EP1443888A2

EP1443888A2 - Oxidation colouring agent with bis (5-amino-2-hydroxyphenyl)-methane

Info

Publication number: EP1443888A2
Application number: EP02779546A
Authority: EP
Inventors: David Rose; Horst Höffkes; Bernd Meinike; Astrid Kleen
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2001-11-17
Filing date: 2002-11-11
Publication date: 2004-08-11
Also published as: AU2002342899A1; WO2003041671A2; WO2003041671A3

Abstract

The invention relates to means for the colouring of keratin fibres, in particular of human hair, comprising a colouring pre-cursor in a medium suitable for colouring a combination of a) bis (5-amino-2-hydroxyphenyl)-methane and/or 4-amino-2-{(4-[5'-amino-2'-hydroxy-phenyl)-methyl]piperazinyl)methyl}phenol tetrahydrochloride and b) at least one further colouring pre-cursor, selected from p-toluylendiamine, 2-(?-hydroxyethyl)-p-phenylenediamine, 4-amino-3-methylphenol, 4-amino-2,6-dichlorophenol, 4-amino-2,6-dibromophenol, 4-amino-3-fluorophenol, 4-amino-2-aminomethylphenol, 4-amino-2-((diethylamino)methyl)phenol, 2-amino-4-methylphenol, 4-amino-2-methylphenol, 2-amino-5-methylphenol, 2-amino-4-chlorophenol, 4-amino-2-chlorophenol, 3,4-methylendioxyaniline, 2-methyl-1-naphthol, 2,6-dimethyl-3-aminophenol, 2-amino-3-hydroxy-5-chloropyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-bis-(2'-hydroxyethylamino)toluol, 3-amino-2,4-dichlorophenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-(2'-hydroxyethyl)amino-2-methylphenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2-methylresorcinol, 4-chlororesorcinol, 2,4-diaminophenoxyethanol, 1,3-bis-(2',4'-diaminophenoxy)propane, resorcinol, 3,5-diamino-2,6-dimethoxypyridine and 1,7- dihydroxynaphthalene, 2,7- dihydroxynaphthalene and 1,5-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole and the physiologically-acceptable salts thereof. Said means permit particularly intense colouration with excellent fastness properties and extraordinarily good toxicological properties.

Description

"Oxidation colorant with bis- (5-amino-2-hydroxyphenylQQ-methane"

The present invention relates to agents for dyeing keratin fibers, the bis (5-amino-2-hydroxyphenyl) methane and / or 4-amino-2- {(4- [(5 '- amino-2' -hydroxyphenyl) - methyl] piperazinyl) methyl} phenol-etrahydrochloride in combination with at least one further, special dye precursor.

Today human hair is treated in a variety of ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with colorants, tinting agents, waving agents and styling preparations. Means for changing or shading the color of the head hair play an outstanding role.

Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These colorations are generally sensitive to shampooing, so that a frequently undesirable shift in nuances or even a visible "discoloration" can occur.

So-called oxidation dyes are used for permanent, intensive dyeings with appropriate fastness properties. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components. The oxidation colorants are characterized by excellent, long-lasting coloring results.

Good oxidation dye precursors should primarily fulfill the following requirements: They must have the desired color shades in the oxidative coupling train sufficient intensity and authenticity. They must also have a good ability to draw onto the fiber, whereby there must be no noticeable differences between stressed and freshly regrown hair, especially with human hair (leveling ability). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g. B. perm fluids. After all, if they are used as a hair dye, they should not stain the scalp too much, and above all they should be harmless from a toxicological and dermatological point of view. Furthermore, the coloration obtained should be easily removed from the hair again by bleaching, if it does not correspond to the individual wishes of the individual and should be reversed.

With a developer component or a special coupler / developer combination alone, it is usually not possible to obtain a color shade that looks natural on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used. There is therefore a constant need for new, improved dye components, in particular for a wide range of shades in the brown area.

It has now surprisingly been found that particularly intensive dyeings with excellent fastness properties and extraordinarily good toxicological properties can be obtained if colorants are used which contain bis- (5-amino-2-hydroxyphenyl) methane in combination with at least one further special dye precursor ,

A first subject of the present invention is therefore an agent for dyeing keratin fibers, in particular human hair, containing, in a medium suitable for dyeing, a combination of a) bis (5-amino-2-hydroxyphenyl) methane and / or as dye precursors 4-amino-2 - {(4- [5'-amino-2'-hydroxyphenyl) methyl] piperazinyl) methyl} phenol tetrahydrochloride and b) at least one further dye precursor selected from p-toluenediamine, 2- ( β-hydroxyethyl) -p-phenylenediamine, 4-amino-3-methylphenol, 4-amino-2,6-dichlorophenol, 4-amino-2,6-dibromophenol, 4-amino-3-fluorophenol, 4-amino-2-aminomethylphenol, 4-amino-2 - ((diethylamino) methyl) phenol, 2-amino-4-methylphenol, 4-amino-2-methylphenol, 2-amino-5-methylphenol, 2-amino- 4-chlorophenol, 4-amino-2-chlorophenol, 3,4-methylenedioxyaniline, 2-methyl-1-naphthol, 2,6-dimethyl-3-aminophenol, 2-amino-3-hydroxy-5-chloropyridine, 2, 6-dihydroxy-3, 4-dimethylpyridine, 2,6-bis- (2'-hydroxyethylamino) toluene, 3-amino-2,4-dichlorophenol, 3-amino-2-chloro-6-methylphenol, 5-amino -4-chloro-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxy pyridine, 2-methylresorcinol, 4-chlororesorcinol, 2,4-diaminophenoxyethanol, 1,3-bis (2,4-diaminophenoxy) propane, resorcinol, 3,5-diamino-2,6-dimethoxypyridine and 1,7- Dihydroxynaphthahn, 2,7-Dihydroxynaphthahn and 1,5-Dihydroxynaphthalin, 4-Hydroxyindol, 6-Hydroxyindol as well as their physiologically compatible salts.

