DE102006028018A1 - Brightening and / or coloring with esters and / or anhydrides - Google Patents

Abstract

Improved and irritation-reduced agents for whitening and / or dyeing keratin fibers, in particular human hair, containing - based on their weight - 0.001 to 15 wt .-% of at least one ester and / or anhydride of the formula (I): $ F1 in the X, Y, Z are independently of one another a hydrogen atom or a halogen atom and R is an optionally substituted aryl group or an optionally substituted (C <SUB> 1 </ SUB> -C <SUB> 6 </ SUB>) alkyl group or a hydroxyalkyl group or a polyhydroxyalkyl group or an optionally substituted (C <SUB> 1 </ SUB> -C <SUB> 6 </ SUB>) alkylene group or a (C <SUB> 1 </ SUB> -C <SUB> 6 </ SUB >) - acyl radical. In addition, preferably from 0.001 to 5 wt .-% of one or more oxidation dye products and / or direct dyes are included.

Description

The The present invention relates to agents for coloring and / or lightening keratinic Fibers, i. Agent for use on keratin fibers, in particular human hair, and their use.

The change The shape and color of the hair represents an important area of the hair This can change the appearance of the hair both current fashion trends as well as the individual wishes adapted to the individual person become. It can Perm and others changing the hair shape Method almost independent be used on the type of hair to be treated. On the other hand are dyeing and bleaching procedures limited to certain initial hair colors. The basics of the Blondierverfahren are known in the art and can in relevant Monographs, e.g. by Kh. Schrader, Foundations and Recipes of Kosmetika, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Umbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, can be read.

simultaneously But there is also often the desire to change the hair color and along with the hair coloring also a whitening of the to be colored To reach hair.

conventional Hair Dye usually consist of at least one developer and at least a coupler substance and optionally contain direct dyes as a nuance. Coupler and developer components are also known as Oxidation dye precursors referred.

In front their application to human hair will be hair dyeing and / or lightening agent in solid or pasty form mixed with dilute aqueous hydrogen peroxide solution. This mixture is then applied to the hair and after a rinsed out certain exposure time again. The exposure time on the Hair to achieve a complete coloration or brightening is between about 30 and 40 minutes. It is obvious, that at There is a need for users of these hair dyes or bleaching agents to do this Reduce exposure time.

Neither the pasty ones still the powdery dyeing and / or bleaching agents that are on the market today can be considered as be optimally viewed. While the dyeing and / or blonding effect on the hair as tailored to consumer needs can be designated, but there are still a number of disadvantages and problems in both manufacturing and handling this means.

So Coloring and bleaching processes usually take place on keratinic fibers at alkaline pH values, in particular between 9.0 and 10.5. These pH values are necessary to an opening of the outer cuticle (cuticle) to ensure and a penetration of the active species (dye precursors and / or Hydrogen peroxide) in the hair. As alkalizing agent is usually ammonia used, however, for the users the disadvantage of intense smell and possible irritation having.

In Market products are used as alternative alkalizing agents to ammonia For example, aminomethylpropanol or monoethanolamine used. However, since they often lag behind ammonia in their performance, they usually become used in admixture with ammonia. But again, the performance of the Ammonia, especially with regard to the parameters gray covering, whitening performance and color result.

It Therefore, there is still a need for active ingredients or drug combinations for brightening and colorants with reduced ammonia content. In particular, should be reduced in ammonia or even -free dye and / or hydrogen peroxide-containing Formulations one with conventional ammonia-based funds comparable performance can be achieved.

