EP1858594A1 - Ammonia-free oxidation dye for dyeing keratin fibers with atmospheric oxygen serving as the sole oxidizing agent - Google Patents

Abstract

The invention relates to agents for dying keratin fibers induced by atmospheric oxygen. These agents contain at least one dye precursor for a nature-analogous dye selected from the group consisting of indole derivatives or indoline derivatives, at least one oxidation dyestuff initial product of the developer type, and at least one oxidation dye initial product of the coupler type, and do not contain ammonia nor additional oxidizing agents. The dyings obtained by using these agents are intense, long-lasting and do not have any red, blue or purple cast.

Description

 AMMONIA-FREE OXIDATIOSCREEN AGENT FOR

FÄRBURG KERATINE-CONTAINING FASEM WITH LIQUID OXYGEN AS A SINGLE OXIDIZING AGENT

The present invention relates to agents for coloring keratin fibers and their use and a corresponding hair dyeing process. The compositions comprise at least one dye-precursor for a naturally-analogous dye selected from the group of the indole or indoline derivatives, at least one developer-type oxidation dye precursor and at least one coupler-type oxidation dye precursor and are free of (a) ammonia and (b) additional oxidants.

Human hair is treated today in a variety of ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures and the bleaching, dyeing and shaping of the hair with dyes, tinting agents, waving agents and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role.

For temporary dyeings usually dyeing or tinting agents are used which contain so-called direct drawers as a coloring component. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the paint. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyes are usually sensitive to shampooing, so that a much undesirable nuance shift or even a visible "discoloration" can occur.

Another way to stain keratin-containing fibers is through the use of stains containing a combination of component A reactive carbonyl compounds, ie compounds having at least one reactive

Carbonyl group, and component

B Compounds selected from (a) CH-acidic compounds, (b) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (c) amino acids, (d) from 2 contain up to 9 amino acids constructed oligopeptides. The aforementioned components A and B are generally not themselves dyes, and therefore are not suitable alone for dyeing keratinhaltiger fibers alone. In combination, they form dyes in a non-oxidative process. However, it is also possible to use corresponding developer and / or coupler-type oxidation dye precursors with or without the use of an oxidizing agent under compounds of component B. Thus, this staining method (hereinafter called oxo staining) can be readily combined with the oxidative staining system. Components A and B are referred to below as Oxofarbstoffvorprodukte. The oxo dyeing is described, for example, in the publications WO-A1-99 / 18916, WO-A1 -00 / 38638, WO-A1-01/34106 and WO-A1-0 01/47483.

The publications WO-A2-99 / 18916 and WO-A1-01 / 47483 disclose the use of onium aldehydes and ketones, in particular of 2- or 4-formyl-1-methylquinolinium compounds, for dyeing keratin-containing fibers which in combination with compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, and / or CH-acidic compounds.

For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, of the so-called developer type

(Developer component) and coupler type (coupler component). The developer components form under the influence of oxidants or of atmospheric oxygen with one another or under coupling with one or more Coupler components from the actual dyes. The oxidation stains are characterized by excellent, long lasting staining results.

Finally, another dyeing process has received much attention. In this method, precursors of the natural hair dye melanin are applied to the hair; These then form naturally-analogous dyes in the course of oxidative processes in the hair. Such a process with 5,6-dihydroxyindoline as dye precursor was described in EP-B1-530 229. In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The dyeing can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agent must be used.

The dyeing is preferably carried out gently with atmospheric oxygen. The dye precursors on indole or indoline base usually used are incorporated for this purpose in a cosmetic carrier, which preferably has a basic pH. The coloration according to this method results in a natural black, brown or blonde coloration of keratin-containing fiber, which, however, especially in the brown and blond area has a slight reddish, bluish or violet color nuance. If additional oxidizing agents are used in the colorants, these color shifts occur negligibly or even not at all.

Dyes based on nature-analogous dyes appeal to those consumers who want to gently restore their gray hair to a natural hair color. The aforementioned color shift is undesirable especially for this consumer. Therefore, the coloration with natural dyes is in this respect in need of improvement.

From the document EP-B1-1 098 627 hair dyes based on dye precursors of indole or Indoltn type are known, which additionally contain at least one amino acid or an oligopeptide to improve the colorations on grayed hair. The dyeings obtained on blond hair all have an undesirable red or blue cast. From EP-B1-613 366 hair dyes are known which, in addition to an indoline-type dye precursor, 0.05 to 5 wt.% Of at least one oxidation dye precursor of the developer type and 0.05 to 5 wt.% Of at least one oxidation dye precursor coupler type. It has been found that the indoline derivatives improve the dyeing properties of conventional developer and coupler based oxidation colorants.

