WO2002026200A1

WO2002026200A1 - Oxidation dyes with 2-amino-5-methylphenol

Info

Publication number: WO2002026200A1
Application number: PCT/EP2001/010850
Authority: WO
Inventors: Horst Höffkes; Doris Oberkobusch; Udo Erkens; Bernd Meinigke
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2000-09-29
Filing date: 2001-09-20
Publication date: 2002-04-04
Also published as: AU2002210510A1; DE20016994U1

Abstract

The invention relates to agents for dyeing keratinous fibres, containing the following dye intermediates in a cosmetically acceptable medium: (A) 2-amino-5-methylphenol; and (B) at least one other dye intermediate, selected from the following: N,N-bis-(2'-hydroxyethyl)-p-phenylendiamine, 2,6-dichloro-4-aminophenol, 2,6-dibrom-4-aminophenol, 4-methylaminophenol, 2-diethylaminomethyl-4-aminophenol, 2-aminophenol, 2-amino-4-methylphenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,5-diaminopyridine, 4,5-diamino-1-(2'-hydroxyethyl)-pyrazol, 2-methylresorcin, 5-(2'-hydroxyethylamino)-2-methylphenol, 5-(3'-hydroxyproplyamino)-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, N,N-dimethyl-3-amino-phenol, N-cyclopentyl-3-aminophenol, 2,4-dichloro-3-aminophenol, 1,3,-bis-(2'-4'-diaminophenyl)-propane, 2,4-diamino-phenoxyethanol, 3,5-diamino-2-methoxy-1-methylbenzol, 2, amino-4-(2'-hydroxyethylamino)-anisol, 2,6-bis-(2'-hydroxyethyl)-1-methylbenzol, 2-amino-3-hydroxypyridine, 5-chloro-2-amino-3-hydroxypyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,6-dihydroxy-3,5-dimethoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,3-diaminopyridine, 1-hydroxy-2-methylnapthaline, 1,5-dihydroxynaphthaline and 2,7-dihydroxynaphthaline. The inventive agents produce particularly intensive colours in the yellow range, with excellent fastness properties, and are also characterised by their extremely good toxicological properties.

Description

"Oxidation colorant with 2-amino-5-methylphenol"

The present invention relates to agents for dyeing keratin fibers which contain 2-amino-5-methylphenol, a method for dyeing keratin fibers with these agents and the use of this dye combination for dyeing keratin fibers.

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 dyes, tinting agents, waving agents and styling preparations. Means for changing or balancing the color of the scalp 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 dyeings are generally sensitive to shampooing, so that a frequently undesirable shift in the shade or even a visible "discoloration" can occur.

So-called oxidation colorants 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 under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more Coupler components from the actual dyes. The oxidation colorants are characterized by excellent, long-lasting coloring results.

Good oxidation dye products should primarily fulfill the following requirements: They must develop the desired color shades with sufficient intensity and authenticity in the oxidative coupling. They must also have a good ability to draw onto the fiber, with no noticeable differences between stressed and freshly regrown hair, especially with human hair (leveling ability). They should be resistant to light, sweat, heat, friction and the influence of chemical reducing agents, e.g. Perm liquids. 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 achieving colorations in the yellow range.

It has now surprisingly been found that particularly intensive colorations with excellent fastness properties and extraordinarily good toxicological properties can be obtained if colorants are used which contain 2-amino-5-methylphenol.

A first object of the present invention is therefore an agent for dyeing keratin fibers, containing in a cosmetically acceptable medium as dye precursors (A) 2-amino-5-methylphenol and

