WO2006018089A1 - Oxidation colorants comprising diaminobenzene derivatives - Google Patents

Abstract

The invention relates to oxidation colorants for colouring keratin fibres, in particular human hair, comprising at least one coupling component and at least one developing component in a carrier containing water. The coupling component is selected from m-phenylene diamine derivatives, naphtholene, resorcin and resorcin derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives and the developing component is selected from the compounds of formula (I), in which R1 and R2 independently of one another represent a hydrogen atom, a linear or cyclic C<sub

Description

"Oxidation Dye with Diaminobenzene Derivatives"

The invention relates to agents for dyeing keratin fibers containing special Diaminobenzolderivate developer component in combination with at least one coupler component, a process for dyeing keratin fibers with these agents, and the use of the dye combinations according to the invention in cosmetic centers, in particular for dyeing keratin fibers.

According to the invention, keratin fibers are understood to mean furs, wool, feathers and, in particular, human hair. Human hair is today treated 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 grow directly on the hair and do not require an oxidative process to form the color. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyes are against Shampooing is usually sensitive, so that a much undesirable nuance shift or even a visible "discoloration" can occur.

For the dyeing of keratin fibers, especially hair, the so-called oxidation dyes play a special role because of their intense colors ¹ and good fastness properties, which are achieved at relatively low dyeing temperature and in short dyeing times. Such colorants contain in a suitable, usually aqueous carrier, a developer component which forms the dye under the influence of atmospheric oxygen or oxidizing agents by oxidative coupling. This dye can be intensified by coupling with another developer component or with so-called coupler components, which themselves can not form dyes, and modified in nuance.

Good oxidation dye precursors are primarily intended to meet the following requirements: They must form the desired color shades in sufficient intensity and authenticity in the oxidative coupling. You must also have a good Aufziehvermögen on the fiber, especially in human hair no significant differences between strained and freshly regrowed hair may exist (leveling ability). They should be resistant to light, heat, friction and the influence of chemical reducing agents, e.g. Perm liquids. Finally, if applied as a hair dye, they should not stain the scalp too much and above all they should be safe in terms of toxicology and dermatology. Furthermore, the coloring achieved by bleaching should be easily removed from the hair, if it does not meet the individual wishes of each person and should be reversed.

For hair dyeing and tinting agents, the color shades in the red and brown areas in particular are of considerable importance, since they are used to produce hair naturally acting hair dyeings are mandatory. Oxidation colorants in the red and brown range, such as those obtainable with the combination of 2,4,5,6-tetraaminopyrimidine and 2-methylresorcinol, are not yet optimal with regard to the uniformity of the color lift. Direct dyes are usually less fast to washing and therefore less suitable for combination with oxidation dyes.

For these reasons, there is a need for novel oxidation dye precursors, which allow an improvement of the above-mentioned parameters. Surprisingly, it has been found that certain diaminobenzene derivatives meet the above requirements in an excellent manner.

A first subject of the invention is therefore an oxidation dye for dyeing keratin fibers, in particular human hair, comprising at least one coupler component and at least one developer component in a water-containing carrier, wherein

^" the ^" coupler component is selected from m-phenylenediamine derivatives,

Naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives and

the developer component is selected from the compounds according to formula (I),

(I) in der R1 und R2 unabhängig voneinander für ein Wasserstoffatom, eine lineare oder cyclische Ci-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine substituierte oder unsubstituierte Arylgruppe, eine substituierte oder unsubstituierte Heteroarylgruppe, eine Arylalkylgruppe, eine CrC₆-Hydroxyalkylgruppe, eine C₂- C₆-Polyhydroxyalkylgruppe, eine Ci-C₆-Alkoxy-C2-C₆-alkylgruppe, eine Aminoalkylgruppe, eine Dialkylaminoalkylgruppe stehen, wobei die Reste R1 und R2 gemeinsam einen gesättigten Ring bilden können, der weitere Heteroatome wie N oder O enthalten kann und der Rest R3 für ein Wasserstoff atom, ein Halogenatom, eine C-i-Cβ-Alkylgruppe, eine C_rC₆-Hydroxyalkylgruppe, eine Hydroxygruppe, eine Aminogruppe, eine Dialkylaminogruppe, eine C₁-C₆- Alkoxygruppe, eine Nitrogruppe, eine Hydroxy-Ci-Cε-alkoxygruppe, eine Carboxygruppe, eine Sulfonylgruppe, eine Sulfonamidogruppe oder eine Carboxamidogruppe stehen und in der n für 3, 4 oder 5 steht, sowie deren Salzen mit einer anorganischen oder organischen Säure.

(I) in which R1 and R2 independently represent a hydrogen atom, a linear or cyclic Ci-C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, an -C ₆ - Hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, an aminoalkyl group, a dialkylaminoalkyl group, where R 1 and R 2 may together form a saturated ring containing further heteroatoms, such as N or O may contain and the radical R3 is a hydrogen atom, a halogen atom, a Ci-Cβ-alkyl group, a C _r C ₆ -hydroxyalkyl group, a hydroxy group, an amino group, a dialkylamino group, a C ₁ -C ₆ - alkoxy group, a nitro group, a hydroxy-C 1 -C 6 alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group and in which n is 3, 4 or 5, and their salts mi t of an inorganic or organic acid.

Examples of C 1 -C 6 -alkyl groups in the compounds according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl. ^"Preferred alkyl groups are methyl and ethyl, methyl is a particularly preferred alkyl group. Preferred C2-C6-alkenyl groups are vinyl, allyl and butenyl, with vinyl and allyl being especially preferred. Preferred CrC ₆ -Monohydroxyalkylgruppen, the groups hydroxymethyl, 2-hydroxyethyl 3-hydroxypropyl or 4-hydroxybutyl; 2-hydroxyethyl is a particularly preferred hydroxyalkyl group Preferred C ₂ -C 6 -polyhydroxyalkyl groups are α, β-dihydroxyethyl and β, γ-dihydroxypropyl Suitable halogen substituents according to the invention are preferably chlorine, bromine and iodine, Chlorine and bromine are particularly preferred. Physiologically acceptable salts are understood as meaning salts of inorganic or organic acids, for example hydrochlorides, sulfates or hydrobromides.

