, 3-amino-2-hydroxypyridine, 1,3-bis-(2,4-diaminophenoxy)propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 2,5-dimethylresorcinol, 4-chlororesorcinol, 3-aminophenol, 2-amino-3-hydroxypyridine, 2-chloro-6-methyl-3-aminophenol, 2,6-dihydroxy-3,4-dimethylpyridine, 2-({3-[(2-hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol, 1-methoxy-2-amino-4- beta-hydroxy-ethylaminobenzene (Lehmann's blue), 2,4-diaminophenoxyethanol, 5-amino- 4-chloro-o-cresol, 2,4-dichloro-m-aminophenol, 2,6-dihydroxy-3,4-dimethylpyridine and/or a physiologically compatible salt of these compounds.

Description

"Hair Dyes Containing Aminopyrimidine Derivatives"

The invention relates to an agent for color change of keratin-containing fibers, in particular human hair, which contains certain substituted Aminopyrimidinderivate in combination with certain coupler components.

The invention further relates to the use of the developer-coupler combination in colorants for improving the dyeing results.

Changing the shape and color of the hair is an important area of modern cosmetics. For the fashionable color design of hairstyles or for the lamination of gray or white hair with fashionable or natural shades, the consumer uses color-modifying agents.

To provide color-changing cosmetic agents, in particular for the skin or keratin-containing fibers such as human hair, the skilled person knows various systems depending on the requirements of the coloration or color change.

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. The developer components form under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components, the actual dyes. The oxidation colorants are characterized by intensive excellent, long-lasting dyeing results. For natural-looking dyeings, a mixture of a larger number of oxidation dye precursors can be used, and in many cases direct substantive dyes are additionally used for shading.

In particular, oxidative hair dyes are often disadvantageous to the user despite their advantageous dyeing properties, so that a constant need for further development exists for oxidation dye precursors.

In the search for oxidation dye precursors with good compatibility profile many compounds have been explored, but often suffer from application problems, especially lack of gray coverage. In addition, in spite of already highly developed dyeing systems, there is still a need for dyeing systems which have excellent luminosity and intensity However, at the same time they have a very good durability, very good fastness properties and excellent homogeneity.

There is room for improvement especially in the field of red dyeing.

Many known dyeing systems with which red color shades can be achieved, have no satisfactory washing fastness and no sufficient leveling ability.

In the published patent application DE 25161 17 Triaminoalkoxypyrimidinderivate are proposed as developer components in oxidative hair dyes, which are toxicologically and dermatologically harmless.

However, it has been found that the shades obtained, which are disclosed in DE 25161 17, are not numerous enough for today's requirements (especially in the red range). Next to it are some of the ones in the o.g. Publications mentioned coupler components suspected of being sensitizing and / or toxicologically harmless.

Object of the present invention is therefore to lower the above-mentioned disadvantages of oxidative hair dyes. The colorants should produce intense colorations with high color and good resistance to external influences, in particular with good lightfastness and wash fastness, which suffer no color attenuation or color shift even after repeated shampooing of the hair. In addition, the stains should be as selective as possible, i. achieve as uniform, uniform staining results on differently pretreated hair as possible. In addition, the colorants should have a toxicologically advantageous profile.

Another object of the invention is to find suitable, toxicologically and dermatologically acceptable coupler components for Triaminoalkoxypyrimidinderivate with which a variety of shades - especially red shades - can be achieved, which have excellent wash fastness and a particularly good leveling power. Finally, it is desirable to achieve the greatest possible nuance of the individual shades.

It has been found that the combination of certain alkoxylated aminopyrimidine derivatives in conjunction with certain coupler components as oxidation dye precursors is outstandingly suitable for dyeing keratin-containing fibers. There are obtained colorations with good fastness properties, high color intensity and excellent brilliance and excellent Egalisierungsvermögen. A first object of the invention is therefore an agent for dyeing keratinic fibers, in particular human hair, which is characterized in that it is in a cosmetic carrier

a) at least one compound of the formula (I) and / or a physiologically acceptable salt of this compound,

in the

R for a C _| C ₄ alkyl group,

R ² represents a hydrogen atom, a d-Cs-alkyl group, a C ₂ -C ₆ alkenyl group, a Ci-C6-hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C1-C6 alkoxy group, a Ci-C6 An alkylamino group, a di-C 1 -C 6 -alkylamino group, a C 1 -C 6 -polyalkoxy group, a C 1 -C 6 -alkylamido (C 1 -C 6) -alkyl group, where the amide function may be substituted by one or two groups X, or an aryl group , and

Y is an NH ₂ or an OH group, and

b) contains at least one coupler component which is selected from the group formed from 3-amino-2-methylamino-6-methoxypyridine, 3-amino-6-methylphenol, 3-amino-2-hydroxypyridine, 1, 3-bis - (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 2,5-dimethylresorcinol, 4-chlororesorcinol, 3-aminophenol, 2-amino-3-hydroxypyridine, 2-chloro-6-methyl- 3-aminophenol, 2,6-dihydroxy-3,4-dimethylpyridine, 2 - ({3- [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3- [ (2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 1-methoxy-2-amino-4-beta-hydroxy-ethylaminobenzene (Lehmann's Blue), 2,4-diaminophenoxyethanol, 5-amino 4-chloro-o-cresol, 2,4-dichloro-m-aminophenol, 2,6-dihydroxy-3,4-dimethylpyridine and / or a physiologically acceptable salt of these compounds.

Keratin fibers are wool, furs, feathers and especially human hair. The colorants of the invention can in principle but also for dyeing other natural fibers such. As cotton, jute, sisal, linen or silk, modified natural fibers, such as regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose can be used. The compositions according to the invention contain components a) and b) in a cosmetic carrier, preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols, foam formulations or other preparations which are suitable for use on the hair. However, it is also conceivable to integrate the compounds of the formula (I) in a pulverulent or tablet-formulated formulation.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C 1 -C 4 -alcohol, in particular ethanol or isopropanol. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.

Examples of a d-Cs-alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl, n-pentyl, i-pentyl, i-hexyl, n-hexyl, i-heptyl , n-heptyl, i-octyl and n-octyl. Examples of a C ₂ -C ₆ -alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl, preferred C ₂ -C ₆ -alkenyl radicals are vinyl and allyl. Preferred examples of a C 1 -C 6 -hydroxyalkyl group are hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6-hydroxyhexyl ; a 2-hydroxyethyl group is particularly preferred. C ₁ -C 6 -alkoxy groups preferred according to the invention are the methoxy, ethoxy or propoxy group. Examples of a C ₂ -C ₆ polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group. Exemplary of C- | -C ₆ -alkylamino the methylamino, the ethylamino and propylamino group can be mentioned. The dimethylamino group, the diethylamino group and the dipropylamino group are examples of a di-C 1 -C 6 -alkylamino group. Exemplary of a C 1 -C 6 -alkylamido-C 1 -C 6 -alkyl group are the N-methyl-2-acetamide group N, N-dimethyl-2-acetamide group, the N-ethyl-2-acetamide group, the N , N-diethyl-2-acetamide group, N-methyl-3-propanamide group, N, N-dimethyl-3-propanamide group, N-ethyl-3-propanamide group and N, N diethyl-3-propanamide group. Preferred examples of polyalkoxy groups according to the invention are the (methoxymethoxy) methoxy group, the 2- (2-methoxyethoxy) ethoxy group, the 3- (3-methoxypropoxy) propoxy group, the (ethoxymethoxy) methoxy group, the 2- (2-methoxyethoxy) ethoxy group. 2-ethoxyethoxy) ethoxy group and the 3- (3-ethoxypropoxy) propoxy group. Preferred examples of aryl groups are phenyl, toluyl and benzyl. In the course of the work leading to this invention, it has been found that it is advantageous if colorants contain at least one compound of the formula (I) in which the radical R is a methoxy, ethoxy, propoxy, 2-methylpropoxy , 3-Methylbutoxy- or a 2-methylbutoxy, and the radical R ^{2 is} a hydrogen atom, a C ¹ -C 5 alkyl group, an aryl group, a Ci-C6-hydroxyalkyl group or a Ci-C6-alkylamino group.

Particularly preferably, the radical R in compounds of the formula (I) is a methoxy, a 2-methylpropoxy or a 3-methylbutoxy group, and the radical R ^{2 is} a hydrogen atom, a C 1 -C ₈ -alkyl group or an aryl group ,

If Y stands for a group NH ₂ , this is likewise particularly favorable for the solution of the problem according to the invention and is therefore preferred.

The compounds of the formula (I) are, in a particularly preferred embodiment, derivatives of 6-hydroxytriaminopyrimidine and thus amino compounds. From these, the known acid addition salts can be prepared in a customary manner. All statements of this document and accordingly the claimed protection range therefore relate both to the compounds present in free form and to their physiologically acceptable salts of organic or inorganic acids. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred. Very particular preference according to the invention is given to the monohydrochlorides, the dihydrochlorides and the trihydrochlorides.