According to the invention, keratin fibers are understood to mean furs, wool, feathers and in particular human hair.

Examples of physiologically tolerable salts of the compounds according to the invention are the hydrochlorides, hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates.

In addition to the dye combination according to the invention, the color-changing agents according to the invention can contain at least one further dye precursor.

With regard to the dye precursors that can be used in the agents according to the invention, the present invention is not subject to any restrictions. The agents according to the invention can be used as dye precursors

• developer and coupler type oxidation dye precursors, and

• contain precursors of nature-analogous dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups.

Primary aromatic amines with a further free or substituted hydroxy group in the para or ortho position are usually used as developer components. or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives.

It can be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as the developer component. P-Phenylenediamine derivatives of the formula (I) are particularly preferred

in which

G ¹ stands for a hydrogen atom, a Ci to C ₄ alkyl radical, a C _\ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C _\ to C ₄ ) alkoxy (Cj - to C ₄ ) alkyl radical, a 4'-aminophenyl radical or a Ci to C - alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a Ci to C ₄ alkyl radical, a Ci to C - monohydroxyalkyl, a C ₂ - to C ₄ -Polyhydroxyalkylradikal, a (- C) - alkoxy- (C _- to C) alkyl radical or a C _\ - to C ₄ alkyl radical substituted with a nitrogenous group;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a Cj to C ₄ alkyl radical, a Ci to C ₄ monohydroxyalkyl radical, a Cj to C ₄ hydroxyalkoxy radical Cj to C ₄ acetylaminoalkoxy radical, a Cp to C ₄ mesylaminoalkoxy radical or a Ci to C ₄ carbamoylaminoalkoxy radical; G ⁴ represents a hydrogen atom, a halogen atom or a Cj to C ₄ alkyl radical or if G ³ and G ^{4 are} in the ortho position to one another, they can together form a bridging α, ω-alkylenedioxo group, such as, for example, an ethylenedioxy group. Examples of the C 1 -C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Ci to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C 1 to C ₄ hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. Examples of halogen atoms according to the invention are F, CI or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (I) are in particular the amino groups, C _\ - to C ₄ - monoalkylamino groups, C _\ - to C ₄ -dialkylamino groups, Cj - to C ₄ - trialkylammonium groups, C _\ - to C ₄ -monohydroxyalkylamino groups, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (I) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) aniline, N, N-bis- (ß-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (ß-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis (ß-hydroxyethyl) amino-2-chloroaniline, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N - (ß-Hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, ß-hydroxyethyl) -p-phenylenediamine, N - (ß, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß-hydroxyethyloxy) -p-phenylenediamine, 2- (ß -Acetylamino-ethyloxy) -p-phenylenediamine, N- (ß-M ethoxyethyl) -p-phenylenediamine and 5,8-diamino-benzo-l, 4-dioxane and their physiologically tolerable salts.

According to the invention, p-phenylenediamine derivatives of the formula (I) which are particularly preferred are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis- (β-hydroxyethyl) -p-phenylenediamine. It can further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted with amino and / or hydroxyl groups.

Among the binuclear developer components which can be used in the coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (II) and their physiologically tolerable salts:

in which:

- Z ¹ and Z ² independently represent a hydroxyl or NH ₂ radical, which is optionally substituted by a C _\ - substituted hydroxyalkyl radical and / or by a bridge Y -, -C ₄ alkyl radical by a _CJ-4 to C or which is optionally part of a bridging ring system,

- The bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be and may be substituted by one or more hydroxyl or Ci to C ₈ alkoxy radicals, or a direct bond,

- G ⁵ and G ⁶ are each independently a hydrogen or halogen atom, a Ci to C ₄ alkyl radical, a Ci to C ₄ -Monohydroxyalkylradikal, a C ₂ - to C ₄ - Polyhydroxyalkylradikal, a _CJ-4 to C -Aminoalkyl radical or a direct connection to the bridging Y, G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridging Y or a Cj to C ₄ alkyl radical, with the provisos that the compounds of the formula ( II) contain only one bridge Y per molecule and the compounds of the formula (II) contain at least one amino group which carries at least one hydrogen atom.

According to the invention, the substituents used in formula (II) are defined analogously to the above statements.