Document EP-A2-1 254 650 discloses hair colorants which, in addition to indoline derivatives as dye precursor, contain at least one selected organic primary amine as alkalizing agent. When using these colorants, brown to black dyeings should be obtained without a reddish color shift. However, the results obtained with these colorants are still unsatisfactory.

It is therefore an object of the present invention to provide a colorant based on naturally-analogous dyes which imparts natural blond, brown or black shades under air oxidation to nucleated fibers without causing undesirable reddish, bluish or violet color shifts. Furthermore, the dyeings should be intense and long-lasting.

It has surprisingly been found that colorants based on indole or indoline derivatives under air oxidation lead to intensive, long-lived and natural colorations without color shift, if in addition at least one alkalizing agent and oxidation dye precursors of the developer type and coupler type are contained in this agent and the agents are free from Ammonia.

A first subject of the invention are therefore agents for the atmospheric oxygen-induced coloring of keratin-containing fibers, in particular human hair, in a cosmetically acceptable carrier

(a) at least one indole and / or indoline derivative as the dye precursor of a naturally-analogous dye,

(b) at least one developer-type oxidation dye precursor,

(c) at least one coupler-type oxidation dye precursor and

(d) at least one alkalizing agent, with the proviso that

- The means are free of ammonia and no additional oxidizing agent for the components (a), (b) and (c) is included.

According to the invention, keratin-containing fibers are understood to mean furs, wool, feathers and in particular human hair. Although the colorants according to the invention are primarily suitable for dyeing keratinic fibers, in principle there is no obstacle to their use also in other areas of coloration, as long as the technical problem underlying the invention is solved.

As indoline derivatives of the feature (a) of the agent according to the invention, preference is given to compounds of the formula (Ia) and / or their physiologically tolerable salts with an organic or inorganic acid in the agents according to the invention,

wherein

R ¹ is hydrogen, a C _r C ₄ -alkyl group or a C 1 -C ₄ -hydroxy-alkyl group,

R ² is hydrogen or a -COOH group, where 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 _r C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C _r C ₄ alkyl group, and

- R ⁵ is one of the groups mentioned under R ⁴ .

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.

Particularly noteworthy 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 5, 6-Dihydroxyindolin.

Derivatives of the 5,6-dihydroxyindole of the formula (Ib) or their physiologically tolerable salts with an organic or inorganic acid are also suitable as precursors of naturally-analogous hair dyes according to feature (a) of the composition according to the invention.

wherein

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

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

R ³ is hydrogen or a C _r C ₄ -alkyl group,

- R ⁴ represents hydrogen, -C ₄ alkyl group or a group -CO-R ⁶ in which R ⁶ represents a C _r C ₄ alkyl group, and

R ⁵ is one of the groups mentioned under R ⁴ ,

- As well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

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. Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.

The indoline and indole derivatives can be used in the colorants of the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for. As the hydrochlorides, sulfates and hydrobromides are used.

The precursors of naturally-analogous dyes are preferably present in the compositions according to the invention in an amount of from 0.01 to 10% by weight, in particular from 0.1 to 5% by weight, based in each case on the weight of the ready-to-use colorant.

The oxidation dye precursors of the developer type of the feature (b) of the agents according to the invention are preferably present in an amount of 0.01 to 5 wt .-%, in particular from 0.1 to 3 wt .-%, each based on the weight of the ready dye.

It may be preferred according to the invention to select the developer components according to the invention from the group which is formed from p-phenylenediamine derivatives, binuclear developer components, p-aminophenol and its derivatives, pyrimidine derivatives, pyrazole derivatives and pyrazolopyrimidine derivatives and the physiologically acceptable salts of these compounds. In the following, preferred developer components are mentioned according to the invention.

Particularly preferred according to the invention are p-phenylenediamine derivatives of the formula (E1)

(El)

G ¹ represents a hydrogen atom, a C ₁ - to C ₄ alkyl, 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 4'-aminophenyl radical or a C ₁ - 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 ₁ - to C ₄ alkyl, 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 or a C ₁ - 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 C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ Polyhydroxyalkyl, C ₁ to C ₄ hydroxyalkoxy, C ₁ to C ₄ acetylaminoalkoxy, C ₁ to C ₄ mesylaminoalkoxy or C ₁ to C ₄ carbamoylaminoalkoxy;

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 α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group ,

Examples of the C ₁ - 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. C ₁ -C ₄ -alkoxy radicals which are preferred 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 hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are 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 (E1) are especially the amino groups, C ₁ - to C ₄ monoalkylamino, C ₁ - to C ₄ dialkylamino, C ₁ - to C ₄ -Trialkylammoniumgruppen, C ₁ - to C ₄ - Monohydroxyalkylaminogruppen, Imidazolinium and ammonium. Particularly preferred p-phenylenediamines of the formula (E1) 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 (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2 methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2 Fluoropenthenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N , N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-ace tylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine and 5 , 8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

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

It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

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 tolerated 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 C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or which is optionally 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, which is one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen , Sulfur or nitrogen atoms may be interrupted or terminated and may possibly be substituted by one or more hydroxyl or C ₁ - to C ₈ -alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently of one another represent 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 -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 independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the proviso that the compounds of the Formula (E2) contain only one bridge Y per molecule.