It it has now been found that certain esters and / or anhydrides with particular advantage in hair dyeing and incorporate brightening agent and to increase performance lead this means.

in der
X, Y, Z stehen unabhängig voneinander für ein Wasserstoffatom oder ein Halogenatom
R steht für eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte (C₁-C₆)-Alkylgruppe oder eine Hydroxyalkylgruppe oder eine Polyhydroxyalkylgruppe oder eine gegebenenfalls substituierte (C₁-C₆)-Alkylengruppe, oder einen (C₁-C₆)Acylrest.The present invention relates, in a first embodiment, to agents for dyeing and / or lightening keratin fibers, in particular human hair, containing-by weight-0.001 to 15% by weight of at least one ester and / or anhydride of the formula (I):

in the
X, Y, Z independently represent a hydrogen atom or a halogen atom
R is an optionally substituted aryl group or an optionally substituted (C ₁ -C ₆ ) -alkyl group or a hydroxyalkyl group or a polyhydroxyalkyl group or an optionally substituted (C ₁ -C ₆ ) -alkylene group, or a (C ₁ -C ₆ ) acyl radical ,

Under Keratin fibers are furs, wool, feathers and especially human ones To understand hair. Although the agents of the invention in the first place to dye and / or whitening keratin fibers is suitable in principle their use in other areas.

• – Essigsäuremethylester und/oder
• – Essigsäureethylester und/oder
• – Monoiodessigsäuremethylester und/oder
• – Monobromessigsäuremethylester und/oder
• – Monochloressigsäuremethylester und/oder
• – Monofluoressigsäuremethylester und/oder
• – Diiodessigsäuremethylester und/oder
• – Dibromessigsäuremethylester und/oder
• – Dichloressigsäuremethylester und/oder
• – Difluoressigsäuremethylester und/oder
• – Triiodessigsäuremethylester und/oder
• – Tribromessigsäuremethylester und/oder
• – Trichloressigsäuremethylester und/oder
• – Trifluoressigsäuremethylester und/oder
• – Monoiodessigsäureethylester und/oder
• – Monobromessigsäureethylester und/oder
• – Monochloressigsäureethylester und/oder
• – Monofluoressigsäureethylester und/oder
• – Diiodessigsäureethylester und/oder
• – Dibromessigsäureethylester und/oder
• – Dichloressigsäureethylester und/oder
• – Difluoressigsäureethylester und/oder
• – Triiodessigsäureethylester und/oder
• – Tribromessigsäureethylester und/oder
• – Trichloressigsäureethylester und/oder
• – Trifluoressigsäureethylester

enthalten.The compositions of the invention contain as essential ingredient at least one ester and / or at least one anhydride of the formula (I), that is, acetic acid ester or anhydrides and / or one of the relevant halo derivatives. According to the invention, especially agents for dyeing and / or lightening keratinic fibers are characterized in that they contain one or more esters from the group

• - Acetic acid methyl ester and / or
• - ethyl acetate and / or
• - Monoiodessigsäuremethylester and / or
• - Monobromessigsäuremethylester and / or
• - Monochloroacetic acid methyl ester and / or
• Monofluoroacetic acid methyl ester and / or
• - Diiodoacetic acid methyl ester and / or
• - Dibromoacetic acid methyl ester and / or
• - Dichloroacetic acid methyl ester and / or
• - Difluoressigsäuremethylester and / or
• - Triiodessigsäuremethylester and / or
• - Tribromessigsäuremethylester and / or
• - Trichloroacetic acid methyl ester and / or
• - Trifluoroacetic acid methyl ester and / or
• - Monoiodessigsäureethylester and / or
• - Monobromessigsäureethylester and / or
• - Monochloroacetic acid ethyl ester and / or
• Monofluoroacetic acid ethyl ester and / or
• - Diiodoacetic acid ethyl ester and / or
• Dibromoacetic acid ethyl ester and / or
• - Dichloressigsäureethylester and / or
• - Difluoroacetic acid ethyl ester and / or
• - Triiodoacetic acid ethyl ester and / or
• Tribromoacetic acid ethyl ester and / or
• Trichloroacetic acid ethyl ester and / or
• - Trifluoroacetic acid ethyl ester

contain.

In addition to the said acetic acid esters or haloacetic acid esters or in their place the agents according to the invention also acetic anhydrides or haloacetic anhydrides contain. It can both "pure" and "mixed Anhydrides "of the respective acetic acid or haloacetic acid are used, i. also anhydrides from the acetic acid or Halogenoessigsäure with other carton acids.