In a preferred embodiment of the present invention, n in the above represented formula (I) is 3 or 4. Preferred Means according to the invention are therefore characterized in that they contain a developer component of the formula (I) in which n is 3 or 4.

In a further preferred embodiment of the present invention, the radicals R 1, R 2 and R 3 in the above represented formula (I) represent a hydrogen atom. Particularly preferred agents according to the invention are characterized in that they contain a developer component of the formula (I) in which the radicals R 1, R 2 and R 3 represent a hydrogen atom.

Particularly preferred oxidation colorants according to the invention are characterized in that the compound according to formula (I) is selected from 4-amino-5,6,7,8-tetrahydro-1-naphthylamine and / or 7-amino-2,3-dihydro-1 H-inden-4-ylamine.

The agents according to the invention preferably contain the compounds of the formula (I) in an amount of from 0.01 to 20% by weight, based on the total colorant.

The diaminobenzene derivatives of the formula I are prepared by known processes of organic synthesis. For example, for the synthesis of 4-amino-5,6,7,8-tetrahydro-1-naphthylamine, for example, on the

Bamberger; Schieffelin; CHBEAM; Ber. 1889; 22; 1376. [2] Schroeter; JLACBF; Jυstυs Liebigs Ann. Chem. 1922; 426; 132. [3] Micklethwait; Winfield; JCSOA9; J. Chem. 1904; 85; 751 [4] Green; Rowe; JCSOA9; J. Chem. 1918; 113 ;; 968th

recourse to known ways.

In addition to the diaminobenzene derivatives according to the invention, the agents according to the invention furthermore comprise at least one coupler component the group of m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives. These will be described below.

Preferred coupler components according to the invention are m-aminophenol and its derivatives, such as, for example, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2 6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'- Hydroxyethyl) - amino-2-methylphenol, 3- (diethylamino) -phenol, 1, 3-dihydroxy-5-

(methylamino) benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol,

o-aminophenol and its derivatives,

m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1-bis-bis-1'-diaminophenoxypropane, 1-methoxy-2-amino-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, o- Diaminobenzene and its derivatives such as 3,4-

Diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol,

Resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2.5-

Dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1, 2,4-

trihydroxybenzene,

Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, Naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

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

Quinoxaline derivatives such as 6-methyl-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-hydroxyindole, - - _ _ ^~

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

Trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or methylenedioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-aminobenzene 3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene,

Particularly preferred coupler components are 2-amino-3-hydroxypyridine, 2-amino-3-hydroxy-5-chloropyridine, 3-amino-2-methylamino-6-methoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 2 ₁ 6-dihydroxy-3,4-dimethylpyridine, m-

Phenylenediamine, 2,6-bis- (2-hydroxyethylamino) -toluene, 3-amino-2,4-dichlorophenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5- (β-hydroxyethyl) -amino-2-methylphenol, 5-amino-2-methylphenol, 2-methylresorcinol, 2- (2 ', 4'-diaminophenoxy) ethanol, 1.S-bis - ^' ^ '- diamino-phenoxy) propane, resorcinol, 4-chlororesorcinol, resorcinol monomethyl ether, m-aminophenol, 1, 7, 2,7- and 1, 5-dihydroxynaphthalene, as well as 4-hydroxyindole and 6-hydroxyindole.

Further preferred coupler components are 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol

2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol

3-Amino-4- (2-methoxyethoxy) -5-methylphenylamine

2 - [(3-morpholin-4-yl-phenyl) -amino] -ethanol dihydrochloride

In summary, preference is given to oxidation dyes according to the invention in which the coupler component is selected from resorcinol, 3-amino-2-one methylamino-6-methoxypyridine, 3-amino-6-methylphenol, 3-amino-2-hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 5-methyl -resorcinol, 2,5-dimethylresorcinol and 4-chlororesorcinol 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3- hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine, 2 - ({ 3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 3-Amino-4- (2-methoxyethoxy) -5-methylphenylamine and 2 - [(3-morpholin-4-ylphenyl) amino] ethanol dihydrochloride.

The oxidation colorants of the present invention preferably contain the coupler component (s) in an amount of 0.01 to 20% by weight, preferably 0.5 to 5% by weight, and the developer component (s) in an amount of 0.01 to 20 wt .-%, preferably from 0.5 to 5 wt .-%, each based on the total oxidation colorant.

In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1 : 2, may be included.

Preferred oxidation colorants according to the invention are characterized in that they contain, in addition to the coupler components from the group consisting of m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives and the compounds of the formula (I) no further oxidation dye precursors. However, with a developer component or a specific coupler / developer combination, it is generally not possible to obtain a color shade which acts naturally on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used. There is therefore a constant need for new, improved dye combinations. Therefore, others may be preferred

Oxidation hair dyes in addition to the compounds of formula (I) further developer components.