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

Preferred binuclear developer component of the formula (E2) are in particular: N, N ^l-bis (.beta.-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) - tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetrannethylenediamine, N, N '-Diethyl- N.N'-bis - ^' - amino-S'-methylphenyO-ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis- (2 ', 5 '- diaminophenyl) -1,4,7,10-tetraoxadecane and its physiologically acceptable 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-hydroxy-5-aminophenyl) -methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4- diazacycloheptane and 1, 10-bis- (2,5-diaminophenyl) -1, 4, 7, 10-tetraoxadecane or one of their physiologically acceptable salts.

Furthermore, it may be preferred according to the invention to use as the developer component p-aminophenol or a p-aminophenol derivative or one of the physiologically tolerated salts of the abovementioned compounds. Particular preference is given to 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 _r to C ₄ ) alkyl, a C ₁ - to C ₄ -Aminoalkylrest, a hydroxy (C _r to C ₄ ) alkylamino, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - C ₄ hydroxyalkyl aminoalkyl (C _r to C _4), or (di-C ₁ - to C ₄ -alkylamino) - alkyl group (Cr to _C4), and

G ¹⁴ is 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 _r to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C _r to C ₄ -cyanoalkyl radical, G ¹⁵ is hydrogen, C ₁ - to C ₄ alkyl, 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 is hydrogen or a halogen atom.

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

Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2 ~ (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino 2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino 2- (diethylaminomethyl) -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-amino-4-chlorophenol.

Further, the developer component may be selected from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazolopyrimidine derivatives and their physiologically acceptable salts.

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-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 selected according to the invention from compounds of the formula (E4),

wherein

G ¹⁷ , G ¹⁸ and G ¹⁹ independently represent a hydrogen atom, a hydroxy group, a (C _r C ₆ ) alkoxy group or an amino group and

G ^{20 represents} a hydroxy group or a group -NG ²¹ G ²² , wherein G ²¹ and

G ²² independently of one another represent a hydrogen atom, a (C ₁ -C ₆ ) -alkyl group, a (C ₁ -C ₆ ) -hydroxyalkyl group, with the proviso that at most two of the groups G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a hydroxy group and at most two of the radicals G ¹⁷ , G ¹⁸ and G ^{19 are} a hydrogen atom.

Particularly preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open specification JP 02019576 A2 or in published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy -2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6 -Triaminopyrimidin.

Preferred pyrazole derivatives are selected according to the invention from compounds of the formula (E5),

wherein

G ²³ , G ²⁴ , G ²⁵ independently of one another represent a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₂ to C ₆ monohydroxyalkyl group, a C ₂ to C ₆ polyhydroxyalkyl group, an optionally substituted aryl group or an optionally substituted aryl-C ₁ to C ₆ alkyl group and

G ²⁶ represents a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₂ to C ₆ -

Monohydroxyalkyl group or a C ₂ to C ₆ polyhydroxyalkyl group.

Particularly preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 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-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4.5 Diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino-pyrazole , 1-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-1- (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-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethyl lpyrazol.

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E6) and its tautomeric forms, provided that a tautomeric equilibrium exists:

G ^27, G ^28, G ²⁹ and G ³⁰ are independently a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a Ci to C ₄ -hydroxyalkyl group, a C ₄ polyhydroxyalkyl radical Gabis a ( C ₁ - to C ^ -Akoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, which may be protected by an acetyl-ureide or a sulfonyl radical, a (C ₁ - to C ₄₎ alkylamino (C _r to C, alkyl group a Di ₄₎ - [(C _r to C ₄₎ alkyl] - (C _r to C ₄₎ aminoalkyl, wherein the dialkyl residues optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (Ci- to C ₄ ) - [hydroxyalkyl] - (C _r to C ₄ ) -aminoalkyl radical, the X radicals are each independently a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, a (C ₁ - b , is C ₄₎ alkylamino (C _r to C alkyl group ₄₎ a DH (C ₁ - to C ₄₎ alkyl] - (C ₁ - to C ₄₎ aminoalkyl, wherein the dialkyl residues optionally a carbon cycle or form a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ - hydroxyalkyl) aminoalkyl, an amino, 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 ²⁷ G ²⁸ and NG ²⁹ G ³⁰ 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 ²⁷ G ²⁸ (or NG ²⁹ G ³⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); The substituents used in formula (E6) are defined according to the invention analogously to the above statements.