(B) at least one further dye precursor selected from N, N-bis (2'-hydroxyethyl) -p-phenylenediamine, 2,6-dichloro-4-aminophenol, 2,6-dibromo-4-aminophenol, 4-methylaminophenol , 2-diethylaminomethyl-4-aminophenol, 2-aminophenol, 2-amino-4-methylphenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5 , 6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,5-diaminopyridine, 4,5-diamino-l- (2'-hydroxyethyl) pyrazole, 2-methyhesorcinol, 5- (2'- Hydroxyethylamino) -2-methylphenol, 5- (3'-hydroxypropylamino) -2-methylphenol, 3 - amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4- methoxy-2-methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 2,4-dichloro-3-aminophenol, 1,3-bis- (2 ', 4'-diaminophenyl ) propane, 2,4-diamino-phenoxyethanol, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2'-hydroxyethylamino) anisole, 2,6-bis- (2nd '- hydroxyethyl) -l-methylbenzene, 2-amino-3-hydroxypyridine, 5-chloro-2-amino-3-hyd roxypyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,6-dihydroxy-3,5-dimethoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,3-diaminopyridine, l-hydroxy-2-methylnaphthalene, 1,5-dihydroxynaphthalene and 2,7-dihydroxynaphthalene.

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

In a preferred embodiment, component (B) is selected from

(A) 2-amino-5-methylphenol and

(B) at least one further dye precursor selected from N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 2,6-dichloro-4-aminophenol, 2,6-dibromo-4-aminophenol, 4-methylaminophenol , 2-diethylaminomethyl-4-aminophenol, 2-aminophenol, 2-amino-4-methylphenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5 , 6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,5-diaminopyridine, 4,5-diamino-l - (2'-hydroxyethyl) - pyrazole, 5- (2'-hydroxyethylamino) -2-methylphenol, 5- (3'-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2- methylphenol, 5-amino-4-methoxy-2-methylphenol, N, N-dimethyl-3-aminophenol, N-

Cyclopentyl-3-aminophenol, 2,4-dichloro-3-aminophenol, 1, 3-bis (2 ', 4'-diaminophenyl) propane, 2,4-diaminophenoxyethanol, 3, 5-diamino-2- methoxy-1-methylbenzene, 2,6-bis- (2'-hydroxyethyl) -l-methylbenzene, 2-amino-3-hydroxypyridine, 5-Cuor-2-amino-3-hydroxypyridine, 2,6-dimethoxy- 3,5-diaminopyridine, 2,6-dihydroxy-3,5-dimethoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,3-diaminopyridine, 1- Hydroxy-2-methylnaphthalene, 1,5-dihydroxynaphthalene and 2,7-

Dihydroxynaphthalene.

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.

The present invention is not subject to any restrictions with regard to the dye precursors which can be used in the agents according to the invention. The agents according to the invention can serve 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 or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof are usually used as developer components ,

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 C_ to C alkyl radical, a to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C to C ₄ ) alkoxy (Cr to C ₄ ) alkyl radical, a 4'-aminophenyl radical or a C to C ₄ alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a C_ to C ₄ alkyl radical, a C to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (Cι to C ₄ ) alkoxy (Cr to C ₄ ) alkyl radical or a Cr to C ₄ alkyl radical which is substituted by a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a Cr to C ₄ alkyl radical, a Cr to C monohydroxyalkyl radical, a Cr to C ₄ hydroxyalkoxy radical, a Cr to C ₄ acetylaminoalkoxy radical , a Cr to C ₄ mesylaminoalkoxy radical or a Cr to C ₄ carbamoylaminoalkoxy radical;

G ⁴ represents a hydrogen atom, a halogen atom or a Cr 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 d- to 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. Cr to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a Cr to C -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4- Hydroxybutyl group can be called. A 2-hydroxyethyl group is particularly preferred. Examples of halogen atoms according to the invention are F, Cl 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, Cr to C ₄ monoalkylamino groups, Cj to C ₄ dialkylamino groups, Cr to C ₄ trialkylammonium groups, Cr 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 -

Acetylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-l, 4-dioxane and their physiologically tolerable salts.

P-Phenylenediamine derivatives of the formula (I) which are particularly preferred according to the invention 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 of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a Cr to C ₄ alkyl radical, by a Cr to C hydroxyalkyl radical and or by a bridging Y or which is optionally part of a bridging one Ring system is, the bridge Y stands for an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is interrupted by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms or may be terminated and may be substituted by one or more hydroxyl or Cr to C ₈ alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently represent a hydrogen or halogen atom, a Cr to C ₄ alkyl radical, a Cr to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Cr to C ₄ aminoalkyl radical or one direct connection to bridge 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 bridge Y or a Cr to C ₄ alkyl radical, with the provisos that the compounds of the formula (II ) contain only one bridging Y per molecule and the compounds of 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- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'- bis (ß-hydroxyethyl) -N, N'-bis- (4 ^, -aminophenyl) -ethylenediamine, N, N'-bis- (4-

Aminophenyl) tetramethylene diamine, N, N'-bis (ß-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methylaminophenyl) 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) -l, 4,7,10-tetraoxadecane and their physiologically acceptable salts.

