DE102004036688A1 - Cationic azo compounds as direct dyes for coloring keratinic fibers - Google Patents

Abstract

Cationic azo compounds of the general formula (I) DOLLAR F1 with the meaning DOLLAR A X O, S, DOLLAR A Y N, CR · 5 ·, DOLLAR A R · 1 · z. B. H, DOLLAR A R · 3 · z. B. C¶6-12¶-aryl, C¶7-13¶-aralkyl or C¶7-13¶-alkaryl, DOLLAR A R · 2 ·, R · 4 ·, R · 5 · z. B. H DOLLAR A are used as substantive dye for dyeing human hair.

Description

The present invention relates to agents for coloring keratinic fibers, which contain special cationic azo compounds, methods for coloring of fibers, especially hair with these agents, as well as the use the cationic azo compounds for this purpose.

For dyeing Keratin fibers, especially human hair, play the so-called An oxidation because of their intense colors and good fastness properties one preferred role. Such colorants contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the Influence of oxidizing agents or of atmospheric oxygen among one another or under coupling with one or more coupler components the actual dyes from.

When Developer components are usually primary aromatic amines with another, in 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.

Specific Representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) -ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxamido-4-amino-pyrazolone-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-Dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -diaminopropan-2-ol.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols used. Particularly suitable coupling agents are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

For dyeing Keratin fibers are above In addition, direct dyes of great importance. This can, for example cationic dyes which are used in an agent for Coloring keratinischer Fibers are applied directly to these.

The WO 95/01772 relates to a process for coloring keratinous fibers, in which cationic dyes are used. Amongst other things can Azo dyes are used, which have an indole residue and a Thiazolrest or oxazole group, see the structures (1) and (9) of WO 95/01772. In the indole residue, however, the 2-position may be in accordance with this Scriptures should not be substituted by groups, the aromatic nuclei contain. The described cationic substantive dyes are only as a combination of different substantive dyes for coloring used by hair.

EP-A-0 No. 875,620 relates to a process for coloring melamine fibers. there In particular melamine-formaldehyde fibers are colored, the needed in flame retardant applications become. It is described that also articles of melamine fibers used in combination with protein fibers for flame retardancy can be. Can do this Mixtures of melamine fibers with protein fibers or animal fibers be used. Examples are wool, silk, cashmere, Called mohair and rabbit hair. On the coloring of human hair is not received. The dyes used are selected from direct dyes, non-metallated acid dyes, metallated acid dyes, Disperse dyes without carrier and mixtures thereof. According to example 1A, a mixture of melamine fibers and p-aramid fibers with C.I. Colored in Direct Red 79. According to example 11C, C.I. Basic Red 29 is used. On combinations of the mentioned Dyes with further dyes is not discussed in the document.

Direct dyes can be an alternative to oxidation dyes or complement their property profile. Good oxidation dye precursors are to form the desired color shades in sufficient intensity and fastness in the oxidative coupling. They should also have a good Aufziehvermögen on the fiber, in particular in human hair no significant differences between strained and freshly regrown hair should exist (leveling). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, eg permanent wave liquids. Finally, they should - if used as a hair dye used - the scalp not they should be very toxic and dermatologically harmless. 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.

Alone with a developer component or a special coupler / developer combination As a rule, it does not succeed, a naturally acting on the hair To get color nuance. In practice, therefore, are usually Combinations of different developer and / or coupler components used with each other and with direct dyes. It therefore exists constantly Need for new, improved dye components, e.g. Direct dye components, which allow achievement of the above property profile and also in terms of toxicological and dermatological unproblematic are.

task The present invention was therefore substantive dyes especially for coloring to provide human hair, especially in combination with oxidation dye precursors that put to these systems Requirements, also in terms of toxicological and dermatological Properties, meet and dyes in a wide color spectrum with good fastness properties.

Especially intended to provide direct dyes for coloring human hair Be that reddish cause.

It was found according to the invention, that special cationic azo compounds are the directing Dyes for coloring human hair requirements to a high degree. she are particularly advantageous in agents for oxidative coloring keratinischer Fibers, especially human hair can be used as they are beneficial can be combined with oxidation dye precursors.

she show a brilliant Nuancenausfall, very good wash fastness, a very good leveling ability and a good cold wave fastness.

mit der Bedeutung
X O, S
Y N, CR⁵,
R¹ H, Halogen, NO₂, C_6-12-Aryl, C_7-13-Aralkyl, C_7-13-Alkaryl, C_1-6-Alkyl, die gegebenenfalls substituiert sind durch:
-OH, Halogen, -CN, -NO₂, gegebenenfalls OH-substituiertes C_1-4-Alkoxy, -NH₂, -NHR, -NR₂ mit R jeweils unabhängig voneinander gegebenenfalls OH-substituiertes C_1-4-Alkyl,
R³ C_6-12-Aryl, C_7-13-Aralkyl oder C_7-13-Alkaryl, die gegebenenfalls substituiert sind durch -OH, Halogen, -CN, -NO₂, gegebenenfalls OH-substituiertes C_1-4-Alkoxy, -NH₂, -NHR, -NR₂ mit R jeweils unabhängig voneinander gegebenenfalls OH-substituiertes C_1-4-Alkyl,
R², R⁴, R⁵ unabhängig voneinander H, C_1-6-Alkyl, C_1-6-Hydroxyalkyl, C_2-6-Alkoxyalkyl, C_1-6-Aminoalkyl, C_2-10-Alkylaminoalkyl, C_3-12-Dialkylaminoalkyl, C_6-12-Aryl, C_7-13-Aralkyl oder C_7-13-Alkaryl,
als direktziehender Farbstoff zur Färbung menschlicher Haare.A first subject of the invention is therefore the use of cationic azo compounds of the general formula (I)