A preferred embodiment of the first subject of the invention is characterized in that the agent comprises at least one compound according to formula (I) which is selected from

6-methoxypyrimidine-2,4,5-triamine 6-ethoxypyrimidine-2,4,5-triamine

6-propoxypyri-mid-2, 4, 5-triam in 6- (2-methylpropoxy) pyrimidine-2,4,5-triamine

6- (3-Methylbutoxy) pyrimidine-2,4,5-triamine 6- (2-methylbutoxy) pyrimidine-2,4,5-triamine

6-methoxy-N ⁴ -methyl pyrim id in 2, 4, 5-triamine n 6-ethoxy-N ⁴ -methylpyrimidine-2,4,5-triamine

6-propoxy-N-methylpyrimidine-2,4,5-triamine 6-isobutoxy-N ⁴ -methylpyrimidine-2,4,5-triamine

6- (3-methylbutoxy) -N-methylpyrimidine-2,4,5-6- (2-methylbutoxy) -N-methylpyrimidiretriamine triamine

6-Methoxy-N-ethylpyrimidine-2,4,5-triamine 6-ethoxy-N-ethyl pyrido id i n-2, 4, 5-triamine in

6-propoxy-N-ethyl-pyrimidine-2,4,5-triamine 6-isobutoxy-N-ethyl-pyrimidine-2,4,5-triamine

6- (3-methylbutoxy) -N-ethyl-pyrimidine-2,4,5-6-methoxy-N-phenyl-pyrimidine-2,4,5-triamine

6-Ethoxy-N-phenylpyrimidine-2,4,5-triamine 6-propoxy-N-phenylpyrimidine-2,4,5-triamine

6-isobutoxy-N-phenylpyrimidine-2,4,5-triamine 6- (3-methyl) butoxy-N-phenylpyrimidir

Within this preferred embodiment of the first subject of the invention, it is particularly preferred if the compound according to formula (I) is 6-methoxy-2,4,5-pyrimidinetriamine, 6- (2-methylpropoxy) -2,4,5-pyrimidinetriamine, 6- (3-methylbutoxy) -2,4,5-pyrimidinetriamine, 6-methoxy-4-N-methylpyrimidine-2,4-diamine and / or a physiologically acceptable salt of these compounds.

Particularly beautiful colorations - especially in the red and in the blue range - can be achieved if, as coupler component b) at least one of the compounds 3-amino-2-methylamino-6-methoxypyridine, 3-amino-2-hydroxypyridine, 1, 3-bis - (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 1-methoxy-2-amino-4-.beta.-hydroxyethylaminobenzene (Lehmann's Blau) and / or a physiologically acceptable salt of these compounds with at least one of the aforementioned aminopyrimidine compounds is combined.

In a further particularly preferred embodiment, the coupler component b) is therefore selected from 3-amino-2-methylamino-6-methoxypyridine, 3-amino-2-hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2 , 7-Dihydroxynaphthalene, 2-methylresorcinol, 1-methoxy-2-amino-4-.beta.-hydroxyethylaminobenzene (Lehmann's blue) and / or a physiologically acceptable salt of these compounds.

Agents preferred according to the invention are characterized in that they contain the compounds of the formula (I) and / or their physiologically tolerable salts in a proportion by weight of from 0.001 to 5.0% by weight, preferably from 0.025 to 2.5% by weight, particularly preferably from 0.05 to 2.0 wt .-% and particularly preferably from 0.1 to 1, 5 wt .-%, based on the total weight of the ready-to-use agent.

Compositions which are likewise preferred according to the invention are characterized in that they contain the at least one coupler component b) and / or their physiologically acceptable salt in a proportion by weight of from 0.001 to 5.0% by weight, more preferably from 0.025 to 2.5% by weight, particularly preferably from 0.05 to 2 wt .-% and in particular from 0.1 to 1, 5 wt .-%, each based on the total weight of the ready-to-use agent included.

The following combinations a) and b) are particularly preferred:

6-methoxy-2,4,5-pyrimidinetriamine and one or more compounds selected from 3-amino

2-methylamino-6-methoxypyridine, 3-amino-2-hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 1-methoxy-2-amino-4 β-hydroxyethylaminobenzene (Lehmanns Blau).

6- (2-methylpropoxy) -2,4,5-pyrimidinetriamine and one or more compounds selected from

3-Amino-2-methylamino-6-methoxypyridine, 3-amino-2-hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 1-methoxy-2 -amino-4-.beta.-hydroxyethylaminobenzene (Lehmanns Blau).

6- (3-methylbutoxy) -2,4,5-pyrimidinetriamine and one or more compounds selected from 3-amino-2-methylamino-6-methoxypyridine, 3-amino-2-hydroxypyridine, 1, 3-bis ( 2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 1-methoxy-2-amino-4-.beta.-hydroxyethylaminobenzene (Lehmanns Blau). 6-Methoxy-4-N-methylpyrimidine-2,4-diamine and one or more compounds selected from 3-amino-2-methylamino-6-methoxypyridine, 3-amino-2-hydroxypyridine, 1, 3-bis ( 2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 1-methoxy-2-amino-4-.beta.-hydroxyethylaminobenzene (Lehmanns Blau).

Especially preferred is the combination of 6-methoxy-2,4,5-pyrimidinetriamine with one or more compounds selected from 1,3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol.

In the above preferred combinations of oxidation dye precursors, it may also be advantageous according to the invention to use a physiologically acceptable salt of this compound instead of the uncharged compound.

In order to achieve a balanced and subtle nuance formation, it is advantageous according to the invention if further coloring components are contained in the composition according to the invention.

It may therefore be preferred according to the invention if the agent contains at least one further coloring component which is selected from additional oxidation dye precursors of the developer type and / or substantive dyes.

In addition to the developer-type oxidation dye precursors according to formula (I), the compositions according to the invention may additionally comprise at least one further developer component.

Preferred further 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-diamino-propan-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, 4-amino-phenol, 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, and the physiologically acceptable salts of this Ve rbindungen. Particularly preferred additional developer components are p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazole-1 yl) propyl] amine, and / or 4,5-diamino-1- (2-hydroxyethyl) pyrazole and their physiologically acceptable salts.

The additional developer components are preferably used in an amount of 0.0001 to 10 wt .-%, preferably 0.001 to 5 wt .-%, each based on the ready-to-use agent.

Furthermore, the agents according to the invention may contain 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 20 wt .-%, in particular from 0.05 to 5 wt .-%, each based on the total application preparation. The total amount of substantive dyes is preferably at most 3% by weight.

Direct dyes may be subdivided into anionic, cationic and nonionic substantive dyes which are selected and used by those skilled in the art for the requirements of the carrier base.

Preferred anionic substantive dyes are those having the international designations or trade names bromophenol blue, tetrabromophenol blue, 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 and Acid Black 52 known compounds.

Preferred cationic substantive dyes are Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347 / Dystar), Basic Blue 99, Basic Brown 16 and Basic Brown 17 and Yellow 87, Basic Orange 31 and Basic Red 51.

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 Red 10, HC Red 1, HC Red 13, HC Red BN, HC Blue 2, HC Blue 1 1, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 Compounds, and 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-nitro - benzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

The agents according to the invention may contain, in addition to the compound of the formula (I), also naturally-analogous dyes. 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, based on the total application preparation. Derivatives of 5,6-dihydroxyindoline, in particular 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6, are particularly suitable as precursors of naturally-analogous hair dyes -dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid, and also derivatives of 5,6-dihydroxyindole, in particular 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 physiologically acceptable salts of the above-mentioned compounds ,

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. This lightening effect may be desired regardless of the staining method. As the oxidizing agent are persulfates, peroxodisulfates, chlorites, hypochlorites and in particular hydrogen peroxide or and / or one of its solid addition products of organic or inorganic compounds in question.

In order to prevent a premature, undesired reaction of the oxidation dye precursors by the oxidizing agent, oxidation dye precursors and oxidizing agents themselves are expediently prepared separately from each other and brought into contact only immediately before use. In a further embodiment of the present invention, therefore, agents are preferred which are characterized in that they are 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 is a colorant (A) which contains in a cosmetic carrier at least one compound a) and at least one compound b), and a further container contains an oxidizing agent preparation (B) containing at least one oxidizing agent.

The oxidizing agent preparation (B) preferably contains as the oxidizing agent hydrogen peroxide and / or one of its solid addition products of organic or inorganic compounds, such as urea, melamine and sodium borate.

The amount of oxidizing agent in the ready-to-use agent is preferably from 0.5 to 12% by weight, preferably from 2 to 10% by weight, more preferably from 3 to 6% by weight (calculated as 100% H 2 O 2), based in each case on the ready to use means.

In a further preferred embodiment, the agent according to the invention is an agent for dyeing and, if appropriate, simultaneous lightening of keratinic fibers, which is preferably 0.5 to 15% by weight, preferably 1 to 12.5% by weight, particularly preferably 1 to 5 to 10 Wt .-% and in particular 2 to 6 wt .-% hydrogen peroxide, each based on the total weight of the ready-to-use agent contains.

Such oxidizer formulations are preferably aqueous, flowable oxidizer formulations. Preferred preparations are characterized in that the flowable oxidizing agent preparation - based on their weight - 40 to 90 wt .-%, preferably 50 to 85 wt .-%, particularly preferably 55 to 80 wt .-%, more preferably 60 to 77, 5 wt .-% and in particular 65 to 75 wt .-% water.