Very particularly preferred dinuclear developer components of the formula (II) are N, N ^, -bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -l, 3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -l, 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 represents a hydrogen atom, a halogen atom, a C to C ₄ alkyl radical, a Cr to C ₄ monohydroxyalkyl radical, a (Cr to C ₄ ) alkoxy (Cr to C ₄ ) alkyl radical, a Cr to C ₄ - Aminoalkyl radical, a hydroxy (Cr to C ₄ ) alkylamino radical, a Cr to C hydroxyalkoxy radical, a Cr to C ₄ hydroxyalkyl (Ci to C ₄ ) aminoalkyl radical or a (di-Cr to C ₄ alkylamino) - (Cr to C ₄ ) - alkyhadical, and

G ¹⁴ represents a hydrogen or halogen atom, a Cr to C ₄ alkyl radical, a Cr to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (Cr to C ₄ ) alkoxy (Cr to C ₄ ) alkyl radical, a Cr to C4 aminoalkyl radical or a Cr to C ₄ cyanoalkyl radical,

G ¹⁵ represents hydrogen, a Cr to C ₄ alkyl radical, a C 1 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-methyl-phenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-amino-phenol , 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-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro-4-aminophenol, 4 -Amino-2 - ((diethylamino) methyl) phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (III) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2-

((Diethylamino) methyl) phenol. 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 which are 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- (β-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds which are 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-tetraa inopyrimidine, 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 -Triaminopyrimidin.

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-1-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-1-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-l, 3-dime thylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5- triaminopyrazole, 3,5-diamino-1-methyl-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, G, G and G independently represent a hydrogen atom, a Cr to C alkyl radical, an aryl radical, a Cr to C hydroxyalkyl radical, a C ₂ to C polyhydroxyalkyl radical a (Cr to C) alkoxy - (Cr to C ₄ ) -alkyl radical, a Cr to C -aminoalkyl radical which can optionally be protected by an acetyl-ureide or sulfonyl radical, a (Cr to C ₄ ) -alkylamino- (Cr to C ₄ ) - alkyl radical, a di - [(Cr to C) alkyl] - (Cr to C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a Cr to C ₄ hydroxyalkyl- or a di- (Cr to C ₄ ) - [hydroxyalkyl] - (Cr to C ₄ ) - aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom, a Cr to C ₄ alkyl radical, an aryl radical, a Cr to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Cr to C ₄ aminoalkyl radical, a (Cr to C ₄ ) alkylamino (C to C ₄ ) alkyl radical adical, a di - [(Cr to C ₄ ) alkyl] - (Cr to C ₄ ) aminoalkyl radical, the dialkyl radicals optionally having a carbon cycle or a heterocycle

Form 5 or 6 chain links, a Cr to C ₄ hydroxyalkyl or a di (Cr to C ₄ hydroxyalkyl) aminoalkyl radical, an amino radical, a Cr to C ₄ alkyl or di (Cr 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, provided that the sum of p + q is not equal to 0 if p + q is 2, n is the value Has 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); when p + q is 1, n is 1 and the groups NG ¹⁷ G ¹⁸ (or NG ^Ϊ9 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 (IV) are defined analogously to the above statements.

If the pyrazole- [1,5-a] pyrimidine of the formula (IV) above contains a hydroxyl 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 above formula (IV) 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 (l, 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 pyrazol- [1,5-a] pyrimidin-7-ylamino) ethanol;

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

2 - [(3-amino pyrazol- [l, 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-dimethyl pyrazole- [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 above formula (IV) 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.

