DE10120915A1 - Dyeing agent for keratin fibers, useful as a hair dye, comprises at least one indole- and indoline derivative, a developing agent and a direct dyestuff - Google Patents

Abstract

An agent (I) for dyeing keratin fibers comprises: (A) at least one indole- and indoline derivative; (B) at least one developing agent; and (C) at least one direct dyestuff. An Independent claim is also included for a process for dyeing keratin fibers using the agent (I).

Description

The present application relates to agents for the oxidative dyeing of keratinic fibers containing oxidation dye precursors, indole and / or indoline derivatives and directzie coloring agents, as well as the use of these agents as colorants.

Human hair is used today in a variety of ways with hair cosmetic preparations treated. These include cleaning the hair with shampoos, taking care and re generation with rinses and cures, as well as the bleaching, dyeing and shaping of the hair with colorants, tinting agents, waving agents and styling preparations. Play it Means for changing or nuancing the color of the hair of the head an outstanding Role.

For temporary dyeings usually dyeing or tinting agents are used, the as a coloring component so-called Direktzieher included. This is Dye molecules that grow directly on the hair and no oxidative process for Need training of the paint. For example, these dyes already belong Henna known from ancient times for coloring body and hair. These dyes are sensitive to shampooing in general, so that a often undesirable Shade shift or even a visible "discoloration" may occur.

For permanent, intense colorations with corresponding fastness properties so-called oxidation colorants used. Such colorants usually contain Oxidation dye precursors, so-called developer components and Kupplerkom  components. The developer components form under the influence of oxidants or of atmospheric oxygen with each other or under coupling with one or more Coupler components from the actual dyes. Draw the oxidation colorants characterized by excellent, long lasting staining results. For natural looking Dyeing is usually a mixture of a larger number of oxidation color substance precursors are used; in many cases will continue to be substantive Dyes used for shade.

But often in practice - especially in the fashion nuances in the red area - also in the oxidative dyeings unwanted nuances shifts by external Ein to observe rivers such as light, shampooing and sweat.

It is therefore still the task of oxidative dyeing - especially in Be rich of red fashions - to improve their authenticity. Overcoming the disadvantages with regard to one of these properties already provides a solution significant improvement of the prior art.

It has now surprisingly been found that these disadvantages of the prior art can be overcome with a special colorant.

A first object of the present invention is therefore a means for coloring kerati African fibers, the

• A) at least one indole and / or indoline derivative,
• B) at least one developing component, and
• C) at least one substantive dye

contains.

According to the invention, keratinic fibers include furs, wool, feathers and, in particular, furs understood human hair.

International Patent Application WO-A1-93 / 09759 discloses the use of spe cial Indolinderivaten as a dye component together with known direct draw  the dyes or with oxidation dye precursors from the coupler and developer described for the production of dyeings. But this font is not a hint to refer to the agent according to the invention.

In a first embodiment of the present invention, the agent contains component (A) as at least one indoline derivative. Indole derivatives of the formula (Ia) are preferred according to the invention.

in the independently of each other
R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or a C ₂ -C ₄ -polyhydroxyalkyl group,
R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ alkyl group, and
R ⁵ represents one of the groups mentioned under R ⁴ ,
or a physiologically acceptable salts of these compounds.

Examples of the C ₁ - to C ₄ -alkyl groups 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 groups. Preferred C ₁ -C ₄ -hydroxyalkyl groups are the groups hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; 2-Hy droxyethyl is a particularly preferred hydroxyalkyl group. Since all he inventive substances are amino compounds, can be prepared from these in the usual way, the known acid addition salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates.

Particularly preferred compounds of the formula (Ia) are selected from 5,6-di hydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-Pro pyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxvindoline-2-car bonsäure. 5,6-Dihydroxyindoline is a very particularly preferred component of Formula (I).

Furthermore, however, the indoline derivatives are 6-hydroxyindoline, 6-aminoindoline and 4-amino indoline is preferred according to the invention.

In a second embodiment of the present invention, the agent as component (A) contains at least one indole derivative. Preference is given to indole derivatives of the formula (Ib)

in the independently of each other
R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkylene or a C ₂ -C ₄ -polyhydroxyalkyl group,
R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ in which
R ⁶ is a C ₁ -C ₄ alkyl group, and
R ⁵ represents one of the groups mentioned under R ⁴ ,
and one of the physiologically acceptable salts of these compounds.