with the meaning
XO, S
YN, CR ⁵ ,
R ^{1 is} H, halogen, NO ₂ , C _6-12 -aryl, C _7-13 -aralkyl, C _7-13 -alkaryl, C _1-6 -alkyl, which are optionally substituted by:
-OH, halogen, -CN, -NO ₂ , optionally OH-substituted C _1-4 -alkoxy, -NH ₂ , -NHR, -NR ₂ with R each independently of one another optionally OH-substituted C _1-4 -alkyl,
R ^{3 is} C _6-12 aryl, C _7-13 aralkyl or C _7-13 alkaryl optionally substituted by -OH, halo, -CN, -NO ₂ , optionally OH-substituted C _1-4 alkoxy , -NH ₂ , -NHR, -NR ₂ with R each independently of one another optionally OH-substituted C _1-4 -alkyl,
R ² , R ⁴ , R ⁵ independently of one another are H, C _1-6 -alkyl, C _1-6 -hydroxyalkyl, C _2-6 -alkoxyalkyl, C _1-6 -aminoalkyl, C _2-10 -alkylaminoalkyl, C _{3- 12-} dialkylaminoalkyl, C _6-12 -aryl, C _7-13 -aralkyl or C _7-13 -alkaryl,
as a direct dye for dyeing human hair.

mit der Bedeutung
X O, S
Y N, CR⁵,
R¹ H, Halogen, NO₂, C_6-12-Aryl, C_7-13-Aralkyl, C_7-13-Alkaryl, C_1-6-Alkyl, die gegebenenfalls substituiert sind durch:
-OH, Halogen, -CN, -NO₂, gegebenenfalls OH-substituiertes C_1-4-Alkoxy, -NH₂, -NHR, -NR² mit R jeweils unabhängig voneinander gegebenenfalls OH-substituiertes C_1-4-Alkyl,
R³ H, C_1-6-Alkyl, C_1-6-Hydroxyalkyl, C_2-6-Alkoxyalkyl, C_1-6-Aminoalkyl, C_2-10-Alkylaminoalkyl, C_3-12-Dialkylaminoalkyl, C_6-12-Aryl, C_7-13-Aralkyl oder C_7-13-Alkaryl, die gegebenenfalls substituiert sind durch -OH, Halogen, -CN, -NO₂, gegebenenfalls OH-substituiertes C_1-4-Alkoxy, -NH₂, -NHR, -NR² mit R jeweils unabhängig voneinander gegebenenfalls OH-substituiertes C_1-4-Alkyl,
R², R⁴, R⁵ unabhängig voneinander H, C_1-6-Alkyl, C_1-6-Hydroxyalkyl, C_2-6-Alkoxyalkyl, C_1-6-Aminoalkyl, C_2-10-Alkylaminoalkyl, C_3-12-Dialkylaminoalkyl, C_6-12-Aryl, C_7-13-Aralkyl oder C_7-13-Alkaryl,
als direktziehender Farbstoff zur Färbung menschlicher Haare.A further subject is the use of cationic azo compounds of the general formula (Ia)

with the meaning
XO, S
YN, CR ⁵ ,
R ^{1 is} H, halogen, NO ₂ , C _6-12 -aryl, C _7-13 -aralkyl, C _7-13 -alkaryl, C _1-6 -alkyl, which are optionally substituted by:
-OH, halogen, -CN, -NO ₂ , optionally OH-substituted C _1-4 -alkoxy, -NH ₂ , -NHR, -NR ² with R each independently of one another optionally OH-substituted C _1-4 -alkyl,
R ^{3 is} H, C _1-6 alkyl, C _1-6 hydroxyalkyl, C _2-6 alkoxyalkyl, C _1-6 aminoalkyl, C _2-10 alkylaminoalkyl, C _3-12 dialkylaminoalkyl, C _6-12 -Aryl, C _7-13 -aralkyl or C _7-13 -alkaryl, which are optionally substituted by -OH, halogen, -CN, -NO ₂ , optionally OH-substituted C _1-4 -alkoxy, -NH ₂ , - NHR, -NR ² with R independently of each other optionally OH-substituted C _1-4 -alkyl,
R ² , R ⁴ , R ⁵ independently of one another are H, C _1-6 -alkyl, C _1-6 -hydroxyalkyl, C _2-6 -alkoxyalkyl, C _1-6 -aminoalkyl, C _2-10 -alkylaminoalkyl, C _{3- 12-} dialkylaminoalkyl, C _6-12 -aryl, C _7-13 -aralkyl or C _7-13 -alkaryl,
as a direct dye for dyeing human hair.

The definition of the cationic azo compounds of the general formulas (I) and (Ia) differ in the breadth of the definition of the radical R ³ .

The cationic azo compounds of the formulas (I) and (Ia) are in particular advantageous as substantive dyes in agents for oxidative coloring keratinic fibers, especially human hair used.

The Invention also relates to means for coloring human hair, the in a cosmetically acceptable carrier as a direct dye at least one cationic azo compound of the general formula (I) included.

moreover the invention relates to agents for the oxidative dyeing of keratinic fibers, In particular, human hair that is in a cosmetically acceptable carrier Oxidation dye precursors and at least one cationic azo compound of the general formula (Ia).

Under Keratinic fibers are according to the invention furs, wool, feathers and especially to understand human hair. Although the oxidation colorants of the invention primarily for dyeing are suitable for keratin fibers, is in principle a use also in other fields, especially in color photography, nothing contrary.

Examples of the substituents mentioned as substituents in the compounds used according to the invention C ₁ to C ₆ alkyl groups, C ₁ -C _4, preferably alkyl groups which may be linear or branched, are the methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl. Ethyl and methyl are preferred alkyl groups. As the preferred C ₁ to C ₆ (mono) hydroxyalkyl group, there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. C _2-6 -alkoxyalklyreste have a total of 2 to 6 carbon atoms, which are distributed over the alkoxy and the alkyl radical. It can thus be present in the alkoxy or alkyl radical in each case up to 5 carbon atoms. It is preferably a C _1-3 -alkoxy-C _1-3 -alkyl radical, particularly preferably C _1-2 -alkoxy-C _1-2 -alkyl radical. Both the alkoxy and the alkyl moiety may be linear or branched. They are preferably linear. C _1-6 -aminoalkyl radicals, preferably C _1-4 -aminoalkyl radicals, C _2-10 -alkylaminoalkyl radicals, preferably C _2-6 -alkylaminoalkyl radicals and C _3-12 -dialkylaminoalkyl radicals, preferably C _3-9 -dialkylaminoalkyl radicals, can each be linear or branched alkyl radicals exhibit. Each individual alkyl group preferably has 1 to 3 carbon atoms. The alkyl radicals present in the respective groups are preferably as defined above for the pure alkyl radicals.