According to the invention, however, the oxidation dye can also be applied to the hair together with a catalyst which activates the oxidation of the dye precursors. Such catalysts are z. For example, certain enzymes, iodides, quinones or metal ions.

Furthermore, it has proven to be advantageous if the oxidizing agent preparations contain at least one stabilizer or complexing agent. Typical complexing agents and stabilizers which are preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediamine disuccinic acid (EDDS), hydroxylamine. ethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserine diacetic acid, N, N-di (2-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxy ethyl) aspartic acid or nitrilotriacetic acid (NTA), ethylenediaminediglutaric acid (EDGA), 2-hydroxypropylenediamine disuccinic acid (HPDS), glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG), 2-hydroxypropylenediamine N-N'-disuccinic acid (HPDDS), diaminoalkyldi (sulfosuccinic acid) (DDS), ethylenedicysteic acid (EDC), ethylenediamine-N-N'-bis (ortho-hydroxyphenyl) acetic acid (EDDHA), N-2-hydroxyethylamine N, N-diacetic acid, glyceryliminodiacetic acid, N-2-hydroxypropylsulfonic acid, Aspartic acid N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonic acid, β-alanine-N, N'-diacetic acid, asparagine - acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid, dipicolinic acid, and their salts and / or derivatives, geminal diphosphonic acids such as 1 -Hydroxyet han-1, 1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1, 1-diphosphonic acid, their higher homologues having up to 8 carbon atoms and Hydroxy- or amino-containing derivatives, aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid) (EDTMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) and their higher homologs, or nitrilotri (methylenephosphonic acid), phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2 4-tricarboxylic acid, cyclodextrins, and alkali stannates (sodium stannate), alkali metal pyrophosphates (tetra sodium pyrophosphate, disodium pyrophosphate), alkali phosphates (sodium phosphate), and phosphoric acid and salts thereof.

In the case of the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Preferred complexing agents according to the invention are nitrogen-containing polycarboxylic acids, in particular EDTA, and phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its Hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta- or Octa sodium salt.

The dyeing preparation and optionally oxidizing agent preparation contain other auxiliaries and additives. Thus, it has proved to be preferred according to the invention if the dyeing preparation and / or the oxidizing agent preparation contains at least one thickener. In terms of This thickener is not subject to any restrictions. Both organic and purely inorganic thickening agents can be used.

In a first preferred embodiment, the thickener is an anionic synthetic polymer. Preferred anionic groups are the carboxylate and sulfonate groups.

Examples of anionic monomers from which the polymeric anionic thickeners may consist are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are maleic anhydride and in particular 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

Preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example available under the trade drawing Carbopol ^® commercially. Also preferred is the homopolymer of 2-acrylamido-2-methylpropanesulfonic is sulfonic acid, which is available for example under the name Rheothik ^® 1 1 -80 in the trade.

Within this first embodiment, it may further be preferred to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic acid esters, methacrylic acid esters, itaconic acid mono- and diesters, vinylpyrrolidinone, vinyl ethers and vinyl esters.

The anionic acrylic acid and / or methacrylic acid polymers or copolymers are preferred in the inventive compositions in an amount of 0, 1 to 10 wt .-%, particularly preferably from 1 to 5 wt .-%, each based on the weight of By means of, included.

Preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C 1 -C ₆ -alkyl esters, as sold under the INCI declaration Acrylates Copolymers. A preferred commercial product is, for example, Aculyn ^® 33 from Rohm & Haas. However, preference is also given to copolymers of acrylic acid, methacrylic acid or their C 1 -C 6 -alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are in particular steareth 20 or Ceteth-20. Such copolymers are sold by Rohm & Haas under the trade name Aculyn ^® 22 and by National Starch under the trade names Structure ^® Structure 2001 ^® 3,001th

Preferred anionic copolymers are also acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer can also be present in crosslinked form, with crosslinking agents preferably being polyolefinically unsaturated compounds such as tetraallyloxythane, allylsucrose, allylpentaerythritol and methylenebisacrylamide. Such a polymer is contained in the commercial products Sepigel ^® 305 and Simulgel® ^® 600 from SEPPIC. The use of these compounds which, in addition to the polymer component, a hydrocarbon mixture (C ₁₃ -C ₁₄ -lsoparaffin or isohexadecane) and a nonionic emulsifier (laureth-7 or polysorbate-80), has proven to be particularly advantageous within the scope of the teaching according to the invention.

Polymers of maleic anhydride and methyl vinyl ether, in particular those with crosslinks, are preferred thickeners. A 1, 9-decadiene crosslinked maleic acid methyl vinyl ether copolymer is available under the name ^® Stabileze QM.

The agent according to the invention may additionally comprise at least one anionic acrylic acid and / or methacrylic acid polymer or copolymer. Preferred polymers of this type are:

Polymers, e.g. from at least 10% by weight of acrylic acid lower alkyl ester, from 25 to 70% by weight of methacrylic acid and optionally up to 40% by weight of a further comonomer,

Copolymers of 50 to 75 wt .-% of ethyl acrylate, 25 to 35 wt .-% acrylic acid and 0 to 25 wt .-% of other comonomers known. Suitable dispersions of this type are commercially available, for example under the trade name Latekoll D ^® (BASF).

Copolymers of 50 to 60% by weight of ethyl acrylate, 30 to 40% by weight of methacrylic acid and 5 to 15% by weight of acrylic acid, crosslinked with ethylene glycol dimethacrylate.

In another embodiment, 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 composed of acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable. Homopolymers of the general formula (HP-1),

(HP-1)

in which R ₁ is -H or -CH ₃ , R 2, R 3 and R ₄ are independently selected from C 1 -C ₄ -alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural one Number and X ^"is a physiologically acceptable organic or inorganic anion, as well as copolymers consisting essentially of the monomer units listed in formula (HP-1) and nonionic monomer units, are particularly preferred cationic polymeric gelling agents preferably, for which at least one of the following conditions applies:

R1 is a methyl group

R2, R3 and R4 stand for methyl groups

m has the value 2,

Suitable physiologically tolerated counterions X ^" are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions, preference being given to halide ions, in particular chloride.

A particularly suitable homopolymer is, if desired, crosslinked, poly (methacryloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. If desired, the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a non-aqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such polymer dispersions are (under the names Salcare ^® SC 95 50% polymer content, an additional component: Mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ^® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol with a mixture of caprylic and Capric acid (INCI name: Propylene Glycol Dicaprylate / Dicaprate) and tridecyl polyoxypropylene polyoxyethylene ether (INCI name: PPG-1-Trideceth-6) are commercially available.

Copolymers with monomer units of the formula (HP-1) contain as nonionic monomer units preferably acrylamide, methacrylamide, acrylic acid-C 1 -C 4 -alkyl esters and methacrylic acid-C 1 -C 4 -alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above for the homopolymers. A preferred copolymer according to the invention is the crosslinked acrylamide-methacroyl-oxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, commercially available as about 50% non-aqueous polymer dispersion under the name Salcare ^® SC 92nd

In a further preferred embodiment, naturally occurring thickeners are used. Preferred thickening agents of this embodiment are, for example, nonionic guar gum. According to the invention, both modified and unmodified guar gums can be used. Unmodified guar gums are marketed under the trade name Jaguar ^® C from Rhone Poulenc. Modified guar gums preferred according to the invention contain C 1 -C 6 -hydroxyalkyl groups. Preferably, the groups are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl. Such modified guar gums are known in the art and can be prepared, for example, by reaction of the guar gums with alkylene oxides. The degree of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed in relation to the number of guar gums of free hydroxy groups, is preferably between 0.4 and 1.2. Such modified guar gums are available under the trade names Jaguar ^® HP8, Jaguar ^® HP60, Jaguar ^® HP120, Jaguar DC 293 and Jaguar ^® ^® HP105 Rhone Poulenc.

Further suitable natural thickening agents are also already known from the prior art.

Also preferred according to this embodiment are biosaccharide gums of microbial origin, such as scleroglucan gums or xanthan gums, gums from plant exudates such as gum arabic, ghatti gum, karaya gum, gum tragacanth, carrageenan gum, agar agar, locust bean gum, pectins, Alginates, starch fractions and derivatives such as amylose, amylopectin and dextrins, cellulose derivatives such as methylcellulose, carboxyalkylcelluloses and hydroxyalkylcelluloses. Preferred are in particular the loose Hydroxyalkylcellu hydroxyethylcelluloses are sold under the names Cellosize ^® Amerchol and Natrosol ^® from Hercules. Suitable carboxyalkyl are especially the carboxymethylcelluloses as sold under the names Blanose ^® by Aqualon, Aquasorb ^® and ambergum ^® from Hercules and Cellgon ^® from Montello.