Examples of the C ₁ - to C ₄ -alkyl groups 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 groups. Preferred C ₁ -C ₄ -hydroxyalkyl groups are the groups hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; 2-Hy droxyethyl is a particularly preferred hydroxyalkyl group. Since all he inventive substances are amino compounds, can be prepared from these in the usual way, the known acid addition salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates.

Particularly preferred indole derivatives of the formula (Ib) are selected from 5,6-di hydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihy droxyindole, N-butyl-5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid. 5,6-Dihydroxyindole is a very particularly preferred indole derivative of the formula (Ib).

Furthermore, the indole derivatives have 6-hydroxyindole, 6-aminoindole and 4-amino indole proved to be suitable according to the invention.

In a further embodiment of the present invention, the agent may be described as Kom component (A) contain at least one indole derivative and at least one indoline derivative.

Furthermore, the agent according to the invention contains as component (B) at least one Ent wicklerkomponente.

It may be preferred according to the invention to use as a developer component a p-phenylene diamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which

• G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ mono-hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkyl koxy (C ₁ to C ₄ ) alkyl radical, a 4'-aminophenyl radical or a C ₁ to C ₄ alkyl radical which is substituted with a nitrogen-containing group, a phenyl or a 4'-amino phenyl radical;
• G ² represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ mono hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkyl koxy (C ₁ to C ₄ ) alkyl radical or a C ₁ to C ₄ alkyl radical substituted with a nitrogen containing group;
• G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₁ to C ₄ -Hydroxyalkoxy radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ acyl aminoalkoxy radical, a C ₁ to C ₄ mesylaminoalkoxy radical or a C ₁ to C ₄ carbamoylaminoalkoxy radical;
• G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ to C ₄ alkyl radical or
• when G ³ and G ⁴ are ortho to each other, they may together form a bridging .alpha.,. omega.-alkylenedioxy 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. Preferred C ₁ -C ₄ -alkoxy radicals according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxy methyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. Examples of halo genatome according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (II) are, in particular, the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups; C ₁ - to C ₄ -monohydroxyalkyl amino groups, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-Phe nylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-pheny lendiamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phe nylenediamine, 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 (β-Hy droxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-Hy droxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phe nylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylene diamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylene diamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-Hy droxyethyloxy) -p-phenylenediamine, 2- (b-acetylaminoethyloxy) -p-phenylenediamine, N- (β-Me thoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physio logically compatible salts.

Very particularly preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

It may further be preferred according to the invention, as a developer component verbin use at least two aromatic nuclei containing amino and / or Hydroxyl groups are substituted.

Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made, in particular, of the compounds corresponding to the following formula (E2) and their physiologically tolerable salts:

in which:

• - Z ¹ and Z ² are each independently a hydroxyl or NH ₂ radical optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -Hy droxyalkylradikal and / or by a bridge Y is substituted or which may be part of a bridging ring system,
• the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring interrupted by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be terminated and may be optionally substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, or a direct bond,
• - G ⁵ and G ⁶ are each independently a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -Monohydroxyalkylradikal, a C ₂ - to C ₄ - poly hydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that
• The compounds of the formula (E2) contain only one bridge Y per molecule and
• - The compounds of formula (E2) contain at least one amino group, the min at least one hydrogen atom.

The substituents used in formula (E2) are analogous to the above according to the invention Executions defined.  

Preferred binuclear developer components of the formula (E2) are in particular:
N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-Hy droxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) -tetra-methylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethyllenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) -N, N'-bis ( 4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,4-bis (4'-aminophenyl) -diazacycloheptane, N, N'-bis ( 2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetra oxadecane and its physiologically tolerable salts.

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hy droxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiologically ver suitable salts.

Furthermore, it may be preferred according to the invention to use as a developer component, a p-amino phenol derivative or one of its physiologically acceptable salts. Particularly preferred are p-aminophenol derivatives of the formula (E3)

in which:

• G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) Alkoxy (C ₁ to C ₄ ) alkyl radical, C ₁ to C ₄ aminoalkyl radical, hydroxy (C ₁ to C ₄ ) alkylaminoradical, C ₁ to C ₄ hydroxyalkoxy radical, C C ₁ to C ₄ hydroxyalkyl (C ₁ to C ₄ ) aminoalkyl radical or (C ₁ to C ₄ alkylamino) (C ₁ to C ₄ ) alkycadical, and
• G ¹⁴ represents a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkoxy - (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ -cyanoalkyl radical,
• G ¹⁵ is hydrogen, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ mono-hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

The substituents used in formula (E3) are analogous to the above according to the invention Executions defined.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-Me ethyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxy methylamino-4-amino-phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (2-hy droxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-Ami no-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hy droxyethyl-aminomethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-di Chloro-4-aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol and its physiological Gisch compatible salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-Ami no-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2 - ((diethyl amino) methyl) phenol.