As further developer components are usually primary aromatic amines with another, located in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

It may be preferred according to the invention to use as additional developer component a p-phenylenediamine 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 CrC ₄ alkyl radical, a CrC ₄ - monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (CrC ₄₎ - alkoxy (CrC ₄₎ alkyl group, a 4'-aminophenyl radical or a C 1 -C ₄ -alkyl radical, which is substituted by a nitrogen-containing group, a phenyl or a 4 ¹ - aminophenyl radical,

- G ² represents a hydrogen atom, a CrC ₄ alkyl radical, a Ci-C ₄ - monohydroxyalkyl radical, a _C2-C4 polyhydroxyalkyl radical, a (Ci-C ₄₎ - alkoxy alkyl (Ci-C ₄₎ or a C 1 -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 CrC ₄ alkyl, C ₁ -C ₄ - monohydroxyalkyl radical, a _C2-C4 polyhydroxyalkyl radical, a C ₁ C ₄ - hydroxyalkoxy, C ₁ -C ₄ -acetylaminoalkoxy, C ₁ -C ₄ -mesylaminoalkoxy or C ₁ -C ₄ -carbamoylaminoalkoxy;

G ⁴ represents a hydrogen atom, a halogen atom or a C 1 -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 -C ₄ -alkyl radicals mentioned as substituents in the context of this application are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Examples of preferred C ₂ -C ₄ alkenyl radicals are vinyl and allyl. C 1 -C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ -C ₄ monohydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. An example of a preferred C ₂ -C ₄ polyhydroxyalkyl group is the α, β-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 (II) are, in particular, the amino groups, C 1 -C ₄ -monoalkylamino groups, C 1 -C ₄ - Dialkylamino groups, CrC4-trialkylammonium groups, Ci-C ₄ -

Monohydroxyalkylamino groups, 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-fluoro-p-phenylenediamine, 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-

Acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine ^" and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

Very particular preferred p-phenylenediamine derivatives of the formula (E 1) 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 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 that can be used in the paint compositions according to the invention, may be mentioned in particular the compounds corresponding to the following formula (E2), and their physiologically acceptable salts:

wobei:

in which:

- Z ¹ and Z ² are each independently a hydroxyl or NH ₂ -ReSt, which is optionally substituted by a Ci-C ₄ alkyl, by a CrC ₄ - monohydroxyalkyl and / or by a bridge Y or which 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 interrupted by - one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms or may be terminated and may optionally be substituted by one or more hydroxyl or C 1 -C ₈ -alkoxy radicals, or a direct bond,

- G ⁵ and G ⁶ are each independently a hydrogen or halogen atom, a CrC ₄ alkyl radical, a -C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ - polyhydroxyalkyl radical, a Ci-C ₄ -aminoalkyl radical or a direct bond to the bridge 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 -C _I - 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 which carries at least one hydrogen atom.

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

Preferred binuclear developer components of the formula (E2) are, in particular: - N, N'-bis-Cβ-hydroxyethyl-N, N'-bis-C'-aminophenyO-i, 3-diamino-propan-2-ol, N 2 ' -Bis-β-hydroxyethyl-N, N'-bis-aminophenyl-ethylenediamine, N, N'-bis- (4-aminophenyl) -tetra-methylenediamine, N, N'-bis- (β-hydroxyethyl) - N, N'-bis (4-aminophenyl) -tetramethylenediamine, N, N'-bis (4-methyl-aminophenyl) -tetramethylenediamine, N.N'-bis-tethy-O-N'-bis- '' amino-S'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,4-bis (4'-aminophenyl) diaza-cycloheptane, N, N'-bis ( 2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane and their physiologically acceptable salts.

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis-Cβ-hydroxyethyl-N, N'-bis-C'-aminophenyO-i, 3-diamino-propan-2-ol, bis (2 -hydroxy-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 acceptable salts.

wobeiFurthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. 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 -C ₄ -alkyl radical, a C 1 -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -hydroxyalkyl radical, a (C 1 -C ₄ ) -alkoxy- (C 1 -C ₄ ) -alkyl radical, a C 1 -C ₄ -alkoxy radical Aminoalkyl radical, a hydroxy

- (Ci-C ₄₎ alkylamino group, a C _r C ₄ -Hydroxyalkoxyrest, a C ₁ -C ₄ - hydroxyalkyl (Crbis C _4), or (di-CrC ₄ alkylamino) aminoalkyl radical - (Ci- _C4 ) -alkyl radical, and

- G ¹⁴ represents a hydrogen or halogen atom, a Ci-C ₄ alkyl radical, a -C ₄ hydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a _(d-C4) - alkoxy- (C ₁ -C ₄ ) -alkyl radical, a C 1 -C ₄ -aminoalkyl radical or a C 1 -C ₄ -cyanoalkyl radical,

- G ¹⁵ is hydrogen, a CrC ₄ alkyl radical, a -C ₄ hydroxyalkyl radical, a C ₂ -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-hydroxy-methylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2- aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2-ol fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro-4-aminophenol, 4-amino-2- ((diethylamino) methyl) phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2- ((diethylamino) methyl) phenol.

Further, the additional developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol or 2-amino-4-chlorophenol.

Further, the additional developer component may be selected from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts. According to the invention, preference is given to pyrimidine or pyrazole derivatives.

Preferred pyrimidine derivatives are in particular the compounds -2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5 , 6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds 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-hydrazinopyrazole, 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- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4 (β-hydroxyethyl) amino-1 - methylpyrazole.

Particularly preferred pyridine derivatives are the compounds 2,5-diamino-pyridine, 2- (4-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxypyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

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

in which:

- G ¹⁷ , »18 G» 19 and G ^ 20 independently represent one another

Hydrogen atom, a Ci-C ₄ alkyl radical, an aryl radical, a Ci-C ₄ - hydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical alkyl group a (Ci-C ₄₎ alkoxy (Ci _C4), a Ci-C ₄ aminoalkyl radical, which may be optionally protected by an acetyl ureide or a sulfonyl residue, a _(Ci-C4) - alkylamino alkyl (CrC _4), a di - [(CrC ₄₎ - alkyl] - (C 1 -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 -C ₄ -hydroxyalkyl or a di (C 1 -C ₄ ) - [hydroxyalkyl] - ( Ci-C ₄₎ aminoalkyl radical, the X radicals are each independently a hydrogen atom, a Ci-C ₄ alkyl radical, an aryl radical, a Ci-C ₄ hydroxyalkyl radical, a C ₂ -C ₄ - Polyhydroxyalkyl, a Ci-C- _t -Aminoalkylrest, a (CrC ₄ ) -Alkylamino- (C ₁ -C ₄ ) alkyl, a di - [(Ci-C4) alkyl] - (Ci-C4) -aminoalkyl, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C 1 -C ₄ -hydroxyalkyl or a di- (C 1 -C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, a C 1 -C 4 -alkyl or di (C 1 -C ₄ ) radical -hydroxyalkyl) -amino, 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 defined according to the invention analogously to the above statements.