Starch and its derivatives are also preferred. Starch is a storage material of plants, which occurs mainly in tubers and roots, in grain seeds and in fruits and can be obtained from a variety of plants in high yield. The polysaccharide which is insoluble in cold water and forms a colloidal solution in boiling water may be, for example, potatoes, cassava, maranta, maize, cereals, rice, legumes such as peas and beans, bananas or certain types of palms (e.g. the sago palm). Natural, plant-derived starches and / or chemically or physically modified starches can be used according to the invention. Modification can be achieved, for example, by introducing different functional groups on one or more of the hydroxyl groups of the starch. These are usually esters, ethers or amides of the starch with optionally substituted C 1 -C ₄₀ radicals. Especially advantageous is a etherified with 2-hydroxypropyl corn starch as it is, for example, sold by National Starch under the trade name Amaze ^®.

But also nonionic, fully synthetic polymers, such as polyvinyl alcohol or polyvinylpyrrolidinone, can be used as thickeners according to the invention. Preferred nonionic, fully synthetic polymers are for example marketed by BASF under the trade name Luviskol ^®. Such nonionic polymers, in addition to their excellent thickening properties, also allow a significant improvement in the sensory feeling of the resulting preparations.

As inorganic thickeners, phyllosilicates (polymeric, crystalline sodium disilicates) have proven to be particularly suitable in the context of the present invention. In particular clays, in particular magnesium aluminum silicates, such as bentonite, especially smectites such as montmorillonite or hectorite, which may optionally be modified also suitable, and synthetic layered silicates such as that sold by Sud Chemie under the trademark Optigel ^® magnesium phyllosilicate, are preferred ,

To further increase the performance of the oxidizing agent preparation, at least one optionally hydrated SiO ₂ compound may additionally be added to the composition according to the invention. It may be preferred according to the invention, optionally hydrated Si0 ₂ compounds in amounts of 0.05 wt .-% to 15 wt .-%, particularly preferably in amounts of 0.15 wt .-% to 10 wt .-% and most preferably in amounts of 0.2 wt .-% to 5 wt .-%, each based on the anhydrous composition of the invention to use. The quantities given in each case the content of Si0 ₂ compounds (without their water content) in the funds again.

With regard to the optionally hydrated Si0 ₂ compounds, the present invention is in principle not limited. Preference is given to silicic acids, their oligomers and polymers and their salts. Preferred salts are the alkali salts, especially the potassium and sodium salts. The sodium salts are very particularly preferred.

The optionally hydrated Si0 ₂ compounds can be present in various forms. According to the invention, the Si0 ₂ compounds are preferably used in the form of silica gels (silica gel) or particularly preferably as water glass. These Si0 ₂ compounds may be partially present in aqueous solution.

Very particularly preferred according to the invention are water glasses which are formed from a silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m (K ₂ O) _p , where n is a positive rational number and m and p are each independently one positive rational number or 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1. Preference is given to metasilicates in which the ratio between n and the sum of m and p is 1: 2 or less.

In addition to the components described by the empirical formula, the water glasses in small amounts may contain other additives, such as phosphates or magnesium salts.

According to the invention particularly preferred water glasses are marketed inter alia by the company Henkel under the names Ferrosil® 1 ^® 19, soda waterglass 40/42, Portil A ^®, ^® Portil AW and Portil ^® W and by Akzo under the name Britesil ^® C20.

Preferably, the preparation (A) and / or optionally the oxidizing agent preparation (B) are formulated as flowable preparations.

Preferably, an emulsifier or a surfactant is further added to the flowable preparations (A) and / or (B), surface-active substances being referred to as surfactants or as emulsifiers, depending on the field of application, and of anionic, cationic, zwitterionic, amphoteric and nonionic surfactants and emulsifiers are selected. These substances will be described in detail below.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group of about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group,

linear and branched fatty acids with 8 to 30 carbon atoms (soaps),

Ethercarbonsäuren the formula RO (CH ₂ CH ₂ 0) _x CH ₂ COOH, in which R is a linear alkyl group having 8 to 30 carbon atoms and x = 0 or 1 to 16,

Acylsarcosides having 8 to 24 carbon atoms in the acyl group,

Acyltaurides having 8 to 24 carbon atoms in the acyl group,

Acyl isethionates having 8 to 24 carbon atoms in the acyl group,

Sulfobernsteinsäuremono- and -dialkylester having 8 to 24 carbon atoms in the alkyl group and

Sulfosuccinic acid mono-alkylpolyoxyethylester having 8 to 24 carbon atoms in the alkyl group and

1 to 6 oxyethyl groups,

linear alkanesulfonates having 8 to 24 C atoms,

linear α-olefinsulfonates having 8 to 24 C atoms,

Sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds, α-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms,

Alkyl sulfates and alkyl ether sulfates of the formula RO (CH ₂ CH ₂ O) _x SO ₃ H, in which R is a preferably linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates,

sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene glycol ethers,

Esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15

Represent molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms,

Alkyl and / or alkenyl ether phosphates of the formula

O

RO (C ₂ H ₄ O) -P-OR '

OH in which R is an aliphatic, optionally unsaturated hydrocarbon radical having 8 to 30 carbon atoms, R 'is hydrogen, a radical (CH ₂ CH ₂ O) _y R and x and y independently of one another are from 1 to 10, sulfated fatty acid alkylene glycol esters of the formula RC (0) 0 (alkO) _n SO ₃ H, in which R is a linear or branched, aliphatic, saturated and / or unsaturated alkyl radical having 6 to 22 C atoms, alk is CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ and n is a number from 0.5 to 5,

Monoglyceride sulfates and monoglyceride ether sulfates.

Preferred anionic surfactants are alkyl sulfates, alkyl ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

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. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Amphoteric surfactants are understood as meaning those surface-active compounds which, apart from a C ₈ -C ₂₄ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts , Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C ₂ -C ₈ - sarcosine.

Furthermore, it has proved to be advantageous if the dyeing and curing agents according to the invention contain further nonionic surfactants. Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example Addition products of 1 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, such as, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl alcohol, fatty acids having 8 to 30 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group,

with a methyl or C ₂ -C ₆ alkyl radical end-capped addition products of 1 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and with alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as those available under the trade names Dehydol ^® LS, LT Dehydol ^® types (Cognis),

Polyglycerol esters and alkoxylated polyglycerol esters, such as poly (3) glycerol diisostearate (commercial product: Lameform ^® TGI (Henkel)) and poly (2) glycerinpolyhydroxy stearate (commercial product: Dehymuls ^® PGPH (Henkel)).

Polyol fatty acid esters, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol types (Cognis),

higher alkoxylated, preferably propoxylated and in particular ethoxylated, mono-, di- and triglycerides, such as glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide,

Amine oxides,

hydroxy mixed,

Sorbitan fatty acid esters and addition products of ethylene oxide onto sorbitan fatty acid esters such as the polysorbates and sorbitan monolaurate + 20 moles of ethylene oxide (EO), sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters, addition products of ethylene oxide onto fatty acid alkanolamides and fatty amines,

Fatty acid N-alkyl glucamides,

Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15 carbon atoms in the alkyl chain and 1 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 9 EO and octylphenol + 8 EO; Alkylpolyglycosides corresponding to the general formula RO- (Z) _x , where R is alkyl, Z is sugar and x is the number of sugar units. The alkyl polyglycosides which can be used according to the invention can only contain one particular alkyl radical R. Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds. The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 2.0 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 8. The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

The anionic, nonionic, zwitterionic or amphoteric surfactants are used in amounts of from 0.1 to 45% by weight, preferably from 1 to 30% by weight and very particularly preferably from 1 to 15% by weight, based on the total amount of the ready-to-use agent ,

Also preferred according to the invention are cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines and are characterized in addition to a good conditioning effect especially by their good biodegradability. An inventively particularly suitable compound from this group of substances under the name Tegoamid ^® S 18 commercial stearamidopropyl dimethylamine is.

Likewise very readily biodegradable are quaternary ester compounds, so-called "ester quats". Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^®, ^® and Dehyquart® Armocare® ^®. The products Armocare ^® VGH- 70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats.

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. Levels of 0.1 to 5% by weight are particularly preferred. In a preferred embodiment, nonionic, zwitterionic and / or amphoteric surfactants and mixtures thereof may be preferred.

In a further preferred embodiment, the effect of the active ingredient according to the invention can be increased by emulsifiers. Such emulsifiers are, for example

Addition products of 4 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C ₂ -C ₂ 2-fatty acid mono- and diesters of addition products of 1 to 30 mol ethylene oxide onto polyols containing 3 to 6 carbon atoms, in particular glycerol,

Ethylene oxide and polyglycerol addition products to methyl glucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides,

C ₈ -C ₂ 2-alkylmono- and -oligoglycosides and their ethoxylated analogues, preference being given to degrees of oligomerization of from 1.1 to 5, in particular from 1.2 to 2.0, and glucose as the sugar component,

Mixtures of alkyl (oligo) glucosides and fatty alcohols, for example the commercially available product Montanov® 68,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil, partial esters of polyols having 3 to 6 carbon atoms with saturated fatty acids having 8 to 22 carbon atoms,

Sterols, sterols being understood as meaning a group of steroids which carry a hydroxyl group on C-atom 3 of the steroid skeleton and are isolated both from animal tissue (zoosterines) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol. Mushrooms and yeasts are also used to isolate sterols, the so-called mycosterols.