If radicals are optionally substituted, depending on the number of carbon atoms in the alkyl or alkoxy radical, preferably 1 to 3, particularly preferably 1 or 2, in particular a substituent, may be present. Substituents may be present for R ¹ and R ³ , some of which may in turn be substituted by -OH. Preferably, only one of these further OH substituents is present. C _1-4 -alkyl radicals and C _1-4 -alk Oxy radicals are in turn linear or branched, preferably linear, and particularly preferably ethyl or methyl. If one of the radicals R ² to R ^{5 contains} a hydroxyl group bonded to an alkylene radical, the hydroxyl group is preferably terminal, and the alkylene radical is linear. A hydroxyethyl radical is thus preferably a 2-hydroxyethyl radical.

aryl are preferably phenyl radicals. In aralkyl radicals is a through an aryl radical substituted alkyl radical. In alkaryl residues an aryl radical substituted by an alkyl radical. there the aryl radical is also preferably a phenyl or phenylene radical.

One preferred aralkyl radical is a benzyl radical. A preferred alkaryl radical is a tolyl residue.

The cationic azo compounds of the general formulas (I) and (Ia) are usually as a salt with corresponding counterions, in particular physiologically acceptable Anions, before. It may, for example, in the counterions halide ions, in particular chloride or sulfate, phosphate, nitrate, acetate, Hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate act.

halogen is generally F, Br, Cl or I, preferably Cl or Br.

Particularly preferably, an azo compound of the general formulas (I) or (Ia) has a total of not more than four OH groups, preferably not more than two OH groups. There are in the azo compound of the general formulas (I) or (Ia) preferably at most four nitrogen atoms, more preferably at most two nitrogen atoms in the radicals R ¹ - R ⁵ before. Overall, apart from the hydroxyl groups, in the azo compound of the general formula (I) are preferably a maximum of two further oxygen atoms.

preferred Meanings of the radicals are listed below.

According to one embodiment of the invention, R ^{1 is} hydrogen or C ₁ -C ₄ -alkyl, in particular hydrogen.

According to one embodiment of the invention, Y is CR ⁵ with R ^{5 is} hydrogen or C _1-4 alkyl. In this case, R ⁵ is particularly preferably hydrogen.

According to one embodiment of the invention, R ² and R ^{4 are} C _1-4 -alkyl, more preferably methyl.

According to one embodiment of the invention, R ^{3 is} phenyl, benzyl or tolyl, in particular phenyl.

X is particularly preferably sulfur.

According to the invention, Basic Red 29 is particularly preferably used. This substantive dye corresponds to the formulas (I) and (Ia) with the meanings R ^{1 is} hydrogen, X is sulfur, Y is CH, R ² , R ^{4 is} methyl, R ^{3 is} phenyl, where the counterion is a chloride ion.

Compositions according to the invention for coloring human hair contained in a cosmetically acceptable carrier as direct dye at least one cationic azo compound of the general formula (I) as defined above. preferred Agents of this type are described, for example, in DE-A-102 59 849.

Especially preferred according to the invention is an agent for oxidative staining keratinic fibers, especially human hair, in one cosmetically acceptable carrier Oxidation dye precursors and at least one cationic azo compound of general formulas (I) or (Ia). Preferably, the agent contains at least one developer component and at least one coupler component, as exemplified below.

The inventive agent may be one or more, for example, at least two different ones Azo compounds of the general formulas (I) or (Ia) included.

The Azo compounds of the formulas (I) or (Ia) can be obtained with the aid of conventional produce organic methods.

The agents according to the invention for coloring keratinic fibers or human hair containing at least an azo compound of the general formulas (I) or (Ia) preferably in an amount of 0.02 to 5 wt .-%, particularly preferably 0.1 to 2 wt .-%, based on the finished agent.

The Means for coloring Keratinischer fibers can be from any suitable means to be selected, especially for coloring human hair are suitable. As a cosmetically acceptable carrier is thereby in particular an otherwise customary carrier of means for coloring human Hair used. The colorants according to the invention can, apart from the Azo compounds of the general formulas (I) or (Ia) correspondingly known colorant be composed or for this usual Contain ingredients. Examples of further suitable and inventively more preferred Ingredients are given below.

Compositions of the invention may contain the following ingredients in the amounts indicated. developer 0.05 - 5% pimp 0.05 - 5 Surfactants, emulsifiers 0.1 - 20% Fatty alcohols and other emulsifiers 0.5 - 20% complexing 0.05 - 10% buffering agents 0.1 - 10% Solubilizer + solvent 0,5 - 15% pH adjusters Upon need perfume oils 0.1 - 0.6% polymers 0.1 - 5% water 50 - 98%

suitable Colorant compositions are for example in DE-U1-299 11 819, DE-A-101 25 451, DE-U1-201 11,036, Kosmetik, ed. W. Umbach, 2nd ed. 1995, G.

Thieme Verlag Stuttgart, New York described.

Next The azo compounds of formulas (I) or (Ia) can colorants of the invention further contain at least one developer component.