When the pyrazole [1,5-a] pyrimidine of the above formula (E4) 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 (E4) may be mentioned in particular:

- pyrazolo [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-dimethyl-pyrazolo [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-tetramethyl-pyrazolo [1,5-a] -pyrimidine-3,7-diamine; and their physiologically acceptable salts and their tautomeric forms when tautomeric equilibrium is present.

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

Additional preferred developer components according to the invention are pyrimidine derivatives, pyrazole derivatives, p-aminophenol derivatives and p-phenylenediamine derivatives. Particularly preferred additional developer components according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N, N'-bis- ( β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hydroxy-5-aminophenyl) -methane, N, N'- Bis (4'-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3 methylphenol, 4-amino-3-fluorophenol, 4-amino-2-aminomethylphenol 4-amino-2- ((diethylamino) methyl) phenol, o-aminophenol, 2-amino-4-methylphenol, 2-amino-5- methylphenol, 2-amino-4-chlorophenol, 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,

2,5,6-triaminopyrimidine, 1- (2'-hydroxy-5'-aminobenzyl) -imidazolidin-2-one and 4,5-diamino-1- (2'-hydroxyethyl) pyrazole.

Very particularly preferred developer components according to the invention are p-toluenediamine and 2,4,5,6-tetraaminopyrimidine.

Another preferred additional developer component is N- (4-amino-3-methylphenyl) -Λ- [3- (1-imidazol-1-yl) propyl] amine trihydrochloride):

In summary, preference is given to oxidation dyes according to the invention which comprise a further developer component which is selected from 3-methyl-1,4-diaminobenzene, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 2- (2,5-)

Diaminophenoxy) ethanol, N, N-bis (2'-hydroxyethyl) -1, 4-diaminobenzene, 3-methyl-4-aminophenol and 2-methylamino-4-aminophenol, p-phenylenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-bis) aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hydroxy-5-aminophenyl) -methane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, 1 , 10-bis (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino 2-aminomethylphenol, 4-amino-2- ((diethylamino) methyl) phenol, o-aminophenol, 2-amino-4-methylphenol, 2-amino-5-methylphenol, 2-amino-4-chlorophenol, 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, 2,5,6-triaminopyrimidine, 1- (2'-hydroxy-5'-aminobenzyl) imidazolidin-2-one, 4,5-diamino-1- (2'-hydroxyethyl) pyrazole and N- (4-Amino-3-methylphenyl) -Λ / - [3- (1H -imidazol-1-yl) propyl] amine trihydrochloride.

Furthermore, the agents according to the invention may contain precursors of naturally-analogous dyes. As precursors of naturally-analogous dyes such indoles and indolines are preferably used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group.

Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IIa),

in the independently of each other R ¹ stands for hydrogen, a Ci-C ₄ alkyl group, a C ₃ -CO- cycloalkyl group, a C2-C ₄ alkenyl group or a C _r C ₄ hydroxyalkyl 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 Ci-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 Ci-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 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.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (IIb),

in der unabhängig voneinander

in the independently of each other

R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₆ -cycloalkyl group, a C ₂ -C -alkenyl group or a C ₁ -C 8 -hydroxyalkyl 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 Ci-C ₄ alkyl group, R ⁴ is hydrogen, a Ci-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 , 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.

Of the group to be emphasized 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 indole or indoline derivatives are usually contained therein in amounts of 0.05-10% by weight, preferably 0.2-5% by weight. In particular, when using dye precursors of the indoline or indole type, it has proven to be advantageous to use as the alkalizing an amino acid and / or an oligopeptide.

In a preferred embodiment, the hair colorants according to the invention additionally contain customary substantive dyes for the further modification of the color shades in addition to the oxidation dye precursors.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN ₁ 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-amino-2-nitrobenzene. (2'-Hydroxyethyl) amino-4,6-dinitrophenol, 1- (2 ¹ -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-nitrodiphenylamine-2'-ca hydrobromic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3 nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Corresponding agents according to the invention which are characterized in that they contain at least one substantive dye which is selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group of the dyes HC Yellow 2, HC known under the international names or trade names HC Yellow 5, 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, Violet 4 Violet, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds and 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 ¹ -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-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and their salts, 2- Amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene are preferred.

Furthermore, the agents according to the invention may contain a cationic substantive dye. Particular preference is given .- .-, _ -

(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, which is incorporated herein by reference, in claims 6 to 11. Preferred cationic substantive dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

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 trademark 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 for the oxidation dye precursors or the direct dyes to be in each case homogeneous 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", published by the European Community, available in disk form from the Federal Association German industrial and commercial enterprise for medicaments, reform goods and personal care registered association, Mannheim, referred to.

In a further embodiment, the agent according to the invention additionally contains a combination of component

A compounds which contain a reactive carbonyl group with component B compounds selected from (a) CH-acidic compounds, (b) compounds having a 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) oligopeptides constructed from 2 to 9 amino acids.

Compounds according to the invention having a reactive carbonyl group (also referred to below as reactive carbonyl compounds or component A) have at least one carbonyl group as reactive group which reacts with the compounds of component B to form a chemical bond linking both components. Furthermore, those compounds according to the invention are also included as component A in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to component B is always present. These derivatives are preferably condensation compounds of reactive carbonyl compounds with a) amines and their derivatives to form imines or oximes as the condensation compound b) of alcohols to form acetals or ketals as a condensation compound.