Preferred dinuclear developer components of the formula (II) are in particular: N, N'- bis (ß-hyckoxyemyl) -N, N'-bis- (4'-ammophenyl) -l, 3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N ^, -bis - (ß-Hydroxyethyl) -N, N ^, -bis- (4-aminophenyl) -tetramethyl-endiamine, N, N'-bis- (4-methyl-aminophenyl) -tetramethylene-diamine, N, N'-bis- (ethyl ) -N, N'- bis- (4'-amino-3'-methylphenyl) -ethylenediamine, bis- (2-hydroxy-5-aminophenyl) methane, 1,4-bis- (4'-aminophenyl) - diaza-cycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and l, 10-bis (2 ', 5'-diaminophenyl ) - 1,4,7,10-tetraoxadecane and its physiologically acceptable salts.

Very particularly preferred dinuclear developer components of the formula (II) are N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) - 1,4-diazacycloheptane and l, 10-bis (2 ', 5'-diaminophenyl) - l, 4,7,10-tetraoxadecane or one of its physiologically acceptable salts.

Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as developer component. P-Aminophenol derivatives of the formula (III) are particularly preferred in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C 1 -C ₄ -alkyl radical, a C 1 -C to Gp monohydroxyalkyl radical, a (C 1 -C ₄ ) -alkoxy- (d- to C ₄ ) -alkyl radical, a Cp to C ₄ -aminoalkyl radical, a hydroxy (Cι- to C ₄₎ - alkylamino radical, a Cp to C ₄ -Hydroxyalkoxyradikal, a Cp to C ₄ hydroxyalkyl (cpuntil _C4) -aminoalkyl radical, or a (di-Cp to C ₄ - Alkylamino) - (Cp to C ₄ ) - alkyl radical, and

G ¹⁴ represents a hydrogen or halogen atom, a Cp to C ₄ alkyl radical, a Cp to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (Cp to C ₄ ) alkoxy (Cp to C ₄ ) -alkyl radical, a Cp to C ₄ aminoalkyl radical or a Cp to C ₄ cyanoalkyl radical,

G ¹⁵ represents hydrogen, a Cp to C ₄ alkyl radical, a Cp to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

- G ¹⁶ represents hydrogen or a halogen atom.

According to the invention, the substituents used in formula (III) are defined analogously to the above statements.

Preferred p-aminophenols of the formula (III) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-2,6-dichlorophenol , 4-amino-2,6-dibromophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol , 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2-fiuorophenol , 4-amino-2-chlθhenol, 2,6-dichloro-4-aminophenol, 4-amino-2- ((diethylamino) methyl) phenol and their physiologically tolerable salts. Very particularly preferred compounds of the formula (III) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2 - ((diethylamino) methyl) phenol and 4-amino-2,6 -dichlorphenol.

Furthermore, the developer component can be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts.

Preferred pyridine derivatives are, in particular, the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4-methoxyphenyl) amino-3-amino-pyridine, 2 , 3-diamino-6-methoxy-pyridine, 2- (ß-

Methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open patent publication JP 02019576 A2 or in laid-open publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-

Dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740931 and DE 195 43 988, such as 4,5- Diamino-l-methylpyrazole, 4,5-diamino-1 - (β-hydroxyethyl) -pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 - (4'-chlorobenzyl) -pyrazole, 4,5-diamino -l, 3-dimethylpyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, 4,5-diamino-l-methyl-3-phenylpyrazole, 4-amino-l, 3-dimethyl-5-hydrazinopyrazole, l -Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5 -Diamino-l- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1 - ethyl-3- (4'-methoxyphenyl) -pyrazole, 4,5-diamino-l-ethyl-3-hydroxymethylpyrazole, 4,5- Diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-l -isopropylpyrazole, 4-amino-5- (2'- aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5-triaminopyrazole, 3,5-diamino-l-methyl 1-4-methylaminopyrazole and 3,5-diamino -4 (β-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyrazole-pyrimidine derivatives are in particular the derivatives of pyrazole- [1,5-a] -pyrimidine of the following formula (IV) and its tautomeric forms, provided that there is a tautomeric equilibrium:

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a Cp to C ₄ alkyl radical, an aryl radical, a Cp to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical ( Cp to C ₄ ) alkoxy- (Cp to C ₄ ) -alkyl radical, a Cp to C ₄ -aminoalkyl radical which can optionally be protected by an acetyl-ureide or sulfonyl radical, a (Cp to C) -alkylamino- (Cp to C) alkyl radical, a di - [(Cp to C ₄ ) alkyl] - (Cp to C ₄ ) aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links Cp to C ₄ hydroxyalkyl or a di (Cp to C ₄ ) - [hydroxyalkyl] - (Cp to C ₄ ) aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom, a Cp to C ₄ alkyl radical, an aryl radical, a Cp to C ₄ -Hydroxyalkyladikal, a C ₂ - to C ₄ - Polyhydroxyalkylradikal, a Cp to C ₄ -aminoalkyl radical, a (Cp to C ₄₎ - alkylamino - (Cp to C ₄ ) -alkyl radical, a di - [(Cp to C ₄ ) alkyl] - (Cp to C ₄ ) - aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a Cp to C ₄ hydroxyalkyl or a di (Cp to C ₄ hydroxyalkyl) aminoalkyl radical, an amino radical, a Cp to C ₄ alkyl or di (Cp to C ₄ hydroxyalkyl) amino radical, a halogen atom , a carboxylic acid group or a sulfonic acid group, - i has the value 0, 1, 2 or 3,

- p has the value 0 or 1,

- q has the value 0 or 1 and

- n has the value 0 or 1, with the proviso that

- the sum of p + q is not equal to 0,

- if p + q is 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

- if p + q is 1, n is 1, and the groups NG ^I7 G ¹⁸ (or NG ^I9 G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

According to the invention, the substituents used in formula (TV) are defined analogously to the above statements.