When the pyrazolo [1,5-a] pyrimidine of the above formula (E6) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium shown, for example, in the following scheme:

Among the pyrazolo [1, 5-a] pyrimidines of the above formula (E6) may be mentioned in particular:

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

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

Pyrazolo [1,5-a] pyrimidine-3,5-diamine;

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

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

3-aminopyrazolo [1,5-a] pyrimidine-5-ol;

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

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

2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

2 - [(7-aminopyrazolo [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;

3-Amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine; and their physiologically acceptable salts and their tautomeric forms when tautomeric equilibrium is present. The pyrazolo [1, 5-a] -pyrimidines of the above formula (E6) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.

The coupler components used are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives. Suitable coupler substances are, in particular, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1 Phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol , 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Coupler components (c) which are preferred according to the invention are selected from at least one member of the group of compounds which is formed from m-aminophenol and its derivatives, such as preferably 5-amino-2-methylphenol, IM-cyclopentyl-3-aminophenol, 3-amino- 2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5 (methylamino) benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol,

o-aminophenol and its derivatives,

m-phenylenediamine and its derivatives, such as preferably 2,4-diaminophenoxyethanol, 1,3-bis (2, ¹ , 4'-diaminophenoxy) -propane, 2-amino-1-methoxy-4- (2-hydroxyethylamino) -benzene, 1 , 3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene , 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 2 - ({3- [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol and 2 - [(3-morpholin-4-ylphenyl) amino] ethanol, o-phenylenediamine and its derivatives such as preferably 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as preferably resorcinol and derivatives (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 preferably 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 preferably mono- or Dihydroxynaphthalinderivate, 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, 1, 3-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives, such as preferably 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as preferably 6-methyl-1,2,3,4-tetrahydroquinoxaline,

- Pyrazolonderivate as preferred 1-phenyl-3-methylpyrazol-5-one and

Methylenedioxybenzene derivatives such as preferably 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

For the purposes of the invention, it is preferable to combine the dye precursors of naturally-occurring dyes of the indole or indoline type with at least one of the following combinations of developer and coupler components according to Table 1: Table 1: preferred combinations of developer and coupler components

The respective developer or coupler components according to Table 1 are preferably selected from their preferred individual representatives and / or their physiologically acceptable salts mentioned above in the context of the respective classes of compounds. It is very particularly preferred that the agents according to the invention comprise at least one of the following feature combinations for the features (b) and (c): Particularly preferred combinations according to K1 from Table 1 are: p-toluenediamine and resorcinol 2- (β-hydroxyethyl) -p-phenylenediamine and resorcinol p-toluenediamine and 2-methylresorcinol 2- (β-hydroxyethyl) -p-phenylenediamine and 2-methylresorcinol p-toluenediamine and 4-chlororesorcinol 2- (β-hydroxyethyl) -p-phenylenediamine and 4-chlororesorcinol

2- (β-hydroxyethyl) -p-phenylenediamine, 2-methylresorcinol and 2-amino-3-hydroxypyridine 2- (β-hydroxyethyl) -p-phenylenediamine, 2-methylresorcinol and 1,5-dihydroxynaphthalene

Particularly preferred combinations according to K2 from Table 1 are: 4,5-diamino-1- (2-hydroxyethyl) pyrazole and resorcinol 4,5-diamino-1- (2-hydroxyethyl) pyrazole and 2-methylresorcinol 4,5-diamino- 1- (2-hydroxyethyl) pyrazole and 4-chlororesorcinol

Particularly preferred combinations according to K3 from Table 1 are: 2,4,5,6-tetraaminopyrimidine and resorcinol 2,4,5,6-tetraaminopyrimidine and 2-methylresorcinol 2,4,5,6-tetraaminopyrimidine and 4-chlororesorcinol 4-hydroxy -2,5,6-triaminopyrimidine and resorcinol 4-hydroxy-2,5,6-triaminopyrimidine and 2-methylresorcinol 4-hydroxy-2,5,6-triaminopyrimidine and 4-chlororesorcinol 2,4,5,6-tetraaminopyrimidine, 2-methylresorcinol and 1, 5-dihydroxynaphthalene

Particularly preferred combinations according to K4 from Table 1 are: bis (2-hydroxy-5-aminophenyl) methane and resorcinol bis (2-hydroxy-5-aminophenyl) methane and 2-methylresorcinol bis (2-hydroxy-5 -aminophenyl) -methane and 4-chlororesorcinol