Phospholipids, especially glucose phospholipids, the z. As lecithins or phosphatidyl cholines from e.g. Egg yolk or plant seeds (e.g., soybeans),

Fatty acid esters of sugars and sugar alcohols, such as sorbitol

Polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hydroxystearate (commercial product Dehymuls® PGPH)

Linear and branched fatty acids with 8 to 30 carbon atoms and their Na, K, ammonium, Ca, Mg and Zn salts. The agents according to the invention preferably contain the emulsifiers in amounts of from 0.1 to 25% by weight, in particular from 0.5 to 15% by weight, based on the total amount of ready-to-use agent.

Nonionic emulsifiers or surfactants having an HLB value of 10-15 may be particularly preferred according to the invention. Among the emulsifier types mentioned, the emulsifiers which do not contain any ethylene oxide and / or propylene oxide in the molecule can be very particularly preferred.

Furthermore, the agents according to the invention may contain other active ingredients, auxiliaries and additives, such as, for example

nonionic polymers such as vinylpyrrolidinone vinyl acrylate copolymers, polyvinylpyrrolidinone, vinylpyrrolidinone vinyl acetate copolymers, polyethylene glycols and polysiloxanes;

Silicones, such as volatile or non-volatile, straight-chain, branched or cyclic, crosslinked or uncrosslinked polyalkylsiloxanes (such as dimethicones or cyclomethicones), polyaryl-siloxanes and / or polyalkylarylsiloxanes, in particular polysiloxanes with organofunctional groups, such as substituted or unsubstituted amines (amodimethicones), carboxyl- , Alkoxy and / or hydroxyl groups (dimethicone copolyols), linear polysiloxane (A) -polyoxyalkylene (B) block copolymers, grafted silicone polymers with non-silicone-containing organic backbone or with polysiloxane backbone, such as, for example, the INCI designation Bis- PEG / PPG-20/20 Dimethicone sold commercial product Abil B 8832 from Degussa, or mixtures thereof;

cationic polymers such as quaternized cellulose ethers, quaternary group polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidinone copolymers, vinylpyrrolidinone-imidazolinium methochloride copolymers, and quaternized polyvinylalcohol;

zwitterionic and amphoteric polymers, for example acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, diallyldimethylammonium chloride / acrylate copolymers, t-butylaminoethyl methacrylate N- (1, 1, 3,3-tetramethylbutyl) acrylamide / acrylate (/ methacrylate) copolymers,

anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidinone vinyl acrylate copolymers, vinyl acetate butyl maleate isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / Nt-butyl acrylamide terpolymers, other thickening agents such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. As methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,

Structurants such as glucose, maleic acid and lactic acid,

hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins and silicone oils,

Perfume oils, dimethylisosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,

fiber-structure-improving active ingredients, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,

quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate

Defoamers like silicones,

Dyes for staining the agent,

Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,

Amino acids and oligopeptides, in particular arginine and / or serine,

Animal and / or plant-based protein hydrolysates, such as elastin, collagen, keratin, silk and milk protein protein hydrolysates, or almond, rice, pea, potato and wheat protein hydrolyzates, as well as in the form of their fatty acid condensation products or optionally anionically or cationically modified derivatives,

vegetable oils, for example, macadamia nut oil, kukui nut oil, palm oil, amaranth seed oil, peach kernel oil, avocado oil, olive oil, coconut oil, rapeseed oil, sesame oil, jojoba oil, soybean oil, peanut oil, evening primrose oil and tea tree oil

Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines, substances for adjusting the pH, for example customary acids, in particular edible acids and bases,

Active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts, and bisabolol,

Polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols;

Ceramides, preferably the sphingolipids such as ceramides I, ceramides II, ceramides 1, ceramides 2, ceramides 3, ceramides 5 and ceramides 6, or pseudoceramides, in particular N- (C ₈ -C ₂ 2-acyl) - (C ₈ -C ₂ -acyl) -hydroxyproline, Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as the extracts of aloe vera, angelica, anise, apricot, benzoin, bergamot, birch, stinging nettle, calmus, cassis, costus, marshmallow, oak bark, elemi, tarragon, spruce needle, galbanum, geranium, ginseng, grapefruit, guaiac wood, green Tea, witch hazel, toadstool, hops, coltsfoot, ginger root, iris, jasmine, chamomile, cardamom, clover, burdock root, pine, kiwi, coconut, cilantro, caraway, peach, lavender, lemongrass, lily, lime, lime blossom, litchi, mace, Mallow, Almond, Mango, Melissa, Melon, Meristem, Myrrh, Neroli, Olibanum, Opoponax, Orange, Patchouli, Petitgrain, Pine, Quendel, Rooibos, Roses, Rosemary, Horse chestnut, Sandalwood, Sage, Horsetail, Yarrow, Celery, Fir, Thyme, juniper, grape leaves, hawthorn, wheat, meadowfoam, ylang-ylang, cedar and lemon.

Cholesterol,

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,

Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,

fatty acid,

Swelling and penetration agents such as glycerol, propylene glycol monoethyl ether, 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

Stabilizing agent for hydrogen peroxide and other oxidizing agents,

Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, C0 ₂ and air,

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. Schräder, bases and formulations of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989, referenced.

The additional active ingredients and auxiliaries are preferably used in the agents according to the invention in amounts of from 0.0001 to 10% by weight, in particular from 0.0005 to 5% by weight, based on the total weight of the application mixture. For the strong lightening of very dark hair, the sole use of hydrogen peroxide or its addition products to organic or inorganic compounds is often not sufficient. The compositions according to the invention may therefore additionally contain further bleaching and / or bleaching agents.

If a strong lightening is desired in addition to the coloring of the keratinic fiber, it is therefore preferred according to the invention if in addition a bleaching preparation (C) containing at least one bleach activator, the mixture of oxidizing agent preparation (B) and the preparation (A) containing at least one oxidation dye precursor according to formula (I) is admixed.

It may be irrelevant whether first a mixture of (A) and (B) is prepared, and then the Blondierzubereitung (C) is added, or whether a different order of mixing of the individual components is used. It is preferred to mix the individual preparations in the earliest possible chronological order and preferably to apply the ready-to-use agent promptly to the keratinic fibers.

A further embodiment of the present application is therefore an agent for bleaching and dyeing keratinic fibers, characterized in that it comprises mixing at least one oxidizing agent preparation (B) containing at least one oxidizing agent selected from hydrogen peroxide, its addition compounds to solid carriers, at least one bleaching preparation ( C) containing at least one bleaching power enhancer, and at least one preparation (A) comprising, in a cosmetic carrier, at least one oxidation dye precursor according to formula (I), prepared before use.

In a further embodiment, it is preferred if the colorant according to the invention additionally contains as bleaching preparation (C) at least one inorganic peroxo compound. Preferably, the inorganic peroxy compound is selected from ammonium persulfate, alkali metal persulfates, ammonium peroxomonosulfate, alkali metal hydrogen peroxomonosulfates, alkali metal peroxodiphosphates and alkaline earth metal peroxides. Particularly preferred inorganic peroxy compounds as bleaching force enhancers are ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxodisulfate, potassium hydrogen peroxomonosulfate, potassium peroxodiphosphate, magnesium peroxide and barium peroxide, in particular ammonium peroxodisulfate, potassium peroxodisulfate and sodium peroxodisulfate.

The inorganic peroxy compounds are preferably contained in an amount of 0.1 to 25% by weight, in particular in an amount of 0.5 to 15% by weight, based on the total weight of the ready-to-use agent. The use of persulfate salts or peroxodisulfate salts is generally carried out in the form of an optionally dedusted powder or a molding pressed into the mold.

However, it may be advantageous according to the invention if the agents are free of inorganic peroxo compounds. However, the compositions according to the invention may therefore instead of and / or in addition to the solid peroxo compounds contain a further bleaching power enhancer.

Additional bleach boosters which can be used in the context of this invention are compounds which give aliphatic peroxycarboxylic acids, for example polyacylated alkylenediamines - in particular tetraacetylethylenediamine (TAED) - and / or substituted perbenzoic acid, carbonic acid derivatives, for example ammonium hydrogencarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium hydrogencarbonate, potassium carbonate and calcium carbonate , Alkyl carbonates and carbamates, as well as silyl carbonates and carbamates.

The bleach boosters used in addition to or instead of peroxo compounds are preferred in amounts of from 0.05 to 10% by weight, in particular in amounts of from 0.2 to 5% by weight, in each case based on the total weight of the ready-to-use cosmetic agents By means of, included.

Although in principle there are no restrictions with regard to the formulation of the blonding preparation (C), it has proved to be preferred according to the invention if the preparation (C) is formulated anhydrous.

Anhydrous in the sense of the present invention means a water content based on the preparation (C) of less than 5 wt .-%, in particular of less than 2 wt .-%. Blondierzubereitungen containing less than 0, 1 wt .-% water, according to the invention may be very particularly preferred. The preparation (C) is preferably formulated as a powder or as an anhydrous paste.

In a further preferred embodiment, the agent in the preparation (C) as bleaching force enhancer may contain at least one cationic pyridinium derivative. In particular, agents according to the invention are preferred which contain as cationic pyridinium derivative at least one compound of 2-acetyl-1-methylpyridinium p-toluenesulfonate and / or 4-acetyl-1-methylpyridinium p-toluenesulfonate and / or N-methyl-3, 4-dihydroisoquinolinium p-toluenesulfonate.