If the pyrazole- [1,5-a] pyrimidine of the formula (IV) above contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated, for example, in the following scheme:

Among the pyrazole- [1,5-a] pyrimidines of the formula (IV) above, one can mention in particular:

- pyrazole- [1,5-a] pyrimidine-3,7-diamine;

- 2,5-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;

- pyrazole (1,5-a) pyrimidine-3,5-diamine;

- 2,7-dimethyl pyrazole- [1,5-a] pyrimidine-3,5-diamine;

- 3-amino pyrazol- [1,5-a] pyrimidin-7-ol;

- 3-amino pyrazol- [1,5-a] pyrimidin-5-ol;

- 2- (3-amino pyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol;

- 2- (7-amino pyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol;

- 2 - [(3-Amino pyrazol- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol; - 2 - [(7-Amino pyrazol- [l, 5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;

- 5,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;

- 2,6-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;

- 2,5, N7, N7-tetramethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine; as well as their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

The pyrazole [1,5-a] pyrimidines of the formula (IV) above can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components.

Preferred coupler components according to the invention are m-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-

Cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro

6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol .

N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3-

Ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4'- diaminophenoxy) propane, 1-

Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2 ', 4'-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -l-methylbenzene and l-amino-3-bis (2'-hydroxyethyl) amino benzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and

2,3-diamino-l-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol,

Resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol,

2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1, 2,4-trihydroxybenzene, Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine,

2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-

Dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine,

2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-

Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene,

1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-

Dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Moφholinderivate such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-l, 2,3,4-tetrahydroquinoxaline,

Pyrazole derivatives such as, for example, l-phenyl-3-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-

hydroxyindole,

Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-

Amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-

Dihydroxy-2-methylpyrimidine, or

Methylenedioxybenzene derivatives such as l-hydroxy-3,4-methylenedioxybenzene, l-amino-3,4-methylenedioxybenzene and l- (2'-hydroxyethyl) - amino-3, 4-methylenedioxybenzene.

Particularly preferred further coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine and 3-amino-2-methylamino-6 -methoxypyridin.

It is not necessary that the oxidation dye precursors or the substantive dyes each represent uniform compounds. Rather, due to the production process for the individual dyes, the hair colorants according to the invention may also contain further components in minor amounts be, as far as these do not adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

With regard to the dyes which can be used in the hair colorants and tints according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European inventory of cosmetic raw materials ", published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicinal Products, Health Care Products and Personal Care Products, Mannheim.

The oxidation dye precursors are preferably present in the agents according to the invention in amounts of 0.01 to 20% by weight, preferably 0.5 to 5% by weight, in each case based on the total agent.

Those indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group.

Derivatives of 5,6-dihydroxyindoline of the formula (Va) are particularly suitable as precursors of naturally analogous hair dyes,

in the independently of each other R ¹ represents hydrogen, a CpC ₄ alkyl group or a CpC ₄ hydroxyalkyl group,

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,

R ³ represents hydrogen or a CpC alkyl group,

R ⁴ represents hydrogen, a CpC ₄ alkyl group or a group -CO-R ⁶ , in which

R ⁶ represents a CpC alkyl group, and

R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially that 5,6-Dihydroxyindolin.

Derivatives of 5,6-dihydroxyindole of the formula (Vb) are also outstandingly suitable as precursors of natural hair dyes,

in the independent

R ¹ represents hydrogen, a CpC alkyl group or a CpC ₄ hydroxyalkyl group,

R ³ represents hydrogen or a CpC ₄ alkyl group, R ⁴ represents hydrogen, a CpC ₄ alkyl group or a group -CO-R ⁶ , in which

R ⁶ represents a CpC ₄ alkyl group, and

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Within this group, particular mention should be made of N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5.6 -Dihydroxyindol.

The indoline and indole derivatives can be used in the colorants used in the process according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for. B. the hydrochlorides, sulfates and hydrobromides, are used. The indole or indoline derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.

In particular when using dye precursors of the indoline or indole type, it has proven to be advantageous to use an amino acid and / or an oligopeptide as the alkalizing agent.

In addition to the dye precursors, the agents according to the invention can contain direct dyes for further shading. These are usually selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 13, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 7, Basic Blue 26, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Basic Violet 2, Basic Violet 14, Acid Violet 43, Disperse Black 9, Acid Black 52, Basic Brown 16 and Basic Brown 17 Compounds and 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 4-amino-2-nitrodiphenylamine-2 '- carboxylic acid, 6-nitro - 1, 2,3, 4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.

The agents according to the invention preferably contain dye precursors in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, aerosols or other preparations which are suitable for use on the hair. However, it is also conceivable to integrate the dye precursors into a powdery or tablet-like formulation.