Particularly preferred combinations according to K5 from Table 1 are: p-aminophenol and 2,4-diaminophenoxyethanol p-aminophenol and 2-amino-1-methoxy-4- (2-hydroxyethylamino) benzene p-aminophenol and 2,6-bis ( 2'-hydroxyethylamino) -1-methylbenzene 4-amino-3-methylphenol and 2,4-diaminophenoxyethanol 4-Amino-3-methylphenol and 2-amino-1-methoxy-4- (2-hydroxyethylamino) -benzene 4-Amino-3-methylphenol and 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene

Particularly preferred combinations according to K6 from Table 1 are: bis (2-hydroxy-5-aminophenyl) methane and 2,4-diaminophenoxyethanol bis (2-hydroxy-5-aminophenyl) methane and 2-amino-1-methoxy -4- (2-hydroxyethylamino) benzene

Bis (2-hydroxy-5-aminophenyl) methane and 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene

Particularly preferred combinations according to K7 from Table 1 are: p-toluenediamine and 2-amino-3-hydroxypyridine 2- (β-hydroxyethyl) -p-phenylenediamine and 2-amino-3-hydroxypyridine p-toluenediamine and 2,6-dihydroxy- 3,4-dimethylpyridine 2- (β-hydroxyethyl) -p-phenylenediamine and 2,6-dihydroxy-3,4-dimethylpyridine 2- (β-hydroxyethyl) -p-phenylenediamine, 2-amino-3-hydroxypyridine and 2- methylresorcinol

Particularly preferred combinations according to K8 from Table 1 are: bis (2-hydroxy-5-aminophenyl) methane and 2-amino-3-hydroxypyridine bis (2-hydroxy-5-aminophenyl) methane and 3-amino-2 -methylamino-6-methoxypyridine Bis- (2-hydroxy-5-aminophenyl) -methane and 2,6-dihydroxy-3,4-dimethylpyridine Bis- (2-hydroxy-5-aminophenyl) -methane and 3,5-diamino -2,6-dimethoxy

Particularly preferred combinations according to K9 from Table 1 are: p-aminophenol and 2-amino-3-hydroxypyridine 4-amino-3-methylphenol and 2-amino-3-hydroxypyridine p-aminophenol and 3-amino-2-methylamino-6 methoxypyridine 4-amino-3-methylphenol and 3-amino-2-methylamino-6-methoxypyridine p-aminophenol and 2,6-dihydroxy-3,4-dimethylpyridine 4-amino-3-methylphenol and 2,6-dihydroxy-3 , 4-dimethylpyridine p-aminophenol and 3,5-diamino-2,6-dimethoxypyridine 4-amino-3-methylphenol and 3,5-diamino-2,6-dimethoxypyridine

The combination of i) a p-phenylenediamine derivative, preferably selected from compounds of

Formula (E1), ii) a pyridine derivative and iii) resorcinol or a derivative thereof, in particular the combination of 2- (β-hydroxyethyl) -p-phenylenediamine, 2-amino-3-hydroxypyridine and 2-methylresorcinol, is in the agents according to the invention most preferably included.

In addition, it is particularly preferred when using resorcinol and its derivatives as coupler component, in particular 2-methylresorcinol, in addition to further improving the technical effect as a further coupler component at least one naphthalene, in particular at least one of the above representatives, more preferably 1, 5-dihydroxynaphthalene to use in the inventive compositions.

In all the above-mentioned preferred combinations, the physiologically tolerated salts of the corresponding enumerated compounds can also be used.

The coupler-type oxidation dye precursors of feature (c) of the compositions according to the invention, hereinafter also referred to as the coupler component, are preferably present in an amount of from 0.01 to 5% by weight, in particular from 0.1 to 3% by weight, based in each case on the weight of the ready-to-use colorant.

The dye precursors of naturally-analogous dyes (a) and the developer components (b) are preferably in a molar ratio of 10 to 1 to 1 to 2, more preferably in a molar ratio of 8 to 1 to 2 to 1, most preferably in a molar ratio of 6 to 1 to 3 to 1 in the inventive compositions.

The coupler components (c) and the developer components (b) are preferably in a molar ratio of 8 to 1 to 1 to 2, more preferably in a molar ratio of 6 to 1 to 2 to 1, most preferably in a molar ratio of 2.5 to 1 to 4.5 to 1 in the inventive compositions. The dye precursors of naturally-analogous dyes (a) and the coupler components (c) are preferably in a molar ratio of 2: 1 to 1: 2, more preferably in a molar ratio of 1.5 to 1 to 1: 1.5, most preferably in one Molar ratio of 1, 5 to 1 to 1 to 1 in the inventive compositions.