• – Essigsäureanhydrid und/oder
• – Monoiodessigsäureanhydrid und/oder
• – Monobromessigsäureanhydrid und/oder
• – Monochloressigsäureanhydrid und/oder
• – Monofluoressigsäureanhydrid und/oder
• – Diiodessigsäureanhydrid und/oder
• – Dibromessigsäureanhydrid und/oder
• – Dichloressigsäureanhydrid und/oder
• – Difluoressigsäureanhydrid und/oder
• – Triiodessigsäureanhydrid und/oder
• – Tribromessigsäureanhydrid und/oder
• – Trichloressigsäureanhydrid und/oder
• – Trifluoressigsäureanhydrid und/oder
• – Propionsäure-Essigsäureanhydrid und/oder
• – Butansäure-Essigsäureanhydrid und/oder
• – Essigsäure-Monoiodessigsäureanhydrid und/oder
• – Essigsäure-Monobromessigsäureanhydrid und/oder
• – Essigsäure-Monochloressigsäureanhydrid und/oder
• – Essigsäure-Monofluoressigsäureanhydrid und/oder
• – Essigsäure-Diiodessigsäureanhydrid und/oder
• – Essigsäure-Dibromessigsäureanhydrid und/oder
• – Essigsäure-Dichloressigsäureanhydrid und/oder
• – Essigsäure-Difluoressigsäureanhydrid und/oder
• – Essigsäure-Triiodessigsäureanhydrid und/oder
• – Essigsäure-Tribromessigsäureanhydrid und/oder
• – Essigsäure-Trichloressigsäureanhydrid und/oder
• – Essigsäure-Trifluoressigsäureanhydrid und/oder
• – Trichloressigsäure-Monoiodessigsäureanhydrid und/oder
• – Trichloressigsäure-Monobromessigsäureanhydrid und/oder
• – Trichloressigsäure-Monochloressigsäureanhydrid und/oder
• – Trichloressigsäure-Monofluoressigsäureanhydrid und/oder
• – Trichloressigsäure-Diiodessigsäureanhydrid und/oder
• – Trichloressigsäure-Dibromessigsäureanhydrid und/oder
• – Trichloressigsäure-Dichloressigsäureanhydrid und/oder
• – Trichloressigsäure-Difluoressigsäureanhydrid und/oder
• – Trichloressigsäure-Triiodessigsäureanhydrid und/oder
• – Trichloressigsäure-Tribromessigsäureanhydrid und/oder
• – Trichloressigsäure-Trifluoressigsäureanhydrid und/oder
• – Trifluoressigsäure-Monoiodessigsäureanhydrid und/oder
• – Trifluoressigsäure-Monobromessigsäureanhydrid und/oder
• – Trifluoressigsäure-Monochloressigsäureanhydrid und/oder
• – Trifluoressigsäure-Monofluoressigsäureanhydrid und/oder
• – Trifluoressigsäure-Diiodessigsäureanhydrid und/oder
• – Trifluoressigsäure-Dibromessigsäureanhydrid und/oder
• – Trifluoressigsäure-Dichloressigsäureanhydrid und/oder
• – Trifluoressigsäure-Difluoressigsäureanhydrid und/oder
• – Trifluoressigsäure-Triiodessigsäureanhydrid und/oder
• – Trifluoressigsäure-Tribromessigsäureanhydrid und/oder
• – Trifluoressigsäure-Trichloressigsäureanhydrid

enthalten.Particularly preferred compositions according to the invention for dyeing and / or lightening keratinic fibers are characterized in that they contain one or more anhydrides from the group