An inventively preferred embodiment of the present invention is that the ready-to-use agent has a pH between 7 and 1 1, in particular between 8 and 10.5, particularly preferably between 8.5 and 10.0. 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.

For the purposes of the present invention, the pH values are pH values which were measured at a temperature of 22 ° C.

Organic alkalizing agents which can be used according to the invention are preferably selected from alkanolamines of primary, secondary or tertiary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group 2-aminoethane-1-ol (monoethanolamine), 2-amino-2-methylpropan-1-ol, 2-amino-2-methyl-propane-1, 3-diol and triethanolamine.

However, it has been found in the context of the investigations of the present invention that furthermore preferred agents according to the invention are characterized in that they additionally contain an inorganic alkalizing agent. The inorganic alkalizing agent of the present invention is preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, sodium carbonate and potassium carbonate. Very particular preference is given to sodium hydroxide and / or potassium hydroxide.

The basic amino acids which can be used as alkalizing agents according to the invention are preferably selected from the group which is formed from L-arginine, D-arginine, D / L-arginine, L-lysine, D-lysine, D / L-lysine, particularly preferably L-arginine. Arginine, D-arginine, D / L-arginine used as an alkalizing agent according to the invention.

Finally, another preferred alkalizing agent is ammonia.

The alkalizing agents are preferably contained in an amount of from 0.05 to 10% by weight, in particular from 0.5 to 5% by weight, based in each case on the total weight of the ready-to-use agent.

As already mentioned, the compositions according to the invention can also be prepared directly before use from two or more separately packaged preparations. This offers itself special to separate incompatible ingredients to avoid premature reaction. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or to be feared. The ready-to-use agent in such systems is manufactured by the consumer just prior to application by mixing the components. A dyeing and / or whitening agent in which the oxidation dye precursors are initially present separately from the oxidizing agent preparation, preferably containing hydrogen peroxide, is preferred.

A preferred dosage form of the agent according to the invention is a packaging unit (kit-of-parts), which is made up of separately packaged containers

in a container A, at least one preparation (A) comprising, in a cosmetic carrier, at least one oxidation dye precursor according to the formula (I), and

in a container B, at least one oxidizing agent preparation (B) containing at least one oxidizing agent in a cosmetic carrier.

If a particularly strong lightening effect is desired, a preferred further dosage form of the agent according to the invention is a packaging unit (kit-of-parts), which is made up of containers which are made up separately

in a container A at least one preparation (A) comprising in a cosmetic carrier at least one compound a) and at least one compound b),

in a container B at least one oxidizing agent preparation (B) containing at least one oxidizing agent, and

in a container C, at least one bleaching preparation (C) containing at least one bleaching power booster.

The multi-component packaging unit (kit-of-parts) preferably additionally contains an instruction manual. In addition, it may be preferred if an application aid, such as a comb or a brush, and / or personal protective equipment, such as disposable gloves, are also included in the kit.

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 actual hair dye is expediently prepared immediately before use by mixing the preparations (A) with (B) and optionally (C). The application temperatures can range between 15 and 40 ° C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used. During the contact time of the agent on the fiber, it may be advantageous to assist the dyeing process by supplying heat. The heat supply can be done by an external heat source, such as warm air of a hot air blower, as well as, especially in a hair dye on living subjects, by the body temperature of the subject. In the latter case, usually the part to be dyed is covered with a hood. In particular, the temperature during the contact time between 10 ° C and 45 ° C, in particular between 20 ° C and 40 ° C. The colorants according to the invention give intensive dyeings even at physiologically compatible temperatures of below 45.degree. They are therefore particularly suitable for dyeing human hair.

Another object of the present invention is the use of an agent according to the invention in human hair colorants for improving the gray coverage, the leveling, the color intensity, the durability and / or the colouration of the dyeing results.

With regard to further preferred embodiments of the use according to the invention, what has been said about the agents according to the invention applies mutatis mutandis.

Examples

1) Synthesis examples

a) 6-methoxy-2,4,5-pyrimidinetriamine, dihydrochloride

(i) Synthesis of 6-methoxy-2,4-diaminopyrimidine

To a solution of 9.2 g (0.40 mol) of sodium in 320 ml of methanol was added 28.9 g (0.20 mol) of 2,4-diamino-6-chloropyrimidine and heated with stirring for 44 h at reflux. After completion of the reaction, the precipitated NaCl was separated and the solution was concentrated to dryness. The residue was boiled in 300 ml of ethanol and filtered hot. Overnight, the product precipitated from the filtrate. Recrystallization of the mother liquor also gave product, after drying gave 6-methoxy-2,4-diaminopyrimidine (58.8 g, 84%) as a white solid. Mp: 166-169 ° C

H NMR (300 MHz, d ₆ -DMSO): δ = 3.18 (s, 3H, 6-OMe), 5.06 (s, 1H, 5-H), 5.94 (s, 2 H, NH ₂ ), 6.05 (s, 2H, NH ₂ ).

C NMR (125 MHz, d ₆ -DMSO): δ = 52.8 (6-OMe), 76.1 (5-C), 163.3 (2-C), 166.3 (4-C ), 170.8 (6-

(ü) Synthesis of 5-nitroso-2,4-diamino-6-methoxy-pyrimidine

To a solution of 7.0 g (0.05 mol) of 6-methoxy-2,4-diaminopyrimidine in 100 ml of acetic acid (10% in water) at 50-60 ° C with stirring, a solution of 4.55 g (0.07 mol) of sodium nitrite 20 ml of water was added dropwise over 30 min. The mixture was then stirred for a further 30 min at this temperature and overnight at room temperature. The precipitate was filtered off with suction, washed with water and dried. 5-Nitroso-2,4-diamino-6-methoxy-pyrimidine (7.80 g, 92%) was obtained as a purple solid.

Mp .: 250 ° C (decomp.)

H NMR (300 MHz, d ₆ -DMSO): δ = 4.04 (s, 3H, 6-OMe), 7.79 (s, 1H, NH ₂ ), 7.85 (s, 1H , NH ₂ ), 8.01 (s, 1 H, NH ₂ ), 10.10 (s, 1 H, NH ₂ ).

3C-NMR (125 MHz, d ₆ -DMSO): δ = 54.5 (6-OMe), 140.0 (5-C), 151, 2 (2-C), 163.8 (4-C) , 171, 4 (6-C).

(Iii)

To a solution of 7.60 g (0.045 mol) of 5-nitroso-2,4-diamino-6-methoxy-pyrimidine from stage 1.2. in 400 ml of ethanol was added 1 .5 g (0.04 mol%) of palladium on carbon (5%) and shaken at room temperature for 16 h under 1 bar hydrogen atmosphere. Subsequently, the reaction mixture was poured into 80 ml of dilute hydrochloric acid (0.23 mol), the catalyst was filtered off and the filtrate was concentrated almost to dryness. The precipitated crystals were filtered off and washed with ferf-butyl methyl ether. 6-Methoxy-2,4,5-pyrimidinetriamine dihydrochloride (8.10 g, 79%) was obtained as pale yellow crystals.

Mp .: about 170 ° C (decomp.)

H NMR (300 MHz, d ₆ -DMSO): δ = 3.91 (s, 3H, 6-OMe), 7.30 (s, 2H, NH ₂ ), 7.46 (s, 2H , NH ₂ ), 7.57 (s, 2H, NH ₂ ).

3C-NMR (125 MHz, d ₆ -DMSO): δ = 55.3 (6-OMe), 84.9 (5-C), 151, 3 (2-C), 153.9 (4-C) , 164.9 (6- C). 6- (2-methylpropoxy) -2, 4, 5-pyrimidinetriamine, dihydrochloride (i) Synthesis of 6- (2-methylpropoxy) -2,4-diaminopyrimidine

To a solution of 6.9 g (0.30 mol) of sodium in 185 ml of isobutyl alcohol was added 43.4 g (0.30 mol) of 2,4-diamino-6-chloropyrimidine and heated with stirring for 10 h at reflux. Subsequently, the reaction was stirred for a further 36 hours at 80.degree. After completion of the reaction, the precipitated NaCl was separated and the solution was concentrated to dryness. The residue was taken up several times in ethanol and concentrated again to remove residual isobutyl alcohol. After drying, 6- (2-methylpropoxy) -2,4-diaminopyrimidine (41.3 g, 75%) was obtained as a yellow oil.

H-NMR (300 MHz, d ₆ -DMSO): δ = 1.49 (d, 6H, 2'-Me), 2.50 (sept, 1H, 2'-H), 4.45 (i.e. , 2 H, V-H ₂ ), 5.71 (s, 1 H, 5-H), 6, 18 (s, 2 H, NH ₂ ), 6.76 (s, 2 H, NH ₂ ).

3C-NMR (125 MHz, d ₆ -DMSO): δ = 19.2 (2'-Me), 27.8 (2'-C), 71, 3 (1'-C), 76.4 (5 -C), 163.1 (2-C), 166.1 (4-C), 170.7 (6-C).