Further, the developer component may be selected from o-aminophenol and its Derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-Ami no-4-chlorophenol.  

Furthermore, the developer component may be selected from heterocyclic Ent components such as the pyridine, pyrimidine, pyrazole, pyrazole Pyrimidine derivatives and their physiologically acceptable salts. In a special off Guidance form, the use of pyrimidine derivatives may be particularly preferred.

Preferred pyridine derivatives are in particular the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4-Me thoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-Me thoxyethyl) amino-3-amino-6-methoxypyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are in particular the compounds described in the German Patent DE 23 59 399, Japanese Patent Application JP 020 19 576 A2 or in the Offenlegungsschrift WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethyl amino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-tri aminopyrimidine. 2,4,5,6-tetraaminopyrimidine is a particularly preferred pyrimi dinderivat.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 38 43 892, DE 41 33 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 4,5-dia Mino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chloro benzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino pyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methyl pyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-me thylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-meth oxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hy droxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-di amino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl pyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-me thylaminopyrazole and 3,5-diamino-4 (β-hydroxyethyl) amino-1-methylpyrazole.  

Preferred pyrazole-pyrimidine derivatives are in particular the derivatives of the pyrazolo [1,5-a] -py-rimidine of the following formula (E4) and its tautomeric forms, provided that a tauto meres equilibrium exists:

in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl radical, a C ₁ to C ₄ aminoalkyl radical optionally protected by an acetyl-ureide or sulfonyl radical may be a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl radical, a di - [(C ₁ to C ₄ alkyl) (C ₁ to C ₄ ) aminoalkyl radical where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) -amino alkyl radical,
• the X radicals independently of one another represent a hydrogen atom, a C ₁ to C ₄ alkyl radical, an aryl radical, a C ₁ to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl radical, a di - [(C ₁ - to C ₄ ) -alkyl] - (C ₁ - to C ₄ ) -aminoalkyl radicals, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, a C ₁ to C ₄ alkyl or di (C ₁ 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 equals 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the 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 ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

The substituents used in formula (E4) are according to the invention analogous to the above Executions defined.

If the pyrazolo [1,5-a] pyrimidine of the above formula (E4) contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is represented, for example, in the following scheme:

Among the pyrazolo [1,5-a] -pyrimidines of the above formula (E4) can be called in particular special:

• - pyrazole [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] -pyrimidine-3,5-diamine;
• 3-amino-pyrazolo [1,5-a] -pyrimidin-7-ol;
• 3-amino-pyrazolo [1,5-a] -pyrimidin-5-ol;
• - 2- (3-amino-pyrazolo [1,5-a] -pyrimidin-7-ylamino) -ethanol;
• - 2- (7-amino-pyrazolo [1,5-a] -pyrimidin-3-ylamino) -ethanol;
• - 2 - [(3-amino-pyrazolo [1,5-a] -pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-amino-pyrazolo [1,5-a] -pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;  
• 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5, N7, N7-tetramethylpyrazolo [1,5-a] -pyrimidine-3,7-diamine;

and their physiologically acceptable salts and their tautomeric forms when a tau tomeres equilibrium is present.

The pyrazolo [1,5-a] -pyrimidines of the above formula (E4) can be used as in the literature described by cyclization starting from an aminopyrazole or hydrazine getting produced.