For the purposes of the present invention, aqueous-alcoholic solutions are understood to mean aqueous solutions containing 3 to 70% by weight of a CpC ₄ alcohol, in particular ethanol or isopropanol. The agents according to the invention can additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. All water-soluble organic solvents are preferred. The actual oxidative coloring of the fibers can basically be done with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially when a lightening effect on human hair is desired in addition to the coloring. Persulfates, chlorites and in particular hydrogen peroxide or its adducts with urea, melamine and sodium borate are suitable as oxidizing agents. But you can also apply the oxidation dye together with a catalyst on the hair, which the oxidation of the dye precursors, for. B. activated. Such catalysts are e.g. B. transition metal compounds, iodides, quinones or certain enzymes. Suitable enzymes are e.g. B. peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as the laccases, or generate small amounts of hydrogen peroxide in situ and thus activate the oxidation of the dye precursors biocatalytically. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific for them, e.g. B.

Pyranose oxidase and e.g. B. D-glucose or galactose,

Glucose oxidase and D-glucose,

Glycerin oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts, - alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and their salts,

Tyrosinase oxidase and tyrosine,

Uricase and uric acid or its salts,

Choline oxidase and choline,

Amino acid oxidase and amino acids. The actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can range between 15 and 40 ° C. After an exposure time of 5 to 45 minutes, the hair dye is applied Rinse removed from the hair to be dyed. Washing with a shampoo is not necessary if a carrier with a high tenside content, such as a coloring shampoo, has been used.

The agents according to the invention can furthermore contain all active substances, additives and auxiliary substances known for such preparations. In many cases, these agents contain at least one surfactant, in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, linear fatty acids with 10 to 22 carbon atoms (soaps )

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear one

Alkyl group with 10 to 22 carbon atoms and x = 0 or 1 to 16,

Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,

Acyl taurides with 10 to 18 carbon atoms in the acyl group,

Acyl isethionates with 10 to 18 carbon atoms in the acyl group,

Monosulfonic succinate and dialkyl esters with 8 to 18 carbon atoms in the

Alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 C-

Atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 12 to 18 C atoms, linear alpha-olefin sulfonates with 12 to 18 C atoms,

Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms, - alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH -CH ₂ O) _x -SO ₃ H, in which

R is a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12, Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6

Double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22

Represent carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid ,

Non-ionic surfactants contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group, Cι ₂ -C ₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues and addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ^! O- (Z) _χ . These connections are characterized by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1- Myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R ¹ . Usually, however, these compounds are made 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 respective working up of these compounds.

Particularly preferred are those alkyl polyglycosides in which R ¹ consists essentially of C ₈ - and Cio-alkyl groups, essentially from C ₁₂ - and C ₁₄ -alkyl groups, essentially from C ₈ - to C ₆ -alkyl groups or essentially from Cj ₂ - C ₁₆ alkyl groups.

Any mono- or oligosaccharides can be used as sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar units are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain an average of 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. In the event that an effect of the perfume oil on the hair beyond the duration of the hair treatment is desired, the person skilled in the art will preferably resort to this substance class as a further ingredient of the preparations according to the invention. The alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(" - or wear. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₈ -alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 1 ₂ - 1 ₈ - acyl isarcosine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound, esterquat and amidoamine type. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the 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.

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 sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A compound from this group of substances which is particularly suitable according to the invention is stearamidopropyldimethylamine, which is commercially available under the name Tegoamid S 18.

The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM- 2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted using alkali metals, alkali metal hydroxides or alkali metal alcoholates. In contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Furthermore, the agents according to the invention can preferably also contain a conditioning active ingredient selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils. Cationic polymers can be preferred as conditioning agents. These are usually polymers that have a quaternary nitrogen atom, for example in the form of a

Ammonium group.

Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. The under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)),

Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer) are examples of such cationic polymers. Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, with diethyl sulfonate quaternonate dimethylaminomethacrylate copolymers. Such compounds are available under the names Gafquat ^® 734 and Gafquat ^® 755 commercially.

Vinylpyrrolidone-Me oimidazoliniumchlorid-copolymers, as they are offered under the name Luviquat ^® , quaternized polyvinyl alcohol and those under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Cationic polymers of the first four groups are particularly preferred; polyquaternium-2, polyquaternium-10 and polyquaternium-22 are very particularly preferred.

Silicone oils, in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethylpolysiloxane and, are also suitable as conditioning agents Methylphenylpolysiloxane, as well as their alkoxylated and quaternized analogues. Examples of such silicones are the products sold by Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 as well as the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxyl-amino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt ; diquaternary polydimethylsiloxanes, Quaternium-80).

Paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents.

Likewise suitable hair-conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephalins.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers,

Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as Acrylamidopropyl- trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-HychOxypropylmethacrylat copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids .

Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers,

Vinyl acetate / butyl maleate / isobomylacrylate copolymers, methyl vinyl ether maleic anhydride copolymers and acrylic acid / ethyl acrylate / Ν-tert-butyl-acrylamide-

terpolymers

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans,

Cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and

Carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as e.g. B. bentonite or fully synthetic hydrocolloids such as

polyvinyl alcohol,

Structurants such as maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin,

Egg lecithin and cephaline,

Protein hydrolyzates, especially elastin, collagen, keratin, milk protein,

Soy protein and wheat protein hydrolyzates, their condensation products with

Fatty acids and quaternized protein hydrolyzates,

Perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and intermediates such as ethanol, isopropanol, ethylene glycol,

Propylene glycol, glycerin and diethylene glycol, active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl l-alkylamidoethyl-2-alkylimidazolinium methosulfate

Defoamers like silicones,

Dyes for coloring the agent,

Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole,

Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and

triazines,

Substances for adjusting the pH, such as customary acids, in particular edible acids and bases,

Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts and bisabolol,

Vitamins, provitamins and vitamin precursors, especially those of groups A, B ₃ ,

B ₅ , B ₆ , C, E, F and H,

Plant extracts such as the extracts from green tea, oak bark, nettle,

Witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers,

Almond, aloe vera, spruce needles, horse chestnut, sandalwood, juniper, coconut,

Mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage,

Rosemary, Birch, Mallow, Cuckoo Flower, Quendel, Yarrow, Thyme,

Melissa, hake, coltsfoot, marshmallow, meristem, ginseng and ginger root,

Cholesterol,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,

Fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids, swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, pigments,

Stabilizing agent for hydrogen peroxide and other oxidizing agents,

- Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants.

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, e.g. B. Kh. Schrader, Basics and Formulations of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

The following examples are intended to clarify the subject matter of the present application without, however, restricting it thereto.

Examples

1. Basic composition of a coloring cream

First, a cream base of the following composition was produced (unless otherwise stated, all information relates to the proportions in g):

Taig fatty alcohol 17.0

Loro techn. ¹ 4.0

Texapon ^® N 28 ² 40.0

Dehyton ^® K ³ 25.0

Eumulgin ^® B2 ⁴ 1.5

Distilled water 12.5

¹ Cι _{2-] 8} fatty alcohol (Cognis)

2 sodium sulfate, uranium, sulfate (approx. 28% active substance; INCI name: sodium

Laureth Sulfate) (Cognis)

Fatty acid amide derivative with betaine structure of the formula

RCONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ CH ₂ COO ^" (approx. 30% active substance; INCI name:

Cocoamidopropyl Betaine) (Cognis)

Cetylstearyl alcohol with approx. 20 mol EO (INCI name: Ceteareth-20) (Cognis)

The following hair color emulsion was then produced on the basis of this cream:

Cream base 50.0

Developer component 7.5 mmol

Coupler component 7.5 mmol

Na ₂ SO ₃ (inhibitor) 1.0

(NH ₄ ) ₂ SO ₄ 1.0 conc. NH ₃ solution ad pH 10

Water ad 100 The ingredients were mixed together in order. After the oxidation dye precursors and the inhibitor had been added, the pH of the emulsion was first adjusted to 10 using concentrated ammonia solution, and the mixture was then made up to 100 g with water.

The oxidative development of the color was carried out with 3% hydrogen peroxide solution as the oxidation solution. For this purpose, 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (3%) and mixed.

The coloring cream was applied to approx. 5 cm long strands of standardized, 90% gray, but not specially pretreated human hair and left there for 30 minutes at 32 ° C. After the dyeing process was completed, the hair was rinsed, washed with a conventional shampoo and then dried.

2. Coloring examples

a)

The combinations according to the invention of bis- (5-amino-2-hydroxyphenyl) methane hydrochloride (E) with the dye precursors and the dyeing results obtained can be seen from the following table:

b) Furthermore, the strands of hair were colored with the following recipes:

Recipe No. 1 / color result: leather brown

(Figures in% by weight)

Fatty alcohol mixture 6.0

Eumulgin ^® B2 ⁴ 0.5

Texapon.RTM ^® NSO ⁵ 10.0

Dehyton ^® K ³ 5.0

Polymer ^JR® 400 (Polyquaternium 10) ⁶ 0.4

Gafquat ^® 755 (Polyquaternium 11) ⁷ 0.2

Celquat ^® L 200 (Polyquaternium 4) ⁸ 0.2

Ascorbic acid 0.4

Ammonium sulfate 0.5

4-Amino-2 - {(4- [5'-Amino-2'-hydroxy-1, 7 phenyl) methyl] piperazinyl) methyl} phenol tetrahydrochloride

2- (2'-hydroxyethyl) -p-phenylene-0.84 diamine sulfate

4-amino-2-aminomethylphenol-0.05 dihydrochloride

4-Amino-2 - ((diethylamino) methy) 0.05 phenol dihydrochloride

4-amino-3-methylphenol 0.30

2-amino-4-methylphenol 0.02

2-amino-3-hydroxypyridine 0.12

5-amino-4-chloro-2-methylphenol 0.12

2-methylresorcinol 0.24

4-chlororesorcinol 0.12

3-aminophenol 0.24

5, 6-dihydroxyindoline hydrobromide 0.06

Ammonia, 25% ad pH 9.8

Water ad 100% Recipe No. 2 / color result: red-brown

(Figures in% by weight)