When Developer components are usually primary aromatic amines with another, in para or ortho position free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

wobei

• – G¹ steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• – G² steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• – G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Acetylaminoalkoxyrest, einen C₁- bis C₄-Mesylaminoalkoxyrest oder einen C₁- bis C₄-Carbamoylaminoalkoxyrest;
• – G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen C₁- bis C₄-Alkylrest oder
• – wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

It may be preferred according to the invention to use as the 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 C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkoxy radical (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• G ² represents a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy radical (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl, C ₁ - to C ₄ -hydroxyalkoxy, C ₁ - to C ₄ -acetylaminoalkoxy, C ₁ - to C ₄ -mesylaminoalkoxy or C ₁ - to C ₄ -carbamoylaminoalkoxy;
• - G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or
• When G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Preferred C ₁ - to C ₄ -alkoxy radicals are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are, in particular, the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups, C ₁ - to C ₄ -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- (α, β-dihydroxyethyl) -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-acetylaminoethyl loxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, wherein also present instead of 3-methylphenyl generally phenyl or C _1-6 alkylphenyl and 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

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

It can continue according to the invention be preferred to use as a developer component compounds, which contain at least two aromatic nuclei which are reactive with amino and / or hydroxyl groups are substituted.

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest, mit den Maßgaben, dass
• – die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• – die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

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

in which:

• - Z ¹ and Z ² independently of one another are a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or is optionally part of a bridging ring system,
• - The bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be and may be substituted by one or more hydroxyl or C ₁ - to C ₈ alkoxy, or a direct bond,
• G ⁵ and G ⁶ independently of one another are a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ alkyl, 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 analogous to the above versions Are defined.

preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methyl-aminophenyl) -tetramethylenediamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) -ethylenediamine, bis- (2- hydroxy-5-aminophenyl) methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically tolerable Salts.

All particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis- (2-hydroxy-5-aminophenyl) methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiologically tolerable Salts.

wobei:

• – G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁- bis C₄)-alkylaminorest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyalkyl-(C₁-bis C₄)-aminoalkylrest oder einen (Di-C₁- bis C₄-Alkylamino)-(C₁- bis C₄)-alkylrest, und
• – G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁- bis C₄-Cyanoalkylrest,
• – G¹⁵ steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• - G¹⁶ steht für Wasserstoff oder ein Halogenatom.

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

The Substituents used in formula (E3) are analogous to the above versions Are defined.

preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) -phenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) -phenol as well as their physiologically tolerable Salts.

All particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) -phenol: Further, the developer component may be selected from o-aminophenol and its derivatives, such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Farther For example, the developer component may be selected from heterocyclic Developer components, such as the pyridine, pyrimidine, Pyrazole, pyrazole pyrimidine derivatives and their physiologically tolerable Salt.

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

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

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892 . DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988 such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3 -dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-damino-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-one 4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-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.

wobei:

• – G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)-[Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]- (C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄-hydroxyalkyl)-aminoalkylrest, einen Aminorest, einen C₁- bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)-aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, dass
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG¹⁹G²⁰ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

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

in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -Polyhydroxyalkylrest a (C ₁ - to C ₄ ) alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, optionally protected by an acetyl-ureide or a sulfonyl radical may be a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl radical, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) aminoalkyl radical, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) aminoalkyl radical,
• - The X radicals independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -Ami noalkyl radical, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl radical, a di - [(C ₁ - to C ₄ ) -alkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, a C ₁ - to C ₄ -alkyl or di- (C ₁ - to C ₄ -hydroxyalkyl) -amino, 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 analogous to the above versions Are defined.

When the pyrazolo [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:

• – Pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – Pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-7-ol;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-5-ol;
• – 2-(3-Aminopyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazol-[1,5-a]-pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.In particular, among the pyrazolo [1,5-a] -pyrimidines of the above formula (E4):

• - pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] -pyrimidine-3,5-diamine;
• 3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
• 3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
• 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
• 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) (2-hydroxyethyl) amino] ethanol;
• - 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) (2-hydroxyethyl) amino] ethanol;
• 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine;

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

The Pyrazole- [1,5-a] -pyrimidines of the above formula (E4) can, as described in the literature by cyclization starting from a Aminopyrazole or produced from hydrazine.

In a further preferred embodiment contain the colorants of the invention at least one coupler component.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives used. Particularly suitable coupling agents are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5,2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

• – m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N-Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6-methylphenol, 5-Amino-4-chlor-2-methylphenol, 5-Amino-4-methoxy-2-methylphenol, 5-(2'-Hydroxyethyl)-amino-2-methylphenol, 3-(Diethylamino)-phenol, N-Cyclopentyl-3-aminophenol, 1,3-Dihydroxy-5-(methylamino)-benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• – o-Aminophenol und dessen Derivate,
• – m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxyethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol, 1-Amino-3-bis-(2'-hydroxyethyl)-aminobenzol, 2-{({3-[2-Hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol, 3-Amino-4-(2-methoxyethoxy)-5-methylphenylamin, 2-({3-[2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol und 2-[(3-Morpholin-4-ylphenyl)amino]ethanol,
• – o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• – Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• – Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• – Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Aminobenzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• – Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol,
• – Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6-dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin, oder
• – Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)-amino-3,4-methylendioxybenzol.

According to the invention, further preferred coupler components are

• - M-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl 3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) - amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro 3-aminophenol,
• O-aminophenol and its derivatives,
• - M-Diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene , 1,3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, 2 - {({3- [2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 2 - ({ 3- [2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol and 2 - [(3-morpholin-4-ylphenyl) amino] ethanol,
• O-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 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly according to the invention preferred further coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, Resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine. 2 - {({3- [2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3- [2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol and 2 - [(3-morpholin-4-ylphenyl) amino] ethanol.

Particularly suitable according to the invention are the following components:
p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, 1- (2-hydroxyethyl) -2,5-diaminobenzene, 1- (2-hydroxyethyl) -4,5-diaminopyrazole, bis (2-hydroxy-5 -aminophenyl) methane, 4-amino-2 - [(5-amino-2-hydroxyphenyl) methyl] phenol x 2HCl.

In a further embodiment of the present invention the colorants contain at least one precursor of a naturally-analogous dye. Preferred precursors of naturally-analogous dyes are those indoles and indolines containing at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups can bear further substituents, for. B. in the form of an etherification or Esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

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 is hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• - R ⁵ is one of the groups mentioned under R ⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially preferred derivatives of indoline are the 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-Dihydroxyindolin-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Especially 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 in particular the 5,6-dihydroxyindoline.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,
• – sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

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

in the independently of each other

• - R ¹ is hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,
• - As well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

Within of this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular the 5,6-dihydroxyindole.