Furthermore, the inventive composition may further contain at least one Kupplerkompo component. According to preferred coupler components are

• M-aminophenol and its derivatives such as 5-amino-2-methylphenol, 3-Amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-amino phenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methyl phenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methyl phenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-di hydroxy-5- (methylamino) -benzene, 3- (ethylamino) -4-methylphenol and 2,4-dichloro-3-amino phenol,
• O-aminophenol and its derivatives,
• - m-diaminobenzene and its derivatives such as 2,4-dia minophenoxyethanol, 1,3-bis (2,4-diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2'-hy droxyethylamino) benzene, 1,3-bis- (2,4-diaminophenyl) -propane, 2,6-bis (2-hy droxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) amino benzene,
• - o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
• - Di- or trihydroxybenzene derivatives such as resorcinol, Re sorcinomonomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chloro resorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-S-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-di  hydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopride, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• - Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-Hy droxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-di hydroxynaphthalene and 2,3-dihydroxynaphthalene,
• - Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-amino benzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-Hy droxyindol,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-di hydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-Ami no-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihy droxy-2-methylpyrimidine, or
• - Methylendioxybenzolderivate such as 1-hydroxy-3,4-methylene dioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-me thylendioxybenzol.

Especially preferred are m-aminophenol type coupler components. Furthermore are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-me thylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-amino phenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-di Methylpyridine according to the invention preferred coupler components. In a special ders preferred embodiment is used as the coupler component 2-methylresorcinol puts. This coupler component is particularly suitable as a coupler component for the educator nuances in the red area with pyrimidine derivatives.

As a third mandatory component (C), the compositions according to the invention contain at least a direct dye. Direct dyes are usually Ni trophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.  

Preferred substantive dyes are those under international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 52 th compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hy droxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-Hy droxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitro benzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitro phenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-car bonsäure, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramine acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Furthermore, the agents according to the invention may contain a cationic substantive dye. Particularly preferred are

• 1. cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• 2. aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well
• 3. substantive dyes containing a heterocycle containing at least one having a quaternary nitrogen atom, as described, for example, in EP-A2-998 908, to which reference is explicitly made at this point, in claims 6 to 11 to be named.

Preferred cationic substantive dyes of the group (C3) are in particular the following compounds:

The compounds of formulas (DZ1), (DZ3) and (DZ5) are most preferred cationic substantive dyes of the group (C3).

The agents according to the invention preferably contain the substantive dyes in one Amount of 0.01 to 20 wt .-%, based on the total colorant.

The agents of the invention preferably contain the active ingredients in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring  such carriers are for example creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other accessories preparations suitable for use on the hair.

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

The oxidative coloring of the fibers can in principle be carried out with atmospheric oxygen. before zugt but a chemical oxidizing agent is used, especially if in addition the coloration is desired a whitening effect on human hair. As oxidizing agent come persulfates, chlorites and in particular hydrogen peroxide or its plant tion products of urea, melamine and sodium borate in question. Furthermore, it is possible to carry out the oxidation with the aid of enzymes, wherein the enzymes for both Generation of oxidizing per-compounds are used as well as Ver Strengthening the effect of a small amount of existing oxidizing agent. So can the Enzymes (Enzyme Class 1: Oxidoreductases) Electrons from suitable developer compo nenten (reducing agent) transferred to atmospheric oxygen. Oxidases are preferred like tyrosinase and laccase but also glucose oxidase, uricase or pyruvate oxidase. Furthermore, the procedure is called the effect of small amounts (eg 1% and less ger, based on the total agent) to amplify hydrogen peroxide by peroxidases. In a preferred embodiment of the present invention, the coloring cream without addition of a preparation containing enzymes applied to the hair.

The actual application preparation is therefore expediently immediately before the application by mixing the preparation of the oxidizing agent with the inventions produced according to the invention means. The resulting ready to use Haarfärbeprä It should preferably have a pH in the range from 6 to 12. Especially be It is preferable to use the hair dye in a weakly alkaline medium. The  Application temperatures can range between 15 and 40 ° C. To In a reaction time of 5 to 45 minutes, the hair dye is removed by rinsing removed from the hair to be dyed. The Nachwaschen with a shampoo is eliminated when a strongly surfactant-containing carrier, for. As a dyeing shampoo was used.

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

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. The se are characterized by a water-solubilizing, anionic group such as. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-; Di- and trialkanolammonium salts with 2 or 3 C 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 alkyl group having 10 to 22 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,
• - Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkylpolyoxyethylester having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,  
• Alpha-sulfofatty acid methyl esters of fatty acids containing 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 having 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulfated Hydroxyalkylpolyethylen- and / or Hydroxyalkylenpropylenglykolether according to DE-A-37 23 354,
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 doublebin 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 having 8 to 22 Represent C atoms.