The ready-to-use hair dye preparation according to the invention should preferably have a pH in the range from 6 to 12. Particularly preferred is the use of the hair dye in an alkaline environment. The alkalizing agents (d) usable in the present invention are preferably selected from the group consisting of basic amino acids, alkali hydroxides, alkanolamines, alkali carbonates, alkali hydrogencarbonates, alkali metal metasilicates, alkali phosphates and alkali hydrogen phosphates. The alkali metal ions used are preferably lithium, sodium, potassium, in particular sodium or potassium.

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

The alkali metal hydroxides which can be used as the alkalizing agent according to the invention are preferably selected from the group formed from sodium hydroxide and potassium hydroxide.

The alkanolamines which can be used as alkalizing agents according to the invention are preferably selected from primary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group formed from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1 -Aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol , 1-amino-2-methylpropan-2-ol, 3-aminopropane-1, 2-diol, 2-amino-2-methylpropane-1,3-diol. Very particularly preferred according to the invention Alkanolamines are selected from the group 2-aminoethane-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methyl-propane-1, 3-diol.

A cosmetically acceptable carrier is understood in particular to be an otherwise customary carrier of agents for coloring human hair. The colorants according to the invention may be composed with regard to the features essential to the invention according to known colorants or contain them for these conventional ingredients. Examples of further suitable and inventively preferred ingredients are given below.

The agents according to the invention preferably contain the components according to the invention 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 preparations which are suitable for use on the hair. But it is also conceivable to integrate the dye precursors in a powdered or tablet-shaped formulation.

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

A general composition is given below, with the proviso that the molar ratio of compound A to compound B according to the invention is maintained:

In addition to the compounds according to the invention, in another embodiment of the present invention, the colorants according to the invention may contain one or more substantive dyes for shading. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those of the HC Yellow 2, HC Yellow 4, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1, 4-diamino-2 ~ nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) -amino-5-chloro-2-nitrobenzene, 4 Amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenyl-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-Hy droxy-1, 4-naphthoquinone, picramic 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

(a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) 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 as

(C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, to which reference is explicitly made at this point in claims 6 to 11 are called.

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

CH ₃ SO ₄ ^'

he

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).

The cationic direct dyes which are sold under the brand Arianor® ^® are, according to the invention also very particularly preferred cationic direct dyes. The agents according to the invention according to this embodiment preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations of the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

It is not necessary that the compounds A or 2 or the substantive dyes each represent uniform compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, further components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

With regard to the dyes which can be used in the hair-dyeing and tinting compositions according to the invention, reference is 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 series "Dermatology" (Editor: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials", Issued by the European Community, available in disk form from the Federal Association of German industrial and commercial enterprises for pharmaceuticals, health products and personal care registered association, Mannheim, reference is made.

The colorants of the invention may further contain all known for such preparations active ingredients, additives and excipients. In many cases, the colorants 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 proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. 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 present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and Trialkanolammoniumsalze with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 carbon atoms (soaps ), Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH ₁ in which R is a linear alkyl group having 10 to 22 C atoms and x = O or 1 to 16, acylsarcosides having 10 to 18 C atoms in the acyl group, acyl taurides having 10 to 18 C atoms in the acyl group, acyl isethionates having 10 to 18 C atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 carbon atoms, linear alpha-olefin sulfonates having 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 12 to 18 carbon atoms , Alkyl sulfates and alkyl polyglycol ether sulfates of the form el 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 = O or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C 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.

Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 moles 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 castor oil.

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. Preference is given to primary linear and methyl-branched in the 2-position aliphatic 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 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 one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case are present as alkyl radicals R mixtures according to the starting compounds or according to the respective workup of these compounds.

Such alkyl polyglycosides are particularly preferred in which R ¹ consists essentially of C ₈ - and C-io-alkyl groups essentially of C ₁₂ - and C - ^ - alkyl groups essentially of C ₈ - to C ₆ -alkyl or substantially from C ₁₂ - to Ci ₆ 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 oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, isose, 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. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The person skilled in the art will therefore prefer to use this substance class as a further constituent of the preparations according to the invention in the event that an effect of the perfume oil on the hair which exceeds the duration of the hair treatment is desired.

The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^H or -SO 3 ^H group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium-glycinate, for example, the cocoalkyl dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammoniumglycinate, for example Kokosacylaminopropyl-dime- thylammoniumglycinat, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines having in each case 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. Ampholytic surfactants are understood to mean those surface-active compounds which, apart from a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and which are capable of forming internal 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 atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

According to the invention, the cationic surfactants used may in particular be those of the quaternary ammonium compounds, esterquats and amidoamines type.

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which have at least one ester function and at least one quaternary ammonium group as structural element. hold. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the brands Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-Palmitoyloxy- ethyl) dimethyl ammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances that available under the brand Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine is.