• Acetic anhydride and / or
• Monoiodoacetic anhydride and / or
• Monobromoacetic anhydride and / or
• Monochloroacetic anhydride and / or
• Monofluoroacetic anhydride and / or
• Diiodoacetic anhydride and / or
• Dibromoacetic anhydride and / or
• - Dichloroacetic anhydride and / or
• Difluoroacetic anhydride and / or
• - Triiodessigsäureanhydrid and / or
• Tribromoacetic anhydride and / or
• Trichloroacetic anhydride and / or
• Trifluoroacetic anhydride and / or
• Propionic acid-acetic anhydride and / or
• Butanoic acid acetic anhydride and / or
• Acetic acid monoiodoacetic anhydride and / or
• Acetic acid monobromoacetic anhydride and / or
• Acetic acid monochloroacetic anhydride and / or
• Acetic acid monofluoroacetic anhydride and / or
• Acetic acid diiodoacetic anhydride and / or
• Acetic acid dibromoacetic anhydride and / or
• Acetic acid dichloroacetic anhydride and / or
• Acetic acid-difluoroacetic anhydride and / or
• Acetic acid triiodoacetic anhydride and / or
• Acetic acid tribromoacetic anhydride and / or
• Acetic acid trichloroacetic anhydride and / or
• Acetic acid trifluoroacetic anhydride and / or
• Trichloroacetic acid monoiodoacetic anhydride and / or
• Trichloroacetic acid monobromoacetic anhydride and / or
• Trichloroacetic acid monochloroacetic anhydride and / or
• Trichloroacetic acid monofluoroacetic anhydride and / or
• Trichloroacetic diiodoacetic anhydride and / or
• Trichloroacetic acid dibromoacetic anhydride and / or
• Trichloroacetic acid-dichloroacetic anhydride and / or
• Trichloroacetic acid-difluoroacetic anhydride and / or
• Trichloroacetic acid triiodoacetic anhydride and / or
• Trichloroacetic acid tribromoacetic anhydride and / or
• Trichloroacetic acid trifluoroacetic anhydride and / or
• Trifluoroacetic acid monoiodoacetic anhydride and / or
• Trifluoroacetic acid monobromoacetic anhydride and / or
• Trifluoroacetic acid monochloroacetic anhydride and / or
• Trifluoroacetic acid monofluoroacetic anhydride and / or
• Trifluoroacetic acid diiodoacetic anhydride and / or
• Trifluoroacetic acid-dibromoacetic anhydride and / or
• Trifluoroacetic acid-dichloroacetic anhydride and / or
• Trifluoroacetic acid-difluoroacetic anhydride and / or
• Trifluoroacetic acid triiodoacetic anhydride and / or
• Trifluoroacetic acid tribromoacetic anhydride and / or
• Trifluoroacetic acid trichloroacetic anhydride

contain.

Preferably the ester (s) or anhydride (s) are within closer Quantity ranges used. Here are means according to the invention to dye and / or brightening keratinic fibers which the ester (s) and / or anhydride (s) in amounts of from 0.1 to 12.5 Wt .-%, preferably from 0.25 to 10 wt .-%, more preferably from 0.5 to 7.5% by weight, and more preferably from 1 to 5% by weight, respectively based on the total mean, included.

The agents according to the invention serve as agents for dyeing and / or lightening keratinic fibers. Pure brighteners, which are also referred to as Blondiermittel, additionally preferably contain oxidizing agents (see below). Preferably, the agents according to the invention are provided as colorants which do not serve (only) to lighten, but also or exclusively to a color change of the keratinic fibers treated with them. Agents which simultaneously have a coloring and lightening effect are also known as brightening colorants called.

preferred inventive agent to dye and / or lightening keratinic fibers are characterized that she additionally - related on her weight - 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes.

The agents according to the invention are preferably colorants, i.e. Means of change the color of keratinous fibers. Among these are in particular the so-called oxidation colorants prefers. Oxidation colorants according to the invention contain at least one coupler and at least one developer component. Coupler and developer components are also known as oxidation dye precursors designated. In addition, you can the oxidation colorants of the invention also contain direct dyes as Nuanceure. According to the invention preferred Dyeing agent and / or lightening keratinic fibers are thus characterized that she additionally - related on her weight - 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes.