The Indoline and indole derivatives can in the colorants of the invention both as free bases and in the form of their physiologically acceptable Salts with inorganic or organic acids, e.g. The hydrochlorides, the sulfates and hydrobromides used. The indole or Indoline derivatives are common in these in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment it may be preferred according to the invention be the indoline or Indole derivative in colorants in combination with at least one amino acid or an oligopeptide use. The amino acid is advantageously an α-amino acid; all particularly preferred α-amino acids Arginine, ornithine, lysine, serine and histidine, especially arginine.

Next the m-phenylenediamine derivatives of the invention of the formula (I) the colorants of the invention in a further preferred embodiment of the present invention Invention for shading one or more further substantive Dyes contain. Such other substantive dyes are common Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred further substantive dyes are under 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 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'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) -amino-5-chloro-2-nitropenzol, 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 and their salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

• (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• (b) aromatische Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
• (c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908, auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

The compositions of the invention may contain a further cationic substantive dye. Particularly preferred are

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

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

The Compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also available under the terms Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic substantive Dyes of group (c).

The cationic direct dyes which are sold under the brand Arianor® ^® are, according to the invention also very particularly preferred cationic direct dyes.

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

Farther can the preparations according to the invention also occurring in nature dyes such as, for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, Sedre and alkano root are included.

It it is not necessary that the oxidation dye precursors or the direct dyes in each case uniform compounds represent. Rather, you can in the inventions to the invention hair dyes, conditionally by the manufacturing processes for the individual dyes, be contained in minor amounts still other components as far as these are not the dyeing result adversely affect or for other reasons, e.g. toxicological, must be excluded.

Regarding the in the hair dyeing and -tönungsmitteln applicable dyes is still expressly on the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pp. 248-250; Dyes) and chapter 8, pages 264-267; Oxidation dye precursors) appeared as volume 7 of the series "Dermatology" (ed. Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of cosmetic raw materials ", issued by the European Community, available in diskette form from the German Association of Industrial and Trade Companies for Medicines, Health food and personal care products e.V., Mannheim.

The Colorants according to the invention can continue all for such preparations contain known active ingredients, additives and excipients. In many cases contain the colorants at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases However, it has proved to be advantageous, the surfactants from anionic, select zwitterionic or nonionic surfactants.

• – lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,
• – Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 or 3 C atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• Sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,
• Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
• - esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.

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

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C₁₂-C₂₂-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin;
• – C₈-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga sowie
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl.

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 onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• - C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol;
• C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, and
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil.

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

The alkyl radical R ¹ contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

• – im wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• – im wesentlichen aus C₁₂- und C₁₄-Alkylgruppen,
• – im wesentlichen aus C₈- bis C₁₆-Alkylgruppen oder
• – im wesentlichen aus C₁₂- bis C₁₆-Alkylgruppen besteht.

Particular preference is given to those alkylpolyglycosides in which R ¹

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

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

The usable according to the invention Alkyl polyglycosides 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 1.1 to 1.4.

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

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

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. 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 meaning those surface-active compounds which, apart from a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and 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-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

According to the invention can as cationic surfactants, especially those of the quaternary ammonium compound type, the esterquats and amidoamines are used.

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, Lauryldimethylbenzylammoniumchlorid and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants are preferred 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the brands 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. An inventively particularly suitable compound from this group of substances that available under the brand Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine. Further inventively usable cationic surfactants, the qua Ternisierten protein hydrolysates.

Also suitable in the present invention are cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Coring, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).

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

at it may be the compounds with alkyl groups used as surfactant each are uniform substances. It is, however, in usually preferred in the preparation of these substances by native to go out with vegetable or animal raw materials, so that one Substance mixtures with different, from the respective raw material dependent alkyl chain lengths receives.

at the surfactants, the adducts of ethylene and / or propylene oxide represent fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood to mean mixtures of homologs which are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. Narrowed homolog distributions are obtained when, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl-ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazolinium-methochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methylmethacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Malein-säureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z.B. Polyvinylalkohol,
• – Strukturanten wie Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• – quaternierte Amine wie Methyl-l-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• – Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• – Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,.
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien,

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

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers, quaternary group polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• Zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacrylate / tert-butylaminoethylmethacrylate / 2-hydroxypropylmethacrylate 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-butylacrylamide terpolymers,
• Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. 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,
• - structurants 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, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Fiber-structure-improving active substances, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• Quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• Defoamers like silicones,
• Dyes for staining the agent,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• - active substances such as allantoin, pyrrolidonecarboxylic acids and their salts, and 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, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• Fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizer for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants,

contain.

Regarding further optional components as well as the amounts of these components used expressly on the specialist manuals known to those skilled in the art, eg. B. Kh. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

The agents according to the invention contain the dye precursors preferably in a suitable aqueous, alcoholic or watery-alcoholic Carrier. For the purpose of hair coloring For example, such carriers are Creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations, the for the application on the hair are suitable. But it is also conceivable the dye precursors in a powdered or tablet-shaped formulation to integrate.

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

The actual oxidative staining the fibers can basically done with atmospheric oxygen. However, preference is given to a chemical Oxidizing agent used, especially if in addition to the coloring, a whitening effect desired on human hair is. The oxidizing agents are persulfates, chlorites and in particular Hydrogen peroxide or its addition products to urea, Melamine and sodium borate in question. However, according to the invention the oxidation colorant also be applied to the hair together with a catalyst, 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⁺ 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.

• – Pyranose-Oxidase und z.B. D-Glucose oder Galactose,
• – Glucose-Oxidase und D-Glucose,
• – Glycerin-Oxidase und Glycerin,
• – Pyruvat-Oxidase und Benztraubensäure oder deren Salze,
• – Alkohol-Oxidase und Alkohol (MeOH, EtOH),
• – Lactat-Oxidase und Milchsäure und deren Salze,
• – Tyrosinase-Oxidase und Tyrosin,
• – Uricase und Harnsäure oder deren Salze,
• – Cholinoxidase und Cholin,
• – Aminosäure-Oxidase und Aminosäuren.