Component A is preferably selected from the group formed from acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxy butyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4- Aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1 acetonaphthone, 1-hydroxy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7-trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, Quercetin, 1- indanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1, 8-dihydroxyanthrone, vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxybenzaldehyde. 2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methyl- benzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxybenzaldehyde 4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2, 3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5 -Dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6 Trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2, 3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4- Dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2- Methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3-methoxy-cinnamaldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylamino-benzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) -benzaldehyde, piperonal, 2,3,6,7-tetrahydro- 1 H, 5H-benzo [ijglinolizine-θ-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2 -Formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde), 2-indolaldehyde, 3-indolealdehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (r, 3 ¹ , 3 ^1- trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, Chin olin-3-aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, chromone-3-aldehyde, 3- (5'-nitro-2'-furyl ) -acrolein, 3- (2'-furyl) -acrolein and imidazole-2-aldehyde, 1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2 - (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) acetophenone, 2- (2'- Pyridoyl) acetophenone and 2- (3'-pyridoyl) acetophenone, benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylidene acetone, 4-methoxybenzylidene acetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4- Methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4-diethylamino-benzylidone-acetone, 3-benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4 ^l Dimethylaminobenzylidene) -2,4-pentanedione, 2-benzylidenecyclohexanone, 2- (4'-hydroxybenzylidene) cyclohexanone, 2- (4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3- (4'-dimethylaminobenzylidene) -1,3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxy-3-methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohex andion, 2-benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene) -cyclopentanone, 2- (4'-dimethylaminobenzylidene) cyclopentanone, 5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-hydroxybenzylidene) cyclopentanone 4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4-dimethoxyphenyl) penta-2,4-dienal, 5- (2 , 4-Dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal, 6- (4-dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) -hexa-3,5-dien-2-one, 6- (4 -Methoxyphenyl) hexa-3,5-dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3 , 5-dien-2-one, 6- (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- ( 4-pyrrolidinophenyl) hexa-3,5-dien-2-one, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl 3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2- Chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5- di- methoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, S-acetyl-θ- methylcafbazole, 1, 4-dimethyl-3-carbazolaldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde, 4-formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium , 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium-r 4-formyl-1-methylquinolinium, 2-formyl-1-methyl-quinolinium, 4-acetyl-1-methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1-methyl-quinolinium, 5-formyl 1-methyl-quinolinium, 6-formyl-1-methyl-quinolinium, 7-formyl-1-methyl-quinolinium, 8-formyl-1-methyl nolinium, 5-formyl-1-ethyl-quinolinium, 6-formyl-1-ethyl-quinolinium, 7-formyl-1-ethyl-quinolinium, 8-formyl-1-ethyl-quinolinium, 5-formyl-1-benzyl-quinolinium, 6 Formyl-1-benzyl-quinolinium, 7-formyl-1-benzyl-quinolinium, 8-formyl-1-benzyl-quinolinium, 5-formyl-1-allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7-formyl 1 ^{'-aHyichinölinium r} and 8-formyl-i-allylchinolinium-, 5-acetyl-1-methylchinolinium- 6-acetyl-1 -methylchinolinium-, 7-acetyl-1 -methylchinolinium-, 8-acetyl-1-methylquinolinium, 5 Acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium, 6-acetyl-1 benzylchinolinium, 7-acetyl-1-benzyl-quinolinium, 8-acetyl-1-benzyl-quinolinium, 5-acetyl-1-allyl-quinolinium, 6-acetyl-1-allyl-quinolinium, 7-acetyl-1-allyl-quinolinium and 8- Acetyl-1-allyl quinolinium, 9-formyl-10-methylacridinium, 4- (2'-formylvinyl) -1-methylpyridinium, 1, 3-dimethyl-2- (4'-formyl 1-phenyl) benzimidazolium, 1,3-dimethyl-2- (4'-formylphenyl) imidazolium, 2- (4'-formylphenyl) -3-methylbenzothiazolinium, 2- (4'-acetylphenyl) -3 -methylbenzothiazolium, 2- (4'-formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-furyl) 3-methylbenzothiazolium, 2- (5'-formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formyl -1-naphthyl) -3-methylbenzo- thiazolium, 5-chloro-2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3,5-dimethylbenzothiazolium beπzolsulfoπat, p-toluenesulfonate, - methanesulfonate, perchlorate, - sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5 -Methoxy-isatin, 5-nitroisatin, 6-nitro-isatin, 5-sulfoisoisine, 5-carboxy-isatin, quinisatin, 1-methylquinisatin, and any mixtures of the above compounds.

As CH-acidic compounds are generally considered to carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents activation of the corresponding carbon-hydrogen bond is effected. According to the invention, CH-acidic compounds also include enamines which are formed by alkaline treatment of quaternized N-heterocycles with a CH-acidic alkyl group in conjugation with the quaternary nitrogen.

The CH-acidic compounds of component B are preferably selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium-p- toluenesulfonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 1, 4- Dimethylquinolinium iodide, 1, 2

Dimethylquinolinium iodide, oxindole, 3-indoxylacetate, 2-coumaranone, 5-hydroxy-2-cumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenyl-pyrazolin-5-one, indan-1, 2- dione, indane-1, 3-dione, indan-1-one, benzoylacetonitrile, 3-dicyanomethylene-indan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 3-ethyl-2-methyl- benzothiazolium iodide, 1-ethyl-4-methyl-quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1, 2,3-trimethylquinoxaluminum iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methyl- benzothiazolium-p-toluenesulfonate, 1-ethyl-methyl-quinolinium-p-toluenesulfonate, 1-ethyl-2- methylquinolinium p-toluenesulfonate, and 1,2,3-trimethylquinoxaluminum p-toluenesulfonate. Particularly preferred CH-acidic compounds are 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium chloride, 1, 2-dihydro-1, 3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium chloride , 1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-bis (2-hydroxyethyl) -4,6-dimethyl 2-oxopyrimidinium chloride, 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2- oxo-pyrimidinium hydrogensulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3-bis (2-hydroxyethyl) -4 _L 6-dimethyl 2-oxo-pyrimidinium hydrogen sulfate, 1 ^~ 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidinium chloride, 1, 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidinium hydrogen sulfate, 1 , 2-Dihydro-1, 3-diethyl-4-methyl-2-oxo-pyrimidinium chloride, 1, 2-dihydro-1, 3-diethyl-4-methyl-2-oxo-pyrimidinium hydrogen sulfate, 1, 2-dihydro 1, 3-dipropyl-4-methyl-2-oxo-pyrimidinium chloride, 1, 2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimi dinium hydrogensulfate, 1,2-dihydro-1,3-bis (2-hydroxyethyl) -4-methyl-2-oxopyrimidinium chloride and 1,2-dihydro-1,3-bis (2-hydroxyethyl) -4-methyl- 2-oxo-pyrimidiniumhydrogensulfat.