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, 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 GIu- Ceth-10 hydroxypropyl dimonium chloride".

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained. In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alkoxides as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, 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 narrow homolog distribution may be preferred.

Furthermore, the colorants according to the invention further active ingredients, auxiliaries and additives, such as

nonionic polymers, for example vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes,

cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate-quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,

zwitterionic and amphoteric polymers, for example acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate hydroxypropyl methacrylate copolymers, anionic polymers, for example polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers , Vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert. Butyl acrylamide terpolymers, amphiphilic polymers, such as, for example, the polymers according to the INCI name: designations acrylates / beheneth-25 methacrylate copolymer, acrylates / C 10-30 alkyl acrylate crosspolymer, acrylates / ceteth-20 itaconates Copolymer, Acrylates / Ceteth-20 Methacrylate Copolymer, Acrylates / Laureth-25 Methacrylate Copolymer, Acrylates / Palmeth-25 Acrylate Copolymer, Acrylates / Palmeth-25 Itaconate Copolymer, Acrylates / Steareth-50 Acrylate Copolymer, Acrylates / Steareth-20 Itaconate Copolymer, Acrylates / Steareth-20 Methacrylate Copolymer, Acrylates / Stearyl Methacrylate Copolymer, Acrylates A / inyl Isodecanoate Crosspolymer,

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabicum, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. Bentonite or fully synthetic hydrocolloids such as e.g. polyvinyl alcohol,

Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,

Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl 2-alkylimidazolinium methosulfate defoamers such as silicones, dyes for staining the agent,

Antidandruff active ingredients 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 substances such as allantoin, pyrrolidonecarboxylic acids and their salts, and also bisabolol, Vitamins, provitamins and vitamin precursors, in particular those of the groups A ₁ B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, 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, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, 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 alkanolamides,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,

- swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

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

Stabilizing agent for hydrogen peroxide and other oxidizing agents,

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

- Antioxidants, included.

With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

According to the invention, however, the colorant can also be applied to the hair together with an oxidation activator, which activates the oxidation of the dye precursors by the atmospheric oxygen. The oxidation activators are preferably selected from the group formed from carbonates, Hydrogen carbonates, carbamates, carboxylic acid esters or their salts, aldehydes, especially aliphatic aldehydes, 1, 3-dihydroxyacetone, imidazole and its derivatives, alkali metal and Ammoniumperoxidisulfaten, metal ions, iodides, quinones and enzymes.

Since the oxidative dyeing is formed by atmospheric oxygen, it may be advantageous according to the invention to use metal ions as the oxidation activator.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

The activators are preferably present in amounts of 0.01 to 5 wt.%, Based on the weight of the total colorant, in the inventive compositions.

The application temperatures can be in a range between 15 and 40 ⁰ C. After a contact time of usually 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.

A second subject matter of the present invention is a process for coloring keratinic fibers, in which a hair colorant according to the invention is applied to the fibers and rinsed off again after a contact time. Examples

The following inventive colorant formulations E1 to E6 (see Table 1) were prepared by a production process known to the person skilled in the art. The following raw materials were used:

Hydrenol ^® D Ci6-Ci ₈ fatty alcohol (INCI name: Cetearyl alcohol) (Cognis Germany) Lorol® ^® techn. C ₂ -C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (Cognis Germany) Eumulgin ^® B 1 Cetylstearylakohol with 12 EO units

(INCI name: Ceteareth-12) (Cognis Germany) Eumulgin ^® B 2 cetylstearyl alcohol with about 20 EO units (INCI name: Ceteareth-20) (Cognis Germany) Akypo Soft 45 NV ^® C _12-14 fatty alcohol acetic acid Sodium salt with 4.5 units of ethylene oxide (INCI name: sodium laureth-5 carboxylate), active substance 21%, (KAO)

Texapon ^® K 14 S lauryl myristyl ether sulfate sodium salt with 3 units of ethylene oxide (INCI name: Sodium Myreth Sulfate), active substance 70%, (Cognis Germany)

Plantacare ^® 1200 UP C- ₁₂ - ₁ 6 Alkylglucoside (INCI name: Lauryl Glucoside), 51% active ingredient, (Cognis Germany) Eutanol ^® G 2-Octyldodecanol (INCI name: Octyldodecanol) (Cognis Germany) AMP ^® 95 2- Amino-2-methylpropan-1-ol (INCI name: Aminomethyl propanol) (DOW)

Table 1:

Each natural hair strand was dyed. The hair each received an intense, permanent natural color without red, blue or purple stitch.