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, with the aid of Atmospheric oxygen directly oxidize the oxidation dye precursors, such as the laccases, or generate in situ small amounts of hydrogen peroxide 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 eg 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,
• Uricase and uric acid or their salts,
• - choline oxidase and choline,
• - amino acid oxidase and amino acids.

The actual hair dye is expediently immediately before use by mixing the preparation of the Oxidizing agent with the preparation containing the dye precursors, produced. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Especially the use of the hair dye in a weakly alkaline is preferred Milieu. The application temperatures can be in a range between 15 and 40 ° C lie. After an exposure time of usually 5 to 45 minutes becomes the hair dye by rinsing of which to be colored Hair removed. The washing with a shampoo is eliminated, if a strong surfactant-containing carrier, e.g. a dyeing shampoo, has been used.

Especially in hard-to-dye Hair can be the preparation with the dye precursors as well without prior mixing with the oxidation component on the Hair will be applied. After an exposure time of 20 to 30 minutes will then - if necessary after an intermediate rinse - the oxidation component applied. After another exposure time of 10 to 20 minutes is then rinsed and if desired shampooed. In this embodiment, according to a first variant, in which the previous application of the dye precursors to effect a better penetration into the hair, the corresponding Medium adjusted to a pH of about 4 to 7. According to one second variant is first an air oxidation, with the applied agent being preferred has a pH of 7 to 10. At the subsequent accelerated Post-oxidation may be the use of acidified peroxydisulfate solutions as Oxidizing agent may be preferred.

One third subject of the present invention is a method for coloring keratinic fibers, in particular human hair, in which a Hair colorant according to the invention is applied to the fibers and after a contact time again rinsed becomes.

The The invention is further illustrated by the following examples.

Examples

To prepare the following recipe examples, these substantive dyes were used: N-N'-bis (2-hydroxyethyl) -2-nitro-l, 4-phenylenediamine Violet 1,4 D 2-amino-6-chloro-4-nitrophenol Rodol 9R Base N '- (2-hydroxyethyl) amino-2-nitro-4-aminobenzene HC Red 3 1- (2-hydroxyethylamino) -2-nitropeenol HC Yellow 2 2 - [(2-amino-4-nitrophenyl) amino] ethanol HC Yellow 5 4-amino-2-nitrodiphenylamine HC Red 1 2-nitro-4'-hydroxydiphenylamine HC Orange 1 N, N, N'-tris (2-hydroxyethyl) -2-nitro-l, 4-phenylenediamine HC Blue 2 4 - [(3-hydroxypropyl) amino] -3-nitrophenol HC Red BN 4 - [(2-hydroxyethyl) amino] -3-nitrophenol HC Red B 54 (4-Methylamino-1-naphthyl) bis- (4-diethylaminophenyl) -carbenium chloride Basic Blue 7 3 - [(4-Amino-6-bromo-5,8-dihydro-1-hydroxy-8-imino-5-oxo-2-naphthyl) amino] -1- [N, N, N-trimethylammonio] benzene chloride Basic Blue 99 [8 - [(4-aminophenyl) azo] -7-hydroxy-2-naphthyl] trimethylammonium chloride Basic Brown 16 [8 - [(4-amino-3-nitrophenyl) azo] -7-hydroxy-2-naphthyl] trimethylammonium chloride Basic Brown 17 1-methyl-4 - [(methylphenylhydrazono) methyl] pyridinium methyl sulfate Basic Yellow 87 2 - [(4-aminophenyl) azo] -1,3-dimethyl-1H-imidazolium chloride Basic Orange 31 2- (4-dimethylamino-phenylazo) -1,3-dimethyl-3H-imidazol-l-ium chloride Basic Red 51 [7-hydroxy-8 - [(2-methoxyphenyl) azo] -2-naphthyl] trimethylammonium chloride Basic Red 76 3 - [(4,5-dihydro-3-methyl-5-oxo-1-phenyl-1H-pyrazol-4-yl) azo] -1- [N, N, N-trimethylammonio] -benzene-chloride Basic Yellow 57 (4-Amino-3-methylphenyl) bis (4-aminophenyl) -carbenium chloride Basic Violet 14 4 - [(2-Hydroxy-1-naphthyl) azo] benzenesulfonic acid sodium salt Acid Orange 7 Naphthalene-2,7-disulfonic acid sodium salt Acid Black 1 2 - [(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthracenyl) -amino] -5-methyl-benzenesulfonic acid sodium salt Acid Violet 43 5-Amino-4-hydroxy-3- (phenylazo) naphthalene-2,7-disulfonic acid sodium salt Acid Red 33 3.6-bis (diethylamino) -9- (2,4-disulfophenyl) -xanthylium sodium, inner salt Acid Red 52