The colorants according to the invention may furthermore contain all active ingredients, additives and auxiliaries known for such preparations. 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 surface active substances suitable for use on the human body. These are characterized by a water-soluble, 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, Be contained ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 C 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 = O or 1 to 16,

Acylsarcosides having 10 to 18 carbon atoms in the acyl group, acyltaurides having 10 to 18 carbon atoms in the acyl group, acyl isethionates having 10 to 18 carbon atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 carbon atoms Atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates having 12 to 18 carbon atoms, linear alpha-olefin sulfonates having 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester of Fatty acids having 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 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 addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide onto fatty alcohols having 8 to 22 C 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 GIy Kolethergruppen in the molecule and in particular salts of saturated and ins¬ particular unsaturated Cs-C ^ 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 G atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C ₂ -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 hardened 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, 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 consists essentially of C ₈ and C 10 -alkyl groups, H m essentially of C 1 - and CU-alkyl groups, essentially of C 1 - to C 1 -alkyl groups or essentially of C 12 - To C-iβ-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, alto-rose, 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. 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 is therefore wished, in the event that an effect of the perfume oil on the hair which goes beyond the duration of the hair treatment is desired, preferably to use this substance class as a further ingredient of Er¬ inventive preparations.

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.sub.1 or -SO.sub.3 group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example cocoacylaminopropyl- Dimethylammoniumglycinat, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethyl- carboxymethylglycinat. 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 as those surface-active compounds which, in addition to a Cβ-C 16 -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkyl-amidopropylglycines, 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 the N-cocoalkyl aminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines.

Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. 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 contain both at least one ester function and at least one quaternary ammonium group as a structural element. 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 trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75 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. A compound according to the invention particularly suitable from this Substance group represents the commercially available under the name Tegoamid ^® S 18 stearamidopropyl-dimethylamine.

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 Gold¬ schmidt; diquatemäre polydimethylsiloxanes, quaternium-80).

An example of a suitable cationic surfactant quaternary Zucker¬ derivative is the commercially available product Glucquat ^® 100 is, according to INCI nomenclature a "lauryl methyl Gluceth-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 homologues which are used in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalyst. received. Narrowed homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products with narrow homolog distribution may be preferred.

Furthermore, the colorants of the invention can be further active ingredients, auxiliary and

Additives such as nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers _τ 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 dimethylamino-ethylmethacrylate-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 / 2-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,

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextran, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as 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 coloring 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 ingredients 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 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, Quenelles, 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,

Blowing agents such as propane-butane mixtures, N ₂ O ₁ 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.

The compositions according to the invention preferably contain the compounds of the formula I 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, for example, shampoos, foam aerosols or other formulations suitable for use on the hair. However, it is also conceivable to integrate the dye precursors into a powdery or tablet-like formulation. For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C 1 -C ₄ -alkoH ₂ O, 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.

An oxidative dyeing of the fibers can in principle be carried out in the presence of oxidation dye precursors - with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. This lightening effect may be desired regardless of the staining method. Accordingly, the presence of oxidation dye precursors is not a mandatory requirement for the use of oxidizing agents in the compositions according to the invention. Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate.

However, according to the invention, the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

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. Suitable enzymes include peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg

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

Glucose oxidase and D-glucose,

- glycerol oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts,

Alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and their salts,

Tyrosinase oxidase and tyrosine,

Uric acid or its salts, choline oxidase and choline,

- amino acid oxidase and amino acids.

In an application of oxidants, the actual colorant is conveniently prepared immediately prior to use by mixing the preparation of the oxidizing agent with the preparation containing the compounds of formula I and optionally dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures can be in a range between 15 and 40 ⁰ C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The after-washing with a A shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.

In particular, in the case of hair that is difficult to dye, an agent according to the invention may optionally be applied to the hair with additional dye precursors but also without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After a further exposure time of 10 to 20 minutes, the product is then rinsed and, if desired, shampooed again. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to effect a better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified Peroxidisulfat- solutions may be preferred as the oxidizing agent.

A second aspect of the present invention is a process for tinting and / or dyeing keratinous fibers, in particular human hair, in which, if desired, a pretreatment agent M1 is applied to the fiber, then a tinting or coloring agent M2 is applied to the fiber, if desired A second agent M3 is added to the agent M2 before application, this colorant M2 is rinsed off the fiber after a period of 5-30 minutes, and after the treatment optionally an aftertreatment agent M4 is applied to the fiber and rinsed off after a reaction time of a few minutes becomes, wherein at least one of the agents M1, M2, M3 or M4 comprises at least one compound according to formula (I) or one or more of its salts with an inorganic or organic acid

in which R1 and R2 independently represent a hydrogen atom, a linear or cyclic Ci-C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, an -C ₆ - hydroxyalkyl group, a C ₂ - C ₆ -polyhydroxyalkyl group, a Ci-C ₆ -alkoxy-C ₂ -C ₆ alkyl group, an aminoalkyl group, a dialkylaminoalkyl group are, where the radicals R1 and R2 together form a saturated ring further heteroatoms such as N or O and the radical R3 is a hydrogen atom, a halogen atom, a Ci-Cβ-alkyl group, a Ci-Cβ-hydroxyalkyl group, a hydroxy group, an amino group, a dialkylamino group, a Ci-Cβ-alkoxy group, a nitro group, a hydroxy-C 1 -C 6 -alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group and in which n is 3, 4 or 5.