Fatty alcohol mixture Cι ₂ -C ₁₈ 6.0

Eumulgin ^® B2 ⁴ 0.5

Texapon.RTM ^® NSO ⁵ 10.0

Dehyton ^® K ³ 5.0

Polymer ^JR® 400 (Polyquaternium 10) ⁶ 0.4

Gafquat ^® 755 (Polyquaternium ll) ⁷ 0.2

Celquat L ^® 200 (Polyquaternium 4) ⁸ 0.2

Ascorbic acid 0.4

Ammonium sulfate 0.5

Bis- (5-amino-2-hydroxyphenyl) - 1.36 methane dihydrochloride

4- Amino-2- {(4- [5 '- Amino-2' -hydroxy-2.12 phenyl) methyl] piperazinyl) methyl} phenol tetrahydrochloride p-toluenediamine sulfate 0.03 p-phenylenediamine dihydrochloride 0.03

2- (2 '-hydroxyethyl) -p-phenylene-0.07 diamine sulfate

N, N-bis (2'-hydroxyethyl) p-phenylene 0.07 diamine sulfate

2-Amino-5-methylphenol 0.01

2-amino-4-chlorophenol 0.02

4-amino-2-chlorohenol 0.01

2-amino-3-hydroxypyridine 0.5

5 - Amino-2-methylphenol 0.03

5 - (2'-Hydroxyethyl) amino-2-methylphenol 0.01

3-amino-2-chloro-6-methylphenol 0.02

6-hydroxyindole 0.1

1, 2,3, 4-tetrahydro-6-nitroquinoxaline 0.05

HC Yellow 5 0.03 HC Red 1 0.01

4- amino-2-nitro-diphenylamine-2 '- 0.01 carboxylic acid

Ammonia, 25% ad pH 9.8

Water ad 100%

Recipe No.:3 / color result: cement gray

(Figures in% by weight)

Fatty alcohol mixture C ₁₂ -Cι ₈ 10.0% Texapon ^® Kl 4 S70C ⁹ 2.5%

Plantars ⁸ '1200 UP 10 2.0%

Akypo Soft ^® 45 NV ^π 12.0%

Eutanol ^® G ¹² 1.0%

Eumulgin ^® Bl ¹³ 0.5%

Eumulgin ^® B2 ⁴ 0.5%

Polymer W ^® 37194 (Stockhausen) ¹⁴ 2.0%

Cosmedia Guar ^® C261 ¹⁵ 0.2%

Mirapol ^® AI 5 (Polyquaternium 2) ¹⁶ 0.5%

Ascorbic acid 0.4%

Ammonium sulfate 0.5%

Bis (5-amino-2-hydroxyphenyl) methane 0.018% dihydrochloride

4- Amino-2- {(4- [5 '- Amino-2' -hydroxy-0.030 phenyl) methyl] piperazinyl) methyl} phenol tetrahydrochloride

2- (2 '-hydroxyethyl) -p-phenylene-0.045 diamine sulfate

1-naphthol 0.015

2-methyl-1-naphthol 0.022

1, 5 -dihydroxynaphthahn 0.005

3-amino-2-methylamino-6-methoxy-0.003 pyridine

2-methylresorcinol 0.009 ammonia, 25% ad pH 9.8 water ad 100%

Recipe No.:4 / color result: agate brown

(Figures in% by weight)

Fatty alcohol mixture C ₁₂ -C ₁₈ '10.0%

Texapon * Kl 4 S70C -χ9 ^y 2.5% 0

Plantaren ^® 1200 UP ¹⁰ 2.0%

Akypo Soft ^® 45 NV ¹ '12.0%

Eutanol ^® G ¹² 1.0

Eumulgin ^® Bl ¹³ 0.5

Eumulgin ^® B2 ⁴ 0.5

Polymer W ^® 37194 (Stockhausen) ¹⁴ 2.0

Cosmedia Guar C261 ^® ¹⁵ 0.2

Mirapol ^® A15 (Polyquaternium 2) ¹⁶ 0.5

Ascorbic acid 0.4

Ammonium sulfate 0.5

Bis (5-amino-2-hydroxyphenyl) methane 2.40 dihydrochloride

4-Amino-2 - ((diethylamino) methyl) phenol-0.18 dihydrochloride

3-amino-2-methylamino-6-meth-2,04 oxypyridine

2,6-dihydroxy-3,4-dimethylpyridine 0.01

3,5-diamino-2,6-dimethoxypyridine 0.02

2-ethylamino-4-nitro-6-chlorophenol 0.07

HC Red BN 0.2

5, 6-dihydroxyindoline hydrobromide 0.12

Ammonia, 25% ad pH 9.8

Water ad 100% Recipe No.:5 / color result: brown orange

(Figures in% by weight)

Fatty alcohol mixture C ₁ -Cj ₈ 8.0

Texapon ^® NSO ⁵ 2.0

Dehyton ^® K ³ 1.0

Potassium oleate 2.0

Potassium isostearate 2.0

Myristic acid 1.0

Eumulgin ^® B2 ⁴ 0.5

Westvaco Diaeid H 240, K salt ²¹ 2.0

Merquat ^® 550 (Polyquaternium 7) ¹⁷ 0.2

Luviquat ^® FC 370 (Polyquaternium 16) ¹⁸ 0.1

Merquat ^® 280 (Polyquaternium 22) ¹⁹ 0.1

Gafquat ^® HS 100 (Polyquaternium 28) ²⁰ 0.1

Ascorbic acid 0.4

Ammonium sulfate 0.5

Bis (5-amino-2-hydroxyphenyl) methane 1.42 dihydrochloride

4- Amino-2- {(4- [5 '- Amino-2' -hydroxy-2,22 phenyl) methyl] piperazinyl) methyl} phenol tetrahydrochloride