The following raw materials were used to prepare the following recipe examples: Texapon.RTM ^® NSO Sodium Lauryl Sulfate (INCI: Sodium Lauryl Sulfate) (Cognis Germany) Lorol® ^® techn. C ₁₂ -C ₁₈ fatty alcohol (INCI name: Coconut Alcohol) (Cognis Germany) Polychol ^® 5 Lanolin alcohol with 5 EO units (INCI name: Laneth-5) (Croda) Eumulgin ^® B1 Cetylstearyl alcohol with 12 EO units (INCI name: Ceteareth-12) (Cognis Germany) Eumulgin ^® B2 Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) Eumulgin ^® RO 40 ethoxylated castor oil (INCI name: PEG-40 Castor Oil) (Cognis Germany) Stenol ^® 1618 C _16-18 fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis Germany) Dehydrol® ^® 100 (INCI name: Laureth-10) (Cognis Germany) Akypo ^® RLM 45 N about 82% active ingredient, (INCI name: Sodium Laureth-5 Carboxylates) (KAO) Dehyton ^® K N, N-dimethyl-N- (C ₈ -C ₁₈ -coconutamidopropyl) -ammonium acetobetaine (about 30% active ingredient; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis Germany) Amine oxide WS 35 N, N-dimethyl-N (C _8-18 -cocoacylamidopropyl) amine N-oxide, 35% active ingredient (INCI name: Cocamidopropylamine oxides) (Goldschmidt) Dehyquart® ^® A Trimethylhexadecylammonium chloride, approx. 27% Active substance (INCI name: Aqua (Water), Cetrimonium Chloride) (Cognis Germany) Dehyquart ^® F 75 Fatty alcohols Methyltriethanolammoniummethylsulfatdialkylester mixture (INCI name: Distearoylethyl Hydroxyethylmonium Methosulfate, Cetearyl Alcohol) (Cognis Germany) Dow Corning 345 ^EU® Decamethylcyclopentasiloxane (INCI name: Cyclomethicones) (Dow Corning) Lipoxol ^® 400 MED Polyethylene glycol (INCI name: PEG-8) (Sasol) Nutrilan® ^® Keratin W enzymatically derived hydrolyzate Merino wool (INCI name: Aqua (Water), Hydrolyzed keratin, phenoxyethanol, methalparaben, Butylparaben, ethylparaben, propylparaben) (Cognis Germany) Aminol A 15 ^® C _13-15 Alkyl Ether Carboxylate Monoethanolamide (INCI name: Trideceth-2 Carboxamide MEA) (KAO) Phenonip ^® about 27% active substance, (INCI name: Phenoxyethanol, methylparaben, ethylparaben, Propylparaben, butylparaben) (Clariant) AMP 95 2-amino-2-methylpropanol (Dow) Carbopol ^® ETD 2001 Polyacrylic acid (INCI name: Carbomer) (Noveon) Aculyn ^® 22 (INCI name: Acrylates / Steareth-20 Methacrylate copolymer) (Rohm & Haas) Aculyn ^® 33 (INCI name: Acrylates Copolymer) (Rohm & Haas) Merquat ^® 280 Dimethyldiallylammonium chloride-acrylic acid copolymer (INCI name: Polyquaternium-22) (Nalco) Merquat ^® 100 Poly (dimethyldiallylammonium chloride) (INCI name: Polyquaternium-6) (Nalco) Natrosol ^® 250 HR Hydroxyethylcellulose (INCI name: Hydroxyethylcellulose) (Hercules) Polymer ^JR® 400 quaternized hydroxyethylcellulose (INCI name: Polyquaternium-10) (Amerchol) Mirapol ^® A 15 Poly [N- (3- (dimethylammonium) propyl] -N '- [3-ethyleneoxyethylene dimethyl ammonium] propyl] urea dichloride (INCI name: Polyquaternium-2) (Rhodia) Luviskol ^® K30 Polyvinylpyrrolidone (INCI name: PVP) (BASF) Geliderm ^® 3000 P Coconut fatty acid collagen hydrolyzate sodium salt (INCI name: Sodium Cocoyl Hydrolyzed Collagen) (DGF German Gelatine Factories Stoess) Tegoamid ^® S 18 N, N-dimethyl-N'-stearoyl-1,3-diaminopropane (INCI name: Stearamidopropyl Dimethylamine) (Degussa) Gluadin® ^® AGP KL Wheat protein hydrolyzate (INCI name: Hydrolyzed Wheat Protein) (Cognis Germany) Henna neutral Cassia auriculata, leaves dried and ground, (INCI name: Cassia Auriculata (Linne) Cassia Auriculata Leaf Powder) (Paul Müggenburg GmbH) Henna red Lawsonia inermis, leaves dried and ground, coloring ingredient 2-hydroxy-1,4-naphthoquinone (INCI name: Lawsonia Inermis (Linne) Henna Extract) (Paul Müggenburg GmbH) Kukui nut oil (INCI name: Kukui Nut Oil Aleurites Moluccana (Linne)) (Worlee) Silkall ^® 100 Silk protein (INCI name: Silk Serica (Linne)) (Ikeda Bussan Kaisha) Turpinal® ^® SL 1-Hydroxyethane-1,1-diphosphonic acid (INCI name: Etidronic Acid, Aqua (Water)) (Solutia) Sodium water glass 40/42 Sodium silicate (Cognis Germany)

foam tint

The following Foam tints according to the table 1 were prepared and in a pressure-release container with a propane-butane mixture assembled as a blowing agent.

Table 1

2 g of a foam tint according to Table 1 were each left for 0.5 g of human hair strand (Kerling, natural white) over a period of 20 minutes. The hair was then rinsed and dried. The strands of hair were dyed as follows: Recipe no. colour 1 brownish copper 2 reddish copper

toning lotion

Fortsetzung Tabelle 2

Tabelle 3

The following tint lotions according to Tables 2 and 3 were prepared: Table 2

Continuation Table 2

Table 3

2.0 g of a tinting lotion according to Table 2 or 3 was applied to 0.5 g of human hair strand (Kerling, Na tur white) for a period of 20 minutes. The hair was then rinsed and dried. The strands of hair were dyed as follows: Recipe no. colour 3 garnet 4 dark red 5 warm brown 6 shining red

color conditioner

Fortsetzung Tabelle 4

The following color conditioners according to Table 4 were prepared: TABLE 4

Continuation Table 4

2.0 g of a color conditioner according to Table 4 were each left for 0.5 g of human hair strands (Kerling, natural white) over a period of 20 minutes. The hair was then rinsed and dried. The strands of hair had a full feel and a silky sheen and were dyed as follows: Recipe no. colour 7 bright violet 8th honey-colored 9 shining red

Powder Hair Color

Fortsetzung Tabelle 5

Powder hair colors are prepared in the form of a fine powder (sieve fraction 0.05-1.0 nm) according to Table 5: Table 5

Continuation Table 5

For each coloration, 25 g of a powder according to Table 5 were mixed with 60 ml of hot water. After the resulting dye mixture had cooled to a temperature of 40 ° C., 2.0 g of the dye mixture were applied to 0.5 g of a human hair strand (Kerling, natural white) and rinsed off again after a contact time of 30 minutes. The strands dyed with the dye mixtures according to Table 5 were dried and obtained the following colorations: Recipe no. colour 10 sandelholzfarben 11 intense violet