In a method which is preferred according to the invention, the agent M2 is added, shortly before use, an agent M3 containing at least one compound of the formula (I).

Particularly preferred methods according to the invention are characterized in that the agent M3 is a preparation according to the invention. A third object of the present invention is the use of compounds of formula (I) or one or more of their salts with an inorganic or organic acid

independently of each other in the R1 and R2 represents a hydrogen atom, a linear or cyclic -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, a Ci-Cβ hydroxyalkyl group , a C ₂ - Cβ-polyhydroxyalkyl group, a Ci-C ₆ -alkoxy-C ₂ -C ₆ alkyl group, an aminoalkyl group, a dialkylaminoalkyl group, are provided, where the radicals R1 and R2 may form a saturated ring together ^{^,} further heteroatoms such as N or O and the radical R3 is a hydrogen atom, a halogen atom, a Ci-Cβ-alkyl group, a C ₁ -CO-hydroxyalkyl group, a hydroxy group, an amino group, a dialkylamino group, a CrC _δ alkoxy group, a nitro group, a hydroxy dC ₆ alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group are and where n is 3, 4 or 5, in cosmetic center ln.

Preferred uses according to the invention are characterized in that the compound of the formula (I) is used in agents for application to keratin fibers, in particular in agents for tinting and / or dyeing keratin fibers, in particular human hair. With regard to preferred embodiments of the method according to the invention and the use according to the invention, the mutatis mutandis applies to the means according to the invention above.

The following examples are intended to illustrate the subject matter of the present application.

Examples

1st Synthesis Example

Synthesis of 4-amino-5,6,7,8-tetrahydro-1-naphthylamine (E1)

24.9 g (0.143 mol) of sulphanilic acid are suspended in 72 ml of 2N sodium hydroxide solution in a beaker, and a solution of 9.8 g (0.143 mol) of sodium nitrite in 120 ml of water is added. It is stirred until complete dissolution. Then, with ice-salt cooling at 0 - 5 ⁰ C 125 ml Ten percent hydrochloric acid added dropwise within one hour. After this, a yellow suspension of the diazonium salt is obtained.

The suspension of the diazonium salt under ice-salt cooling (0 - 5 ⁰ C) within 30 minutes to a solution of 21 g (0.143 rrtol) 5,6,7,8-tetrahydro-1-naphthylamine in 800 ml of half-concentrated hydrochloric acid dripped. After a stirring time of 1.5 hours, 75.7 g (0.382 mol) of sodium dithionite are added to the reaction solution. Then it is heated to 75 ⁰ C for 20 minutes.

After cooling to room temperature, a pH of 11 is set by dropwise addition of concentrated sodium hydroxide solution. If the temperature of the reaction solution exceeds 20 ⁰ C, is cooled with ice water. The precipitated blue-violet solid is filtered off and washed with plenty of water. After recrystallization from water, a white solid is obtained. Yield: 18.6 g (80%) mp 78 ^° C. (lit. [2]: 83 ^° C.)

2. Application examples

I) Preparation of the coloring cream

Partial mixture A:

Hydrenol D ^{® 1} 8.50 g

Lorol® ^® techn. ² 2.00 g

Eumulgin ^® B2 ³ 0.75 g

Texapon ^® NSO ⁴ 20.00 g

Dehyton ^® K ⁵ 12.50 g

Water 30.00 g ¹ Ci6-Ci ₈ fatty alcohol (INCI name: Cetearyl alcohol) (COGNIS)

² Ci2-C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (COGNIS)

³ Cetearylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (COGNIS)

⁴ lauryl ether sulfate, sodium salt (about 27.5% active ingredient; (INCI name: Sodium Laureth Sulfate) (COGNIS)

⁵ N, N-dimethyl-N- (C ₈ -C ₈ -cocosamidopropyl) ammonium acetobetaine (about 30% active substance, INCI name: Aqua (Water), Cocamidopropyl Betaine) (COGNIS)

The substances Hydrenol ^® D, Lorol ^® and Eumulgin ^® B2 were melted at 80 ⁰ C, with the 80 ⁰ C hot water containing Texapon ^® NSO and Dehyton ^® K, mixed and emulsified with vigorous stirring. Thereafter, the emulsion was cooled with gentle stirring.

Partial mixture B

Sodium sulfite 1.00 g

Ammonium sulfate 1.00 g

Dye precursors in each case 7.5 mmol

Ammonia (25% solution) ad pH = 10.0

Water 10.00 g

The dye precursors were in the 5O ⁰ C hot water with the addition of

Dissolved sodium sulfite, ammonium sulfite and ammonia.

The dye precursor solution (Part B) became the emulsion

(Sub-mixture A), adjusted to pH = 10 with ammonia and made up to 100 g with water. It was stirred until it reached room temperature. II) staining of the fibers

The dyeing cream obtained according to I) was mixed in a ratio of 2: 1 with a 1% H ₂ O ₂ solution and applied to 5 cm long strands of standardized, 80% gray, but not particularly pretreated human hair (Kerling). After 30 minutes exposure time at 32 ⁰ C, the hair was rinsed, washed with a conventional shampoo and then dried.

The results are shown in the table below.