5 - Amino-2-methylphenol 0.6

5- (2'-Hydroxyethyl) amino-2-methyl-0.3 phenol

3 - Amino-2-chloro-6-methylphenol 0.5

Ammonia, 25% ad pH 9.8

Water ad 100% Sodium lauryl ether sulfate (approx. 27% active substance); INCI name: Sodium Laureth Sulfate quaternized hydroxyethyl cellulose; INCI name: Polyquaternium- 10 (Amerchol)

Dimethylaminoethyl methacrylate-vinyl pyrrolidone copolymer, quaternized with diethyl sulfate; INCI name: Polyquaternium-11 (ISP) quaternized cellulose derivative; INCI name: Polyquatemium-4 (National Starch & Chemical)

Sodium lauryl myristyl laurel ether sulfate (68-73% active ingredient); INCI name: Sodium Myreth Sulfate; (Cognis)

C ₁₂ -C ₁₆ fatty alcohol-1,4-glucoside (50-53% active ingredient); INCI name: Lauryl Glucoside; (Cognis)

Cι ₂ -C ₁₄ fatty alcohol 4.5-EO acetic acid sodium salt (21% active substance); INCI name: Sodium Laureth-6 carboxylate; (KAO) 2-octyl decanol; INCI name: Octyl Decanol; (Cognis) cetearyl alcohol with 12 moles of EO; INCI name: Ceteareth-12; (Cognis) acrylic acid-sodium salt-acrylamidopropyltrimethylammonium chloride copolymer; INCI name: Acrylamidopropyltrimoniumchloride / Acrylates Copolymer; (Stockhausen)

Guarhydroxypropyltrimethylammoniumchlorid; INCI name: guar hydroxypropyltrimonium chloride; (Cognis) poly [N-3- (dimethylammonium) propyl] -N '- [3-ethyleneoxyethylene dimethylammonium) propyl] urea dichloride; INCI name:

Polyquaternium-2; (Rhodia)

Dimethyldiallylammonium chloride-acrylamide copolymer (8-9% active ingredient); INCI name: Polyquaternium-7 (Chemviron)

Vinylimidazoliummethochloride-vinylpyrrolidone copolymer; INCI

Name: Polyquaternium- 16) (BASF)

Dimethyldiallylammonium chloride-acrylic acid copolymer (35% active substance); INCI name: Polyquaternium-22 (Chemviron) Vinylpyrrolidone-methacrylamidopropyltrimemylammonium chloride copolymer (19-21% active ingredient); INCI name: Polyquaternium-28 (General Anilin Firm Coφ.) 4-Hexyl-5 (6) -carboxy-2-cyclohexen-1-octanoic acid, potassium salt; (Westvaco Chemicals)

Claims

Expectations

1. Agent for dyeing keratin fibers, in particular human hair, containing a combination of a) bis (5-amino-2-hydroxyphenyl) methane and / or 4-amino-2- { (4- [5'-amino-2'-hydroxyphenyl) methyl] piperazinyl) methyl} phenol tetrahydrochloride and b) at least one further dye product selected from p-toluenediamine, 2- (β-hydroxyethyl) -p- phenylenediamine, 4-amino-3-methylphenol, 4-amino-2,6-dichloro-phenol, 4-amino-2,6-dibromophenol, 4-amino-3-fluoφhenol, 4-amino-2-aminomethylphenol, 4-amino- 2 - ((diethylamino) methyl) phenol, 2-amino-4-methylphenol, 4-amino-2-methylphenol, 2-amino-5-methylphenol, 2-amino-4-chlθφhenol, 4-amino-2-chlθφhenol, 3,4-methylenedioxyaniline, 2-methyl-1-naphthol, 2,6-dimethyl-3-aminophenol, 2-amino-3-hydroxy-5-chloropyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2, 6-bis (2'-hydroxyethylamino) toluene, 3-amino-2,4-dichloro-phenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4- ch lor-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2- Methylresorcinol, 4-chlororesorcinol, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4'-diaminophenoxy) propane, resorcinol, 3,5-diamino-2,6-dimethoxypyridine and 1,7-dihydroxynaphthahnahn, 2 , 7-Dihydroxynaphthahn and 1, 5-Dihydroxynaphthalin, 4-Hydroxyindol, 6-Hydroxyindol and their physiologically compatible salts.

2. Composition according to claim 1, characterized in that it further comprises at least one substantive dye selected from HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 13, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 7, Basic Blue 26, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Basic Violet 2, Basic Violet 14, Acid Violet 43, Disperse Black 9, Acid Black 52, Basic Brown 16 and Basic Brown 17 known compounds as well as 1,4-bis- (ß-hydroxyethyl) -amino-2- nitrobenzene, 3-nitro-4- (ß-hydroxyethyl) aminophenol, 4-amino-2-nitrodiphenylamine-2 '-carboxylic acid, 6-nitro- 1, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-Chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.