Oxidation hair

Fortsetzung Tabelle 6

Tabelle 7: Oxidationsmittelzubereitung

The following coloring creams are prepared according to Table 6: Table 6: Dyeing creams

Continuation Table 6

Table 7: Oxidizing agent preparation

Shortly before use, a coloring cream according to Table 6 was mixed with the oxidizing agent preparation according to Table 7 in a weight ratio of 1: 1. X g of this mixture was left on Y g of a human hair strand (Kerling natural white) for 30 minutes at 32 ° C on the hair and then rinsed. The strand of hair was dried and the color result was assessed. Nuance No colour 12 intense red 13 intense violet 14 intense copper

Claims (17)

Use of cationic azo compounds of general formula (n

in which X is O, SYN, CR ⁵ , R ^{1 is} H, halogen, NO ₂ , C _6-12 -aryl, C _7-13 -aralkyl, C _7-13 -alkaryl, C _1-6 -alkyl, which are optionally substituted are by: -OH, halogen, -CN, -NO ₂ , optionally OH-substituted C _1-4 alkoxy, -NH ₂ , -NHR, -NR ₂ with R each independently of one another optionally OH-substituted C _1-4 - Alkyl, R ³ C _6-12 -aryl, C _7-13 -aralkyl or C _7-13 -alkaryl, which are optionally substituted by: -OH, halogen, -CN, -NO ₂ , optionally OH-substituted C _{1- 4} -alkoxy, -NH ₂ , -NHR, -NR ₂ with R each independently of one another optionally OH-substituted C _1-4 -alkyl, R ² , R ⁴ , R ⁵ independently of one another H, C _1-6 -alkyl, C _1-6 hydroxyalkyl, C _2-6 alkoxyalkyl, C _1-6 aminoalkyl, C _2-10 alkylaminoalkyl, C _3-12 dialkylaminoalkyl, C _6-12 aryl, C _7-13 aralkyl or C _{7 -13-} alkaryl, as a direct dye for dyeing human hair. Use according to claim 1, characterized in that in the azo compounds of the general formula (I) R ^{3 is} C _6-12 -aryl. Use according to claim 1 or 2, characterized in that in the azo compounds of general formula (I) R ^{1 is} hydrogen or C _1-4 alkyl. Use according to one of claims 1 to 3, characterized in that in the azo compounds of general formula (I) Y is CR ⁵ with R ^{5 is} hydrogen or C _1-4 alkyl. Use according to one of claims 1 to 4, characterized in that in the azo compounds of the general formula (I) R ² and R ⁴ signify C _1-4 -alkyl. Means for coloring human hair, contained in a cosmetically acceptable carrier direct dye at least one cationic azo compound of the general formula (I) as claimed in any one of claims 1 to 5 is defined. Use of cationic azo compounds of the general formula (Ia)

with the meaning X is O, SYN, CR ⁵ , R ^{1 is} H, halogen, NO ₂ , C _6-12 -aryl, C _7-13 -aralkyl, C _7-13 -aralkyl, C _1-6 -alkyl, which are optionally substituted by: -OH, halogen, -CN, -NO ₂ , optionally OH-substituted C _1-4 -alkoxy, -NH ₂ , -NHR, -NR ² with R each independently of one another optionally OH-substituted C _1-4 -alkyl, R ³ H, C _1-6 alkyl, C _1-6 hydroxyalkyl, C _2-6 alkoxyalkyl, C _1-6 aminoalkyl, C _2-10 alkylaminoalkyl, C _3-12 dialkylaminoalkyl, C _6-12 Aryl, C _7-13 -aralkyl or C _7-13 -alkaryl, which are optionally substituted by: -OH, halogen, -CN, -NO ₂ , optionally OH-substituted C _1-4 -alkoxy, -NH ₂ , - NHR, -NR ² with R independently of one another optionally OH-substituted C _1-4 -alkyl, R ² , R ⁴ , R ⁵ independently of one another H, C _1-6 -alkyl, C _1-6 -hydroxyalkyl, C _{2- 6} alkoxyalkyl, C _1-6 aminoalkyl, C _2-10 alkylaminoalkyl, C _3-12 dialkylaminoalkyl, C _6-12 aryl, C _7-13 aralkyl or C _7-13 alkaryl, as a direct dye in Funds for oxidative staining of keratinic fibers, especially human hair. Use according to claim 7, characterized in that in the azo compounds of general formula (Ia) R ^{3 is} C _6-12 -aryl. Use according to claim 7 or 8, characterized in that in the azo compounds of general formula (Ia) R ^{1 is} hydrogen or C _1-4 alkyl. Use according to one of claims 7 to 9, characterized in that in the azo compounds of general formula (Ia) Y CR ⁵ with R ^{5 is} hydrogen, C _1-4 alkyl. Use according to one of claims 7 to 10, characterized in that in the azo compounds of the general formula (Ia) R ² and R ⁴ signify C _1-4 -alkyl. Agent for the oxidative dyeing of keratinic fibers, especially human hair, containing in a cosmetic acceptable carrier at least one oxidation dye precursor and at least one cationic azo compound of the general formula (Ia), as described in one of the claims 7 to 11 is defined. Agent according to claim 12, characterized in that that there is at least one developer component and at least one Coupler component contains. Agent according to claim 12 or 13, characterized that as developer components primary aromatic amines having a further, in para- or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives, 2,4,5,6-tetraaminopyrimidine and its derivatives and mixtures thereof. Agent according to one of claims 12 to 14, characterized in that the coupler components m-phenylenediamine derivatives, naphthols, Resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols as well Mixtures thereof are used. Method of coloring human hair, in which an agent according to claim 6 on the hair is applied and rinsed again after a contact time. Method of coloring keratinic fibers, wherein an agent according to any one of claims 12 to 15 is applied to the fibers and after a contact time again rinsed becomes.