Claims

Patent claim: 1. oxidation dye for dyeing Keratinfasem, in particular human hair, containing at least one Kupplerkompoήente and at least one developer component in an aqueous carrier, characterized in that the coupler component is selected from m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives and the developer component is selected from the compounds according to formula (I),

in which R1 and R2 independently represent a hydrogen atom, a linear or cyclic -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, a Ci-C ₆ - Hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy C ₂ -C ₆ alkyl group, an aminoalkyl group, a Dialkylaminoalkyl group, wherein the radicals R1 and R2 may together form a saturated ring which may contain further heteroatoms such as N or O and the radical R3 is a hydrogen atom, a halogen atom, a Ci-C ₆ alkyl group, a Ci-C _δ - Hydroxyalkyl group, a hydroxy group, an amino group, a dialkylamino group, a C 1 -C ₆ -alkoxy group, a nitro group, a hydroxyCrO- alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group and in which n is 3, 4 or 5, and their salts with an inorganic or organic acid. 2. oxidation dye according to claim 1, characterized in that it contains a developer component of the formula (I), in which n represents 3 or 4. 3. oxidation dye according to one of claims 1 or 2, characterized in that it contains a developer component of the formula (I), in which the radicals R 1, R 2 and R 3 represent a hydrogen atom. 4. oxidation colorant according to one of claims 1 to 3, characterized in that the compound according to formula (I) is selected from 4-amino-5,6,7,8-tetrahydro-1-naphthylamine and / or 7-amino-2 , 3-dihydro-1H-inden-4-ylamine. 5. oxidation colorant according to one of claims 1 to 4, characterized in that it in addition to the coupler components from the group of m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives and the compounds of formula (I) no contains further oxidation dye precursors. 6. oxidation colorant according to one of claims 1 to 5, characterized in that it contains a further developer component which is selected from 3-methyl-1, 4-diaminobenzene, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 2- (2,5-diaminophenoxy) ethanol, N, N-bis (2'-hydroxyethyl) -1, 4-diaminobenzene, 3-methyl-4-aminophenol and 2-methylamino-4-aminophenol, p-phenylenediamine, 2- (beta-hydroxyethyl) -p- phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1, 3-diamino -propan-2-ol, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis- (2 ' , 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-2-aminomethylphenol, 4-amino-2 - ((diethylamino) methyl) phenol, o-aminophenol, 2-amino-4-methylphenol, 2-amino-5-methylphenol, 2-amino-4-chlorophenol, 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, 2,5,6- Triaminopyrimidine, 1- (2'-hydroxy-5'-aminobenzyl) -imidazolidin-2-one, 4,5-diamino-1- (2'-hydroxyethyl) pyrazole and Λ / - (4-amino-3-methylphenyl) -Λ / - [3- (1H-imidazol-1-yl) propyl] amine trihydrochloride. 7. oxidation dye according to one of claims 1 to 4 or 6, characterized in that the coupler component is selected from resorcinol, 3-amino-2-methylamino-6-methoxypyridine, 3-amino-6-methylphenol, 3-amino-2 hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 4-chlororesorcinol 1-naphthol, 1, 5 , 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine, 2 - ({3 - [(2- Hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3- [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine and 2 - [(3-morpholin-4-ylphenyl) amino] ethanol dihydrochloride. 8. Oxidation colorant according to one of claims 1 to 7, characterized in that it contains the coupler component (s) in an amount of 0.01 to 20 wt .-%, preferably from 0.5 to 5 wt .-%, and the developer component (n) in an amount of 0.01 to 20 wt .-%, preferably from 0.5 to 5 wt .-%, each based on the total oxidation colorant. 9. oxidation dye according to one of claims 1 to 8, characterized in that it contains at least one substantive dye --der selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group of the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, 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-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino -1-hydroxy-4-nitrobenzene. 10. A process for tinting and / or coloring keratin fibers, more particularly human hair, in which, if desired, a pretreatment agent is applied to the fiber M1, then a tinting or coloring M2 arrives at the ^• fiber are used, while, if desired, the means M2 before Application of a further agent M3 is added, this colorant M2 is rinsed from the fiber after a time of 5-30 minutes and after treatment - if necessary Aftertreatment agent M4 is applied to the fiber and rinsed again after an exposure time of a few minutes, characterized in that at least one of the means M1, M2, M3 or M4 at least one compound of formula (I) or one or more of its salts with an inorganic or contains organic acid

independently of each other in the R1 and R2 represents a hydrogen atom, a linear or cyclic -C ₆ alkyl group, a C ₂ -C ₆ - alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, an Ci-C6-hydroxyalkyl a C ₂ -C ₆ - polyhydroxyalkyl group, a Ci-C ₆ -alkoxy-C ₂ -C ₆ alkyl group, are an aminoalkyl group, a dialkylaminoalkyl group, wherein the R 1 and R 2 together may form a saturated ring which may contain further heteroatoms such as N or O and R 3 represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a hydroxy group, a Aminogrυppe, a dialkylamino group, a Ci-C _θ -alkoxy, a nitro group, a hydroxy-Ci-Cβ-alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group stand and in which n is 3, 4 or 5. 11. The method according to claim 10, characterized in that the means M2 shortly before use, an agent M3, containing at least one compound of formula (I) is added. 12. The method according to any one of claims 10 or 11, characterized in that the means M3 is a preparation according to one of claims 1 to 9. 13. Use of compounds of the formula (I) or one or more of their salts with an inorganic or organic acid

in the R1 and R2 independently of one another represent a hydrogen atom, a linear or cyclic C _r C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, a Ci-C ₆ - Hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy C ₂ -C ₆ alkyl group, an aminoalkyl group, a Dialkylaminoalkylgruppe, where the radicals R1 and ^' R2 may together form a saturated ring which may contain other heteroatoms such as N or O and the radical' R3 is a hydrogen atom, a halogen atom, a Ci-Cβ-alkyl group, a CrCβ- hydroxyalkyl group , a hydroxy group, an amino group, a dialkylamino group, a C ₁ -C ₆ -alkoxy group, a nitro group, a hydroxy-C ₁ -C ₆ -alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group and in n for 3, 4 or 5, in cosmetic products. 14. Use according to claim 13, characterized in that the compound of formula (I) is used in agents for application to keratin fibers, in particular in agents for tinting and / or dyeing keratin fibers, in particular human hair.