Claims

Patent claims

An agent for the atmospheric oxygen-induced staining of nucleated fibers, in particular human hair, in a cosmetically acceptable carrier

(a) at least one indole and / or indoline derivative as the dye precursor of a naturally-analogous dye,

(b) at least one developer-type oxidation dye precursor,

(c) at least one coupler-type oxidation dye precursor and

(d) at least one alkalizing agent, with the proviso that

- the agent is free of ammonia and

- No additional oxidizing agent for components (a), (b) and (c) is included.

2. Composition according to claim 1, characterized in that the indoline derivatives of the feature (a) are selected from compounds of the formula (Ia) and / or their physiologically tolerable salts with an organic or inorganic acid,

(Ia)

R ¹ in which

R ¹ is hydrogen, a C _r C ₄ -alkyl group or a dC ₄ -hydroxy-alkyl group,

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

R ³ is hydrogen or a C _r C ₄ -alkyl group,

R ⁴ is hydrogen, a C _r 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 is one of the groups mentioned under R ⁴ .

3. Composition according to one of claims 1 or 2, characterized in that the indole derivatives of the feature (a) are selected from compounds according to formula (Ib) and / or their physiologically acceptable salts with an organic or inorganic acid,

wherein

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

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

R ³ is hydrogen or a C _r C ₄ alkyl group,

- R ⁴ is hydrogen, a C _r C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C _r C ₄ alkyl group and

R ⁵ is one of the groups mentioned under R ⁴ .

4. Composition according to one of claims 1 to 3, characterized in that the dye precursors of the naturally-analogous dye (a) are contained in an amount of 0.01 to 10 wt .-% based on the weight of the ready-to-use agent.

5. Composition according to one of claims 1 to 4, characterized in that the oxidation dye precursors of the developer type (b) are selected from the group formed from p-phenylenediamine derivatives, binuclear developer components, p-aminophenol and its derivatives, pyrimidine derivatives, Pyrazole derivatives and Pyrazolopyrimidinderivaten and the physiologically acceptable salts of these compounds.

6. Composition according to one of claims 1 to 5, characterized in that the oxidation dye precursors of the developer type (b) are contained in an amount of 0.01 to 5 wt .-% based on the weight of the ready-to-use agent.

7. Composition according to one of claims 1 to 6, characterized in that the oxidation dye precursors of the coupler type (c) are selected from the group formed from m-aminophenol and its derivatives, o-aminophenol and its derivatives, m-phenylenediamine and its derivatives, o-phenylenediamine and its derivatives, dihydroxybenzene derivatives, trihydroxybenzene derivatives, pyridine derivatives, naphthalene derivatives, morpholine derivatives, quinoxaline derivatives, pyrazolone derivatives and methylenedioxybenzene derivatives.

8. Composition according to one of claims 1 to 7, characterized in that the oxidation dye precursors of the coupler type (c) in an amount of 0.01 to 5 wt .-% based on the weight of the ready dye is included.

9. Composition according to one of claims 1 to 8, characterized in that the dye precursors of naturally-analogous dyes (a) and the developer components (b) in a molar ratio of 10 to 1 to 1 to 2, particularly preferably in a molar ratio of 8 to 1 to 2 to 1, most preferably in a molar ratio of 6 to 1 to 3 to 1 are included.

10. Composition according to one of claims 1 to 9, characterized in that the coupler components (c) and developer components (b) in a molar ratio of 8 to 1 to 1 to 2, more preferably in a molar ratio of 6 to 1 to 2 to 1, most preferably in a molar ratio of 2.5 to 1 to 4.5 to 1 are included.

11. Composition according to one of claims 1 to 10, characterized in that the dye precursors of naturally-analogous dyes (a) and the coupler components (c) in a molar ratio of 2 to 1 to 1 to 2, particularly preferably in one Molar ratio of 1, 5 to 1 to 1 to 1, 5, most preferably in a molar ratio of 1, 5 to 1 to 1 to 1 are included.

12. A composition according to any one of claims 1 to 11, characterized in that the alkalizing agent (d) is selected from the group consisting of basic amino acids, alkali hydroxides, alkanolamines, alkali carbonates, alkali hydrogen carbonates, alkali metal metasilicates, alkali phosphates and alkali hydrogen phosphates.

13. Composition according to one of claims 1 to 12, characterized in that it has a pH in the range of pH 6 to 12.

14. Composition according to one of claims 1 to 13, characterized in that it additionally contains at least one surfactant selected from the group consisting of anionic surfactants, zwitterionic surfactants, ampholytic surfactants, nonionic surfactants and cationic surfactants.

15. Composition according to one of claims 1 to 14, characterized in that it additionally contains at least one polymer selected from the group of anionic polymers, cationic polymers, amphoteric polymers and amphiphilic polymers.

16. A process for coloring keratinous fibers, wherein an agent according to any one of claims 1 to 15 is applied to the fibers and rinsed again after a contact time.