Coupler components preferred 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-cyclopentene 1-3 -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 ^I -hydroxyethyl) aminobenzene, o-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-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,

Morpholine derivatives 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-methy 1-3 -aminophenol, 2-Me- thyl-resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

It is not necessary that the oxidation dye precursors or the substantive dyes each represent uniform compounds. Rather, the hair colorants according to the invention, due to the manufacturing process for the individual dyes, may contain minor components in minor amounts, provided that 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 dyeing and tinting agents 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 CrC alkyl group or a CrC 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 CrC ₄ alkyl group,

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

R ⁶ represents a C _\ - C ₄ 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, (Vb)

in the independently of each other

R ¹ represents hydrogen, a C ¹ -C ₄ -alkyl group or a C 1 -C ₄ -hydroxyalkyl group,

R ³ represents hydrogen or a CrC ₄ alkyl group,

R ⁶ represents a Cr 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 hydrochloride, sulfates and hydrobromides can be 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 direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yelow 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-l, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-l, 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, rotten tree bark, 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 colorings are such carriers, 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 products 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 CrC ₄ alcohol, in particular ethanol or isopropanol. The agents according to the invention can additionally contain further organic solvents, such as, for example, 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 if, in addition to the coloring, an anti-bleaching effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents. It is also possible to carry out the oxidation with the aid of enzymes, the enzymes being used both for producing oxidizing per compounds and for enhancing the action of a small amount of oxidizing agents present. The enzymes (enzyme class 1: oxidoreductases) can transfer electrons from suitable developer components (reducing agents) to atmospheric oxygen. Oxidases such as tyrosinase, ascorbate oxidase and laccase are preferred, but also glucose oxidase, uricase or pyruvate oxidase. Furthermore, the procedure should be mentioned to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

The actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye products. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. The use of hair colorants in a weakly alkaline environment is particularly preferred. The application temperatures can range between 15 and 40 ° C.

After an exposure time of 5 to 45 minutes, the hair dye is rinsed off from the hair to be colored. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was 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, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. 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, Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-3725 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene angry 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-3926 344,

Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 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, Ct 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 ^J O- (Z) _χ . These connections are characterized by the following parameters.

I

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 are preferred. Examples of such alkyl radicals are 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 essentially consists of C ₈ - and C_o-alkyl groups, essentially from C ₁₂ - and C ₁₄ -alkyl groups, essentially from C ₈ - to C ₆ -alkyl groups or essentially from C ₁₂ - Cι ₆ 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 -SO ^ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium 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 understood to mean those surface-active compounds which contain in addition to a C ₈ -C ₁₈ alkyl or acyl group in the molecule 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 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 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C ₁₂ - ₁₈ - sarcosine.

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 trialkylmemylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylarnmonium chloride and tricetylmethylammonium chloride, as well as the compounds known under the INCI names Quaternium-27 and Quaternium-83 compounds imidazolium. 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, and 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. An inventively particularly suitable compound from this group is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine.

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 homologs that are used in the implementation of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. 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 grape.

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. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)), Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer commercially available products copolymers are examples of such cationic polymers. Of vinylpyrrolidone acrylate with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, quaternized with diethyl sulfate vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. such compounds are available under the names Gafquat ^® 734 and Gafquat ^® 755 commercially. vinylpyrrolidone methoimidazolinium chloride copolymers, such as 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.

Also suitable as conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethyipolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. 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 and the commercial products Q2-7224 (manufacturer: Dow Coming; 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).

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 vinylpyrrolidone-vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl-methacrylate / methyl-methacrylate / methyl-methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobomylacrylate copolymers, methyl vinyl ether and maleic acid / acrylic acid anhydride anhydrides tert-butyl-acrylamide polymers,

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. B. bentonite or fully synthetic hydrocolloids such as e.g. Polyvinyl alcohol,

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

Protein hydrolyzates, in particular 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 substances which improve the fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl l-alkylamidoethyl -2-alkylimidazolinium methosulfate defoamers such as 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, for example, 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, in particular 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, white dome, 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, Lemon Balm, Pickled Horn, Coltsfoot, Marshmallow, Meristem, Ginseng and Ginger Root .

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 alkanolamides,

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 agents for hydrogen peroxide and other oxidizing agents,

Propellants 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. A second object of the present invention is a process for dyeing keratin fibers, in which an agent according to the invention is applied to the fibers and is rinsed out again after an exposure time.