(ii) Synthesis of 5-nitroso-2,4-diamino-6- (2-methylpropoxy) -pyrimidine

To a solution of 18.2 g (0.100 mol) of 6- (2-methylpropoxy) -2,4-diaminopyrimidine in 100 ml of acetic acid (10% in water) at 6 ° C with stirring, a solution of 9.1 1 g (0.132 mol Sodium nitrite in 40 ml of water was added dropwise over 1 h, whereupon the temperature was allowed to rise to 32 ° C. The mixture was then stirred for a further 2 h at room temperature. The resulting precipitate was filtered off, washed with water and dried. 5-Nitroso-2,4-diamino-6- (2-methylpropoxy) -pyrimidine (18.3 g, 81%) was obtained as a purple solid. Mp .: 201-212 ° C (decomp.)

H-NMR (300 MHz, d ₆ -DMSO): δ = 0.90 (s, 6H, 2 x 2'-Me), 2.05 (m, 1 H, 2'-H), 4, 19 ( s, 2H, 1'-H ₂ ), 7.71 (s, 1H, NH ₂ ), 7.78 (s, 1H, NH ₂ ), 7.95 (s, 1H, NH ₂ ), 10.05 (s, 1H, NH ₂ ).

3C-NMR (125 MHz, d ₆ -DMSO): δ = 19.0 (2'-Me), 27.5 (2'-C), 72.7 (1'-C), 139.6 (5 -C), 150.9 (2-C), 163.6 (4-C), 170.9 (6-C). (iii) Synthesis of 6- (2-methylpropoxy) -2,4,5-pyrimidinetriamine, dihydrochloride

To a solution of 16.9 g (0.08 mol) of 5-nitroso-2,4-diamino-6- (2-methylpropoxy) -pyrimidine from step 2.2. in 400 ml of ethanol was added 1.5 g (0.04 mol%) of palladium on carbon (5%) and shaken at room temperature for 16 h under 1 hydrogen atmosphere. Subsequently, the reaction mixture was diluted in 105 ml. Hydrochloric acid (0.30 mol) poured, the catalyst was filtered off and the filtrate was concentrated almost to dryness. The precipitated crystals were filtered off and washed with ferf-butyl methyl ether. There was obtained 6- (2-methylpropoxy) -2,4,5-pyrimidinetriamine dihydrochloride (14.6 g, 68%) as pale yellow crystals.

Mp .: 164 ° C (decomp.)

H-NMR (300 MHz, D ₂ O): δ = 0.96 (s, 3 H, 2'-Me), 0.97 (s, 3 H, 2'-Me), 2.1 (sept , 1H, 2'-H), 4.28 (d, 2H, 1'-H ₂ ).

3C-NMR (125 MHz, D ₂ O): δ = 21, 0 (2'-Me), 30.2 (2'-C), 78.2 (1'-C), 87.0 (5) C), 153.6 (2-C), 157.0 (4-C), 168.6 (6-C).

6- (3-methylbutoxy) pyrimidine-2, 4, 5-triamine, dihydrochloride

(i) Synthesis of 6- (3-methylbutoxy) pyrimidine-2,4-diamine

43.4 g (0.30 mol) of 2,4-diamino-6-chloropyrimidine were added to a solution of 6.9 g (0.30 mol) of sodium in 200 ml of isopentyl alcohol and heated under reflux for 1 h with stirring. Subsequently, the reaction was stirred for a further 36 hours at 80.degree. After completion of the reaction, the precipitated NaCl was separated and the solution was concentrated to dryness. The residue was taken up several times in ethanol and reconcentrated to remove residual isopentyl alcohol. Drying gave 6- (3-methylbutoxy) -2,4-diaminopyrimidine (51.8 g, 88%) as a yellow oil.

H-NMR (300 MHz, d ₆ -DMSO): δ = 0.92 (d, 6H, 2 x 3'-Me), 1, 53 (dt, 2H, 2'-H ₂ ), 1, 71 (sept, 1H, 3'-H), 4.12 (t, 2H, 1'-H ₂ ), 5.05 (s, 1H, 5-H), 5.90 (s, 2 H, NH ₂ ), 6.05 (s, 2H, NH ₂ ). ³ C-NMR (125 MHz, d ₆ -DMSO): δ = 23.0 (2'-Me), 25.2 (3'-C), 38.1 (2'-C), 63.6 ( 1'-C), 76.7 (5-C), 3.6 (2-C), 166.5 (4-C), 170.8 (6-C).

(ü) Synthesis of 5-nitroso-2,4-diamino-6- (3-methylbutoxy) -pyrimidine

To a solution of 51.0 g (0.26 mol) of 6- (3-methylbutoxy) -2,4-diaminopyrimidine in 520 ml of acetic acid (10% in water) at 55-60 ° C with stirring, a solution of 23.5 g (0.34 mol) sodium nitrite in 105 ml of water was added dropwise over 25 min. The mixture was then stirred for 1 h at 50 - 55 ° C and overnight at room temperature. The resulting precipitate was filtered off, washed with water and dried. The crude product was recrystallized from a 1: 1 mixture of water / ethanol to give 5-nitroso-2,4-diamino-6- (2-methylbutoxy) -pyrimidine (19.0 g, 32%) as a purple solid.

Mp: 221-223 ° C

H-NMR (300 MHz, d ₆ -DMSO): δ = 0.92 (s, 6H, 2 x 3'-Me), 1.67 (m, 1H, 2'-H ₂ ), 1.76 (m, 1H, 3'-H), 4.51 (s, 2H, 1'-H ₂ ), 7.75 (s, 1H, NH ₂ ), 7.79 (s, 1H, NH ₂ ), 7.97 (s, 1H, NH ₂ ), 10, 1 1 (s, 1H, NH ₂ ).

3C NMR (125 MHz, d ₆ -DMSO): δ = 22.7 (3'-Me), 25.0 (2'-C), 37.3 (3'-C), 65.6 (1 '-C), 139.9 (5- C), 151, 2 (2-C), 163.9 (4-C), 171, 1 (6-C).

(iii) Synthesis of 6- (2-methylbutoxy) -2,4,5-pyrimidinetriamine, dihydrochloride

To a solution of 19.0 g (0.084 mol) of 5-nitroso-2,4-diamino-6- (2-methylbutoxy) -pyrimidine from stage 3.2. in 400 ml of ethanol was added 4.0 g (0.04 mol%) of palladium on carbon (5%) and shaken at room temperature for 18 h under 1 hydrogen atmosphere. The reaction mixture was then poured into 150 ml of dilute hydrochloric acid (0.30 mol), the catalyst was filtered off and the filtrate was concentrated almost to dryness. The precipitated crystals were filtered off and washed with ferf-butyl methyl ether. There was obtained 6- (2-methylbutoxy) -2,4,5-pyrimidinetriamine dihydrochloride (19.5 g, 81%) as pale yellow crystals.

Mp .: 181 ° C (decomp.) H-NMR (300 MHz, d ₆ -DMSO): δ = 0.87 (s, 3H, 6-OMe), 1.58 (m, 2H, 2'-H ₂ ), 1.76 (m , 1H, 3'-H), 4.36 (t, 2H, 1'-H ₂ ).

3C-NMR (125 MHz, d ₆ -DMSO): δ = 22.9 (3'-Me), 24.6 (3'-C), 41, 0 (2'-C), 59.2 (1 '-C), 85.2 (5-C), 151, 5 (2-C), 154.1 (4-C), 164.9 (6-C).

2) Ausfärbunqen

Preparation of the coloring cream

A coloring cream of the following composition was prepared:

Hydrenor D 8.5% by weight

Lorol® ^® tech. ² 2.0% by weight

Texapon ^® NSO ³ 20.0 wt .-%

Dehyton ^® K ⁴ 12.5 wt .-%

Eumulgin B2 ^® ⁵ 0.75 wt .-%

Sodium sulfite 1, 0% by weight

Ammonium sulfate 1, 0 wt .-%

Developer component 3 mmol

Coupler component 3 mmol

Water ad 100

Ci6-i8 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

² Ci2-i8 fatty alcohol (INCI name: Coconut alcohol) (Cognis)

³ lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)

⁴ N, N-dimethyl-N- (C ₈ -8-cocoamidopropyl) ammonium acetobetaine (about 30% active;

INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

⁵ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)

Hydrenol D and Lorol techn. were melted together with Texapon NSO, Dehyton K and Eumulgin B2 at 80 ° C. Then, the melt was emulsified with the sodium sulfite dissolved in a part of the water and ammonium sulfate. The developer according to the invention was dissolved in a further portion of the indicated amount of water with heating and added with stirring. The coupler was also dissolved in a portion of the indicated amount of water and added with stirring. Then the formulation was made up to 100% with water and stirred cold. The dyeing cream thus obtained was mixed in a ratio of 1: 1 with the following developer dispersion having a hydrogen peroxide content of 6%.