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

Nonionic surfactants contain as hydrophilic group z. As a polyol group, a Po lyalkylenglykolethergruppe or a combination of polyol and polyglycol ether group. Such compounds are, for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 C atoms, to fatty acids having 12 to 22 C atoms and alkylphenols having 8 to 15 C atoms in the alkyl group,
• C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, and
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated Ri zinusöl.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These connections are identified by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and may be both linear and branched ver. Preference is given to primary linear and methyl-branched in the 2-position aliphati cal radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When so-called "oxo-alcohols" are used 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 one particular alkyl radical R ¹ . Usually, however, these compounds are made starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

Particular preference is given to those alkylpolyglycosides in which R ¹

• consisting essentially of C ₈ and C ₁₀ -alkyl groups,
• essentially of C ₁₂ and C ₁₄ alkyl groups,
• - Essentially from C ₈ - to C ₁₆ alkyl groups or
• - Consists essentially of C ₁₂ - to C ₁₆ -alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding Used oligosaccharides. Such sugars are, for example, glucose, fructose, galac tose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 Sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. All particularly preferred are alkyl glycosides in which x is 1.1 to 1.4.

The alkyl glycosides can also serve, in addition to their surfactant effect, the fixation to improve fragrance components on the hair. The person skilled in the art will therefore be  that on the duration of the hair treatment beyond the effect of the perfume oil on the hair is desired, preferably to this class of substance as further ingredient resort to the preparations of the invention.

The alkoxylated homologs of said alkylpolyglycosides can also be invented be used according to. These homologs can average up to 10 ethylene contain oxide and / or propylene oxide per alkyl glycoside unit.

Furthermore, especially as co-surfactants, zwitterionic surfactants who used the. As zwitterionic surfactants are those surface-active compounds be distinguished, which carry in the molecule at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammoniumglycinate, for example, the cocoalkyl dimethylammoniumglycinat, N-acyl-aminopropyl-N, N-dimethyl ammoniumglycinate, for example Kokosacylaminopropyl-dimethyl ammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethyl hydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Under on pholytic surfactants are those surface-active compounds understood that 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 capable of forming inner salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C-Ato men in the alkyl group. Particularly preferred ampholytic surfactants are N-coco alkylaminopropionate, Kokosacylaminoethylaminopropionat and C _12-18 -Acylsarco sin.

According to the invention as cationic surfactants in particular those of the type of quar ammonium compounds, esterquats and amidoamines.

Preferred quaternary ammonium compounds are ammonium halides, in particular These are chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethyl ammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylam ammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, Lauryldimethylbenzylammoniumchlorid and tricetyl methylammonium chloride, as well as those under the INCI names Quatemium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants mentioned preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain at least one ester radio tion 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 esters salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are included For example, sold under the trademarks StepanteKx®, Dehyquart® and Armocare®. The products Armocare® VGH-70, an N, N-bis (2-palmitoyloxyethyl) di Methyl ammonium chloride, as well as Dehyquart® F-75 and Dehyquart® AU-35 are examples for such esterquats.

The Alkylamidoamine are usually by amidation natural or synthetic fatty acids and fatty acid sections prepared with dialkylaminoamines. An inventor According to the invention, particularly suitable compound from this group of substances provides that the name Tegoamid® S 18 commercially available Stearamidopropyl-dimethylamine represents.

Further cationic surfactants which can be used according to the invention are the quaternized Protein hydrolysates.  

Also suitable according to the invention are cationic silicone oils, such as, for example, those described in US Pat Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trim thylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-mo modified silicone, 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 cationic surfactant employable quaternary sugar derivative the commercial product Glucquat®100, according to INCI nomenclature a "Lauryl Methyl Glu ceth-10 hydroxypropyl dimonium chlorides ".

Further preferred cationic surfactants which also have nourishing properties are the compounds of the formula (II)

In the formula (II), y is an integer of 0 to 2, x is an integer of 1 to 3 with the proviso that the sum of x and y is equal to 3.

In the compounds of the formula (II), M is also hydrogen, one equivalent of one Alkali or alkaline earth metal cations, an ammonium cation or an alkyl radical having 1 to 4 Carbon atoms, optionally with one or more hydroxy group (s) sub is substituted. Particularly preferred are compounds in which M is a sodium cation stands.

Furthermore, B in the formula (II) is the surfactants to be used according to the invention Equivalent to a physiologically acceptable anion. As an anion are beispielswei chloride, bromide, iodide, sulfate, perchlorate, tetrafluoroborate, tetraphenyl borate and Te trachlorozinkat. Preferably, the chloride ion.