A third object of the present invention is the use of a dye combination

(A) 2-amino-5-methylphenol and

(B) at least one further dye product selected from N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 2,6-dichloro-4-aminophenol, 2,6-dibromo-4-aminophenol, 4-methylaminophenol , 2-diethylaminomethyl-4-aminophenol, 2-aminophenol, 2-amino-4-methylphenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5 , 6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,5-diaminopyridine, 4,5-diamino-l- (2'-hydroxyethyl) pyrazole, 2-methylresorsin, 5- (2 '- Hydroxyethylamino) -2-methylphenol, 5 - (3'-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4 -methoxy-2-methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 2,4-dichloro-3-aminophenol, 1,3-bis- (2 ', 4'- diaminophenyl) propane, 2,4-diaminophenoxyethanol, 3, 5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2 '- hydroxyethylamino) anisole, 2,6-bis- (2nd '-hydroxyethyl) -l-methylbenzene, 2-amino-3-hydroxypyridine, 5-chloro-2-amino- 3-hydroxypyridine, 2,6-dimethoxy-3, 5-diaminopyridine, 2,6-dihydroxy-3, 5-dimethoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2-methylamino-3-amino-6- methoxypyridine, 2,3-diaminopyridine, l-hydroxy-2-methylnaphthalene, 1,5-dihydroxynaphthalene and 2,7-dihydroxynaphthalene for coloring keratin fibers.

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

The amounts in the examples are in percent by weight, unless otherwise stated.

1. Production of the coloring cream

Hydrenol ^® D ¹ 8.5

Lorol ^® techn. ² 2.0

Eumulgin ^® B2 ³ 0.75

Texapon ^® NSO ⁴ 20.0

Dehyton ^® K ⁵ 12.5

Sodium sulfite 0.5

Ammonium sulfate 0.4

Dye precursors see Tables I to IV

Ammonia (25% solution) ad pH = l 0.0

Propylene glycol 2.0

Water ad 100

Ci6-ι ₈ fatty alcohol (INCI name: Cetearyl alcohol) (Cognis) C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis) Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20 ) (Cognis)

Lauryl ether sulfate, sodium salt (approx. 27.5% active substance; INCI name: Sodium Laureth Sulfate) (Cognis)

N, N-dimethyl-N- (C _{_8-18} -kokosamidopropyl) ammoniumacetobetain (ca. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

The substances Hydrenol ^® D, Lorol ^® and Eumulgin ^® B2 were melted at 80 ° C, mixed with the 80 ° C hot water containing Texapon ^® NSO and Dehyton ^® K, and emulsified with vigorous stirring. The emulsion was then cooled with gentle stirring. The Dye Voφrodukte were in the 60 ° C. hot water with the addition of sodium sulfite, ammonium sulfate, ammonia and propylene glycol. This dye product solution was added to the emulsion, adjusted to pH = 10 with ammonia and made up to 100% by weight with water. The stirring was continued until the room temperature was reached.

2. Staining of the keratin fibers

The coloring cream obtained in this way was mixed in a ratio of 1: 1 with a 3% (experiments 1 to 14) or a 6% H ₂ O ₂ solution (experiments 15 to 17) and applied to 5 cm long strands of standardized, natural white, but not specially pretreated human hair (Kerling) applied (quantitative ratio of dye mixture: hair was 5: 1). After a contact time of 30 minutes at 32 ° C., the hair was rinsed, washed out with a customary shampoo and then dried. The coloring results according to the German Color Atlas can be found in Tables I to IV.