Dipicolinic acid 0.1% by weight

Sodium pyrophosphate 0.03% by weight

Turpinal SL ^® ⁶ 1, 50 wt .-%

Texapon ^® N28 ⁷ 2.00 wt .-%

Acrysol ^® 22 ⁸ 0.60 wt .-%

Hydrogen peroxide, 50% 6.00% by weight

Sodium hydroxide, 45% 0.80% by weight

Water ad 100% by weight

1-Hydroxyethane-1, 1-diphosphonic acid (about 58 - 61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

⁷ lauryl ether sulfate sodium salt (at least 26.5% active substance content; INCI name:

Sodium Laureth Sulfate) (Cognis)

⁸ acrylic polymer (about 29.5 - 30.5% solids in water, INCI name:

Acrylates / Steareth-20 Methacrylate Copolyme)

For the dyeing process, 4 times the amount of ready-to-use mixture was applied to one strand of 80% gray hair (Kerling). After a contact time of 30 minutes at 32 ° C, the locks were rinsed and washed out with a conventional shampoo. The streaking of the streaks was visually assessed under the daylight lamp after drying. The staining results are summarized in the table below.

a) colorations with 6-methoxy-2,4,5-pyrimidinetriamine, dihydrochloride

Example coupler component Obtained shade / color intensity

1 resorcinol raspberry red / +++

2 3-Amino-2-methylamino-6-methoxypyridine blue-gray / +++

3 5-amino-2-methylphenol gray magenta / ++

4 3-Amino-2-hydroxypyridine taned / +

5 1, 3-bis (2,4-diaminophenoxy) propane dark purple / +++

6 2,7-Dihydroxynaphthalene graure red / ++

7 2-Methylresorcin blood red / +++

+++ high intensity ++ medium intensity + low intensity b) dyeing with 6- (2-methylpropoxy) -2,4,5-pyrimidinetriamine, dihydrochloride Example coupler component Obtained shade / color intensity

1 resorcinol reddish brown / +++

2 3-Amino-2-methylamino-6-methoxypyridine nickel green / +++

3 5-amino-2-methylphenol graubin / ++

4 3-amino-2-hydroxypyridine red / +

5 1, 3-bis (2,4-diaminophenoxy) propane dark blue / +++

6 2,7-dihydroxynaphthalene mattrot / +

7 2-methylresorcinol brown-red / +++

+++ high intensity ++ medium intensity + low intensity c) dyeing with 6- (2-methylpropoxy) -2,4,5-pyrimidinetriamine, dihydrochloride Example coupler component Obtained shade / color intensity

1 resorcinol reddish brown / +++

2 3-Amino-2-methylamino-6-methoxypyridine fir green / +++

3 5-amino-2-methylphenol gray magenta / ++

4 3-amino-2-hydroxypyridine light brown / +

5 1, 3-bis (2,4-diaminophenoxy) propane thunderstorm blue / +++

6 2,7-dihydroxynaphthalene mattrot / +

7 2-Methylresorcin blood red / +++

+++ high intensity ++ medium intensity + low intensity The colorations give a variety of different shades of red, which have excellent fastness properties.

In particular, the reds obtained have been found to have excellent washfastness.

In the colorations with 2,7-dihydroxynaphthalene, a particularly good leveling could be observed.

Claims

claims

1. means for dyeing keratinic fibers, in particular human hair, characterized in that it is in a cosmetic carrier

in the

R is a C 1 -C 4 -alkyl group,

R ² represents a hydrogen atom, a Ci-Cs alkyl group, a C ₂ -C ₆ alkenyl group, a Ci-C6-hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a Ci-C ₆ - alkoxy group, a Ci-C6 -Alkylamino group, a di-C 1 -C 6 -alkylamino group, a C 1 -C 6 -polyalkoxy group, a C 1 -C 6 -alkylamido (C 1 -C 6) -alkyl group, where the amide function may be substituted by one or two groups X, or an aryl group .

Y is an NH ₂ or an OH group,

b) contains at least one coupler component which is selected from the group formed from 3-amino-2-methylamino-6-methoxypyridine, 3-amino-6-methylphenol, 3-amino-2-hydroxypyridine, 1, 3-bis - (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 2,5-dimethylresorcinol, 4-chlororesorcinol, 3-aminophenol, 2-amino-3-hydroxypyridine, 2-chloro-6-methyl- 3-aminophenol, 2,6-dihydroxy-3,4-dimethylpyridine, 2- ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3- [ (2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 1-methoxy-2-amino-4-beta-hydroxy-ethylaminobenzene (Lehmann's Blue), 2,4-diaminophenoxyethanol, 5-amino 4-chloro-o-cresol, 2,4-dichloro-m-aminophenol, 2,6-dihydroxy-3,4-dimethylpyridine and / or a physiologically acceptable salt of these compounds.

2. Composition according to claim 1, characterized in that it contains at least one compound of formula (I) in which the radical R is a methoxy, ethoxy, propoxy, 2-methylpropoxy, 3-methylbutoxy or a second Methylbutoxygruppe, and the radical R ^{2 is} a hydrogen atom, a Ci-Cs-alkyl group, an aryl group, a Ci-C6-hydroxyalkyl group or a Ci-C6-alkylamino group.

3. Composition according to one of claims 1 or 2, characterized in that the radical R is a methoxy, a 2-methylpropoxy or a 3-methylbutoxy, and the radical R ^{2 is} a hydrogen atom, a Ci-Cs-alkyl group or an aryl group is.

4. Composition according to one of claims 1 to 3, characterized in that Y is an NH ₂ - group.

5. Composition according to one of claims 1 to 4, characterized in that the compound according to formula (I) 6-methoxy-2,4,5-pyrimidinetriamine, 6- (2-methylpropoxy) -2,4,5-pyrimidinetriamine, 6- (3-methylbutoxy) -2,4,5-pyrimidinetriamine, 6-methoxy-4-N-methylpyrimidine-2,4-diamine and / or a physiologically acceptable salt of these compounds.

6. Composition according to one of claims 1 to 5, characterized in that the coupler component is selected from 3-amino-2-methylamino-6-methoxypyridine, 3-amino-2-hydroxypyridine, 1, 3-bis (2,4 -diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 1-methoxy-2-amino-4-.beta.-hydroxy-ethylaminobenzene (Lehmanns Blau) and / or a physiologically acceptable salt of these compounds.

7. Composition according to one of claims 1 to 6, characterized in that it is 6-methoxy-2,4,5-pyrimidinetriamine and one or more compounds selected from 3-amino-2-methylamino-6-methoxypyridine, 3-amino 2-hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 1-methoxy-2-amino-4-.beta.-hydroxyethylaminobenzene (Lehmanns Blau) and / or a physiologically acceptable salt of these compounds.

8. Composition according to claim 7, characterized in that it comprises 6-methoxy-2,4,5-pyrimidinetriamine and one or more compounds selected from 1, 3-bis (2,4-diaminophenoxy) propane, 2,7- Dihydroxynaphthalene, 2-methylresorcinol and / or a physiologically acceptable salt of these compounds.

9. Composition according to one of claims 1 to 6, characterized in that it is 6- (2-methylpropoxy) -2,4,5-pyrimidinetriamine and one or more compounds selected from 3-amino-2-methylamino-6-methoxypyridine , 3-amino-2-hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 1-methoxy-2-amino-4-.beta.-hydroxyethylaminobenzene ( Lehmann's Blau) and / or a physiologically acceptable salt of these compounds.

10. Composition according to one of claims 1 to 6, characterized in that it is 6- (3-methylbutoxy) -2,4,5-pyrimidinetriamine and one or more compounds selected from 3-amino-2-methylamino-6-methoxypyridine , 3-amino-2-hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 1-methoxy-2-amino-4-.beta.-hydroxyethylaminobenzene ( Lehmann's Blau) and / or a physiologically acceptable salt of these compounds.

1. A composition according to any one of claims 1 to 6, characterized in that it is 6-methoxy-4-N-methylpyrimidine-2,4-diamine and one or more compounds selected from 3-amino-2-methylamino-6 methoxypyridine, 3-amino-2-hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 1-methoxy-2-amino-4-.beta.-hydroxyethylaminobenzene (Lehman's blue) and / or a physiologically acceptable salt of these compounds.

12. Composition according to one of claims 1 to 1 1, characterized in that it contains the compounds) of the formula (I) in an amount by weight of 0.001 to 5.0 wt .-%, preferably from 0.025 to 2.5 wt .-% , particularly preferably from 0.05 to 2.0 wt .-% and particularly preferably from 0.1 to 1, 5 wt .-%, each based on the total weight of the ready-to-use agent contains.

13. Composition according to one of claims 1 to 12, characterized in that it contains the at least one coupler component b) and / or its physiologically acceptable salt in a weight fraction of 0.001 to 5.0 wt .-%, preferably from 0.025 to 2.5 Wt .-%, particularly preferably from 0.05 to 2.0 wt .-% and particularly preferably from 0, 1 to 1, 5 wt .-%, each based on the total weight of the ready-to-use agent contains.

14. An agent for dyeing and optionally simultaneous whitening of keratinic fibers according to any one of claims 1 to 13, characterized in that it is 0.5 to 15 wt .-%, preferably 1 to 12.5 wt .-%, particularly preferably 1, 5 to 10 wt .-% and in particular 2 to 6 wt .-% hydrogen peroxide, each based on the total weight of the ready-to-use agent contains.

15. Use of a composition according to any one of claims 1 to 14 in colorants for human hair to improve the gray coverage, the leveling, the color intensity, and / or the durability of the dyeings.