R in the surfactants of the formula (II) according to the invention is a radical of the formula (III)

in which z is an integer from 1 to 4, in particular 3, and
R ¹ and R ² independently of one another are a C ₁ - to C ₄ -alkyl radical which, if appropriate, is substituted by one or more hydroxy group (s) or an acyl group.

A represents, according to the invention, one of the moieties -O-CH ₂ -CH ₂ -CH ₂ -, -O-CH ₂ -CH ₂ - or -O-CH ₂ -CHOH-CH ₂ -, where the moiety is -O-CH ₂ -CHOH-CH ₂ - is particularly preferred.

The radical R ³ stands for

• a) a branched or unbranched, saturated C ₈ - to C ₁₈ -acyl radical or
• b) a branched or unbranched, mono- or polyunsaturated C ₈ - to C ₁₈ -acyl radical.

Particularly preferred saturated radicals R ³ are the radical of stearic acid and also the radicals of the mixture of the fatty acids which are obtained from coconut oil.

A particularly preferred unsaturated radical R ³ is the radical of linoleic acid. Surprisingly, it has been found that compounds of the formula (II) in which R ^{3 is} the radical of linoleic acid are distinguished by a higher compatibility with emulsifier systems. This means that these substances are easier to incorporate into the formulations. Furthermore, formulations with compounds of the formula (II) in which R ^{3 is} the radical of linoleic acid have a significantly higher care effect in comparison with compounds having saturated fatty acid residues.

Very particularly preferred compounds of the formula (II) are those mentioned under the INCI Designations Linoleamidopropyl PG-Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate and Stearamidopropyl PG-Dimonium Chloride Phos phate known substances. These are, for example, by the company Mona under the Trade names Phospholipid EFA®, Phospholipid PTC® and Phospholipid SV® distributed.  

The compounds used as surfactant with alkyl groups may be in each case act uniform substances. However, it is usually preferred in the production These substances are based on native plant or animal raw materials, so that one Substance mixtures with different, dependent on the particular raw alkyl chain ten lengths.

For the surfactants, the adducts of ethylene and / or propylene oxide to fat Alcohols or derivatives of these addition products may represent both products with a "normal" homolog distribution as well as those with a narrow homologue genverteilung be used. Under "normal" homolog distribution are thereby Mixtures of homologues understood in the reaction of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or alkali obtained metal alkoxides as catalysts. Narrow homolog distributions become when, for example, hydrotalcites, alkaline earth metal salts of ethercar bonsäuren, alkaline earth metal oxides, hydroxides or alcoholates used as catalysts become. The use of products with restricted homolog distribution can be be preferred.

Furthermore, the agents used in the context of the method according to the invention also prefers a conditioning agent selected from the group consisting of cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, plant formed from oils and synthetic oils.

Cationic polymers may be preferred as conditioning agents. These are in usually polymers containing a quaternary nitrogen atom, for example in the form of an Am monium group.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as they are known under the names Celquat® and Po lymer JR® are commercially available. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.
• - Dimethyldiallylammoniumsalze polymeric and their copolymers with acrylic acid so such as esters and amides of acrylic acid and methacrylic acid. The under the designation  Merquat®100 (poly (dimethyldiallylammonium chloride)), Merquat®SSO (Di methyldiallylammonium chloride-acrylamide copolymer) and Merquat® 280 (Dime thyldiallylammonium chloride-acrylic acid copolymer commercially available products are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylates and methacrylates such as vinyl quaternized with diethyl sulfate pyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are under the names Gafquat®734 and Gafquat®755 commercially available.
• - Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, as described under the name Luviquat®.
• - Quaternized polyvinyl alcohol

as well as those under the designations

• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the Po lymerhauptkette.

Particularly preferred are cationic polymers of the first four groups, very be Polyquaternium-2, Polyquaternium-10 and Polyquaternium-22 are particularly preferred.

As conditioning agents further suitable silicone oils, especially dialkyl and Alkylarylsiloxanes such as dimethylpolysiloxane and methylphenylpolysi loxan, as well as their alkoxylated and quaternized analogs. Examples of such silicones are those of Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 distributed products as well as the commercial products Q2-7224 (manufacturer: Dow Coming; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino-modified silicone, which may also be described as amodimethicones characterized), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil® Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary Polydime methylsiloxanes, quaternium-80).  