Table I

Table II

Table III

Table IV

Claims

claims

1. Agent for coloring keratin fibers, containing in a cosmetically acceptable medium as Dye Voφrodukte

(A) 2-amino-5-methylphenol and

(B) at least one further dye product selected from N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 2,6-dichloro-4-aminophenol, 2,6-dibromo-4-aminophenol, 4-methylaminophenol , 2-diethylaminomethyl-4-aminophenol, 2-aminophenol, 2-amino-4-methylphenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5 , 6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,5-diaminopyridine, 4,5-diamino-1 - (2 '-hydroxyethyl) -pyrazole, 2-methyhesorsin, 5 - (2' - Hydroxyethylamino) -2-methylphenol, 5- (3'-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4 -methoxy-2-methylphenol, N, N-dimethyl-3-amino-phenol, N-cyclopentyl-3-aminophenol, 2,4-dichloro-3-aminophenol, 1, 3-bis- (2 ', 4'- diaminophenyl) propane, 2,4-diaminophenoxyethanol, 3,5-diamino-2-methoxy-l-methylbenzene, 2-amino-4- (2'-hydroxyethylamino) anisole, 2,6-bis- (2nd '-hydroxyethyl) -l-methylbenzene, 2-amino-3-hydroxypyridine, 5-chloro-2-amino-3-hy hydroxypyridine, 2,6-dimethoxy-3, 5-diaminopyridine, 2,6-dihydroxy-3, 5-dimethoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,3-diaminopyridine, l-hydroxy-2-methylnaphthalene, 1,5-dihydroxynaphthalene and 2,7-dihydroxynaphthalene.

2. Composition according spoke 1, characterized in that component (B) is selected from

(A) 2-amino-5-methylphenol and

(B) at least one further dye product selected from N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 2,6-dichloro-4-aminophenol, 2,6-dibromo-4-aminophenol, 4-methylaminophenol , 2-diethylaminomethyl-4-aminophenol, 2-aminophenol, 2-amino-4-methylphenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5, 6-triaminopyrimidine, 2-hydroxy-4,5 , 6-triaminopyrimidine, 2- Dimethylamino-4,5,6-triaminopyrimidine, 2,5-diaminopyridine, 4,5-diamino-1 - (2'-hydroxyethyl) -pyrazole, 5 - (2'-hydroxyethylamino) -2-methylphenol, 5 - (3 '- hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, N, N-dimethyl-3-amino-phenol, N-cyclopentyl-3-aminophenol, 2,4-dichloro-3-aminophenol, 1,3-bis- (2 ', 4'-diaminophenyl) -propane, 2,4- Diaminophenoxyethanol, 3,5-diamino-2-methoxy-l-methylbenzene, 2,6-bis- (2'-hydroxyethyl) -l-methylbenzene, 2-amino-3-hydroxypyridine, 5-chloro-2- amino-3-hydroxypyridine, 2,6-dimethoxy-3, 5-diaminopyridine, 2,6-dihydroxy-3, 5-dimethoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2-methylamino-3-amino- 6-methoxypyridine, 2,3-diaminopyridine, 1-hydroxy-2-methylnaphthalene, 1,5-dihydroxynaphthalene and 2,7-dihydroxynaphthalene.

3. Composition according to one of claims 1 or 2, characterized in that it further contains at least one substantive dye.

4. A process for dyeing keratin fibers, characterized in that an agent according to one of claims 1 to 3 is applied to the fibers and is rinsed out again after an exposure time.

5. Use a dye combination

(A) 2-amino-5-methylphenol and

(B) at least one further dye product selected from N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 2,6-dichloro-4-aminophenol, 2,6-dibromo-4-aminophenol, 4-methylaminophenol , 2-diethylaminomethyl-4-aminophenol, 2-aminophenol, 2-amino-4-methylphenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5 , 6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,5-diaminopyridine, 4,5-diamino-1 - (2 '-hydroxyethyl) -pyrazole, 2-methyhesorsin, 5- (2' - hydroxyethylamino) -2- methylphenol, 5- (3'-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methy Iphenol, N, N-dimethyl-3-amino-phenol, N-cyclopentyl-3 aminophenol, 2,4-dichloro-3 aminophenol, 1, 3-bis ^(2, ^4, -diaminophenyl) propane, 2,4-diamino-phenoxyethanol, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2'-hydroxyethylamino) anisole, 2,6-bis (2'-hydroxyethyl) - l-methylbenzene, 2-amino-3-hydroxypyridine, 5-chloro-2-amino-3-hydroxypyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,6-dihydroxy-3,5-dimethoxypyridine, 2, 6-dihydroxy-3,4-dimethylpyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,3-

Diaminopyridine, l-hydroxy-2-methylnaphthalene, 1,5-dihydroxynaphthalene and 2,7-dihydroxynaphthalene for dyeing keratin fibers.