Also usable as conditioning agents are paraffin oils, synthetically herge introduced oligomeric alkenes as well as vegetable oils such as jojoba oil, sunflower oil, orange oil, Almond oil, wheat germ oil and peach kernel oil.

Likewise suitable hair conditioning compounds are phospholipids, for example soy lecithin, E1 lecithin and cephaline.

Other active ingredients, auxiliaries and additives are, for example

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, Polyvinylpyrrolidone and Viaylpyrrolidon / vinyl acetate copolymers and polysiloxanes,
• Zwitterionic and amphoteric polymers such as acrylamidopropyl tri methylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate lat / tert-butylaminoethyl 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 / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide ter polymeric
• - Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum ara bicum, karaya gum, locust bean gum, linseed gums, dextran, cellu loose derivatives, e.g. Methylcellulose, hydroxyalkylcellulose and carboxymethylcel cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, To ne, such as As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair conditioning compounds such as phospholipids, for example soya lecithin, Egg lecithin and cephalins,
• - Protein hydrolysates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,  
• - Fiber structure improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose,
• Quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• Defoamers like silicones,
• Dyes for staining the agent,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - Sunscreens, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• - Substances for adjusting the pH, such as conventional acids, in particular special edible acids and bases;
• - active substances such as allantoin; Pyrrolidonecarboxylic 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 of green tea, oak bark, stinging nettle, Hama melis, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, Almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, Mango, Apricot, Lime, Wheat, Kiwi, Melon, Orange, Grapefruit, Sage, Ros male, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, Hominy, coltsfoot, marshmallow, meristem, ginseng and ginger root,
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• - fatty acid,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids, Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbo nate, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizing agent for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants.

Regarding further optional components as well as the amounts of this com components is expressly referred to the relevant manuals known to those skilled in the art, z. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989, referenced.

A second object of the present invention is the use of an inventive proper agent for coloring keratinic fibers.

A preferred embodiment of this article is the use of an invent A composition according to the invention for achieving intensive dyeings - especially in the field of Modenuancen - with an increased wash fastness.

A third object of the present invention is a method for coloring keratini shear fibers in which an agent according to the invention is applied to the fibers and after a contact time is rinsed off.

In a preferred embodiment, the agent used in the context of the Invention according to the method is applied to the fibers, further at least one Oxidati onsmittel, in particular hydrogen peroxide.  

Unless otherwise noted, the following information is by weight.

example 1

The formulations V1 and E1 would be in the half-page test on the heads of 10 Proban the tested. For this purpose, 60 g of the respective dyeing cream with 60 g of a 6% aqueous Mixed hydrogen peroxide preparation and the resulting application each applied to the fibers on one side of the subject's head. After a contact time of 30 minutes, the hair was rinsed thoroughly. After every Coloring and after each 3, 6, 12 and 18 times shampooing became the hair coloring assessed by 3 hairdressers visually on both sides. This process was at 3 aufeinan repeated staining at intervals of 4 weeks.

It showed consistently a more intense initial color and a significantly improved color containing the formulations with the addition of 5,6-dihydroxyindoline (E1). The color difference The hair halves of the volunteers emerged particularly after several washes clearly.  

Example 2

Ammoniumcarbopollsg. 1% ⁸ 10.00 Ammoniumrohagitlsg. 6% ⁹ 3.00 Hycryl Mulgol® 012 ¹⁰ 4.50 Potassium salt 12.5% pure 6.50 Potassium castor soap 12.5% 2.00 Plantaren® 2000 CS / UP ¹¹ 0.50 Titanium dioxide 0.20 Cetiol®V ¹² 2.50 cetyl alcohol 10.00 Glycerol monostearate NSE ¹³ 2.00 Phospholipid EFA 0.50 Tetrasodium EDTA 0.30 Mirapol A-15 0.15 ascorbic acid 0.10 sodium 0.10 Ammonia 25% 4.00 Perfume 0.50 3-methyl-4-aminophenol 0.50 p-toluenediamine 0.05 α-naphthol 0.50 5-amino-2-methylphenol 0.10 HC Red BN 0.50 HC Red 3 0.30 5,6-Dihydroxyindolin 0.25 water ad 100.00 ⁸ Solution of an ammonium salt of a methacrylic acid-methyl acrylate copolymer (INCI name: Ammonium Polyacrylate) (Röhm GmbH) @ ⁹ Solution of an ammonium salt of an acrylic acid polymer (INCI name: Ammonium Acrylates Copolymer) (Goodrich) @ ¹⁰ oleyl alcohol with 10 EO units (Chemische Fabrik Dr. Angele GmbH) @ ¹¹ C _8-16 -alkyl-1,4-polyglucoside (about 51% active ingredient, INCI name: decyl glucoside) (Henkel) @ ¹² Oleic acid decyl ester (INCI name: Decyl Oleate) (Henkel) @ ¹³ (INCI name: Glyceryl Strearate) (Oleofina)

60 g of the dyeing cream were prepared with 60 g of a 6% aqueous hydrogen peroxide mixed and the resulting application preparation applied to the fibers. After a contact time of 30 minutes, the hair was rinsed thoroughly.

Claims (21)

1. agent for coloring keratinic fibers, characterized in that it

• A) at least one indole and / or indoline derivative,
• B) at least one developing component, and
• C) contains at least one substantive dye.

2. Composition according to claim 1, characterized in that at least one indoline derivative of the formula (Ia) as component (A)
in the independently of each other
R ₁ is hydrogen, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or a C ₂ -C ₄ -polyhydroxyalkyl group,
R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-Rt in the
R ⁶ is a C ₁ -C ₄ alkyl group, and
R5 stands for one of the groups mentioned under R ⁴ ,
or a physiologically acceptable salts of these compounds. 3. Composition according to claim 2, characterized in that the compound of formula (Ia) is selected from 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-di hydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid. 4. Composition according to claim 3, characterized in that the compound of formula (Ia) 5,6-dihydroxyindoline.   5. Composition according to one of claims 1 to 4, characterized in that it as compo nent (A) at least one indole derivative of the formula (Ib)
in the independently of each other
R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or a C ₂ -C ₄ -polyhydroxyalkyl group;
R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ in which
R ⁶ is a C ₁ -C ₄ alkyl group, and
R ⁵ represents one of the groups mentioned under R ⁴ ,
and one of the physiologically acceptable salts of this compound. 6. Composition according to claim 5, characterized in that the indole derivative of the formula (Ib) is selected from 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-di hydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and 5,6-di hydroxyindole-2-carboxylic acid. 7. Composition according to claim 6, characterized in that the indole derivative of the formula (Ib) 5,6-dihydroxyindole. 8. Composition according to one of claims 1 to 7, characterized in that it as Ent Winder component (B) contains at least one Pyrimidinderivat. 9. Composition according to claim 8, characterized in that the pyrimidine derivative 2,4,5,6-Te is traaminopyrimidine.   10. Composition according to one of claims 1 to 9, characterized in that it as Ent Winder component (B) contains at least one p-aminophenol derivative. 11. Composition according to claim 10, characterized in that the p-aminophenol derivative is selected from p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methyl phenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-amino-phenol, 4-amino-3-hy droxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methyl phenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-Ami no-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) -phenol, 4-Ami no-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro-4-aminophenol, 4-Ami no-2 - ((diethylamino) methyl) phenol and its physiologically acceptable salts Zen. 12. Composition according to one of claims 1 to 11, characterized in that it continues contains at least one coupler component. 13. Composition according to claim 12, characterized in that the coupler component is a m- Aminophenolderivat is. 14. Composition according to claim 13, characterized in that the m-aminophenol derivative is selected from 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-Hy hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetyl amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-meth oxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) - phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3- (ethyl amino) -4-methylphenol and 2,4-dichloro-3-aminophenol. 15. Composition according to one of claims 1 to 14, characterized in that it as Kupp lerkomponente contains at least one resorcinol derivative. 16. A composition according to claim 15, characterized in that the resorcinol derivative is selected from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-Me thylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene.   17. Composition according to claim 16, characterized in that the resorcinol derivative 2- Methylresorcin is. 18. Use of a composition according to any one of claims 1 to 17 for coloring keratini shear fibers. 19. Use according to claim 18 for increasing the wash fastness of the resulting Coloring, especially in the area of red nuances. 20. A process for coloring keratinic fibers, in which an agent containing

• A) at least one indole and / or indoline derivative,
• B) at least one developing component, and
• C) at least one substantive dye is applied to the fibers and rinsed after a contact time.

21. The method according to claim 20, characterized in that the means further comprises Oxidizing agent, in particular hydrogen peroxide.