The agents according to the invention serve as a dyeing agent and / or lightening keratinic fibers. Pure lightening agents that also be referred to as Blondiermittel additionally preferably contain Oxidizing agent (see below). Preferably, the agents according to the invention as a colorant provided, which serve not (only) a brightening, but also or exclusively a color change the keratinic fibers treated with them. Means at the same time coloring and whitening, are also called whitening colorants designated.

preferred inventive agent to dye and / or lightening keratinic fibers are characterized that she additionally - related on her weight - 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes.

The agents according to the invention are preferably colorants, i.e. Means of change the color of keratinous fibers. Among these are in particular the so-called oxidation colorants prefers. Oxidation colorants according to the invention contain at least one coupler and at least one developer component. Coupler and developer components are also known as oxidation dye precursors designated. In addition, you can the oxidation colorants of the invention also contain direct dyes as Nuanceure. According to the invention preferred Dyeing agent and / or lightening keratinic fibers are thus characterized that she additionally - related on her weight - 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes.

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-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives. As coupler substances Particularly suitable are α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, Resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 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, 3-amino-6-methoxy-2-methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

• – Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kuppler-Typ, und
• – Vorstufen naturanaloger Farbstoffe, wie Indol- und Indolin-Derivate, sowie Mischungen von Vertretern dieser Gruppen enthalten.

With regard to the further dyestuff precursors which can be used in the dyestuffs according to the invention, the present invention is not subject to any restrictions. The colorants according to the invention can be used as further dye precursors

• - Developer and / or coupler type oxidation dye precursors, and
• - Precursors of natural-analogous dyes, such as indole and indoline derivatives, and mixtures of representatives the contained in these groups.

In a first preferred embodiment contains the colorant at least one developer component. As developer components become common 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 according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are, 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.

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

Very particular according to the invention preferred p-phenylenediamine derivatives of the formula (E1) are 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 colorants according to the invention, mention may be made in particular of the compounds which correspond 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 used in formula (E2) substituents are analogous to the invention to the above statements 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-methylaminophenyl) 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 acceptable 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. Particularly preferred are p-aminophe Nol 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 used in formula (E3) substituents are analogous to the invention to the above statements 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- (⎕-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 For example, the developer component can 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 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 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 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'- chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1 , 3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert. -butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3 - (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1 isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (D-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 -methylpyrazol.

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); Die in Formel (E4) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.

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 having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C _{1 to} C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) aminoalkyl radical,
• - the X radicals are each independently a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, a C ₁ - to C ₄ -alkyl or di- (C ₁ - to C ₄ -hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1, with the proviso that
• The sum of p + q is not equal to 0,
• If p + q equals 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);
• When p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); The substituents used in formula (E4) are defined according to the invention analogously to the above statements.

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-hydroxy-ethyl) 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.

Particularly according to the invention preferred means of dyeing and / or lightening keratinic fibers are characterized that she as oxidation dye precursor at least one developer component containing preferred developer components are selected from p-phenylenediamine, p-toluenediamine ,, N, N-bis (2-hydroxyethyl) amino-p-phenylenediamine, 1,3-bis - [(2-hydroxyethyl-4'-aminophenyl) amino] propane-2-ol, 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane, 4-aminophenol, 4-amino-3-methylphenol, bis (5-amino-2-hydroxyphenyl) methane, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4,5-diamino-1- (2-hydroxyethyl) pyrazole.

The Colorants according to the invention can furthermore contain 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-chlororesorcinol, 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 und 1-Amino-3-bis-(2'-hydroxyethyl)aminobenzol,
• – 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-hydioxypyridin, 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-Amino-benzomorpholin,
• – 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 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 and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• O-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
• Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino 4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly according to the invention preferred 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.

When Precursors of naturally-analogous dyes are preferably those indoles and indolines containing at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups can carry further substituents, e.g. in the form of 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
• – R⁶ 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 (IIIa),

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C 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 ⁶ 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-dihydroxyindoline-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 (IIIb),

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 especially the 5,6-dihydroxyindole.

The Indoline and indole derivatives can in the used in the context of the method according to the invention coloring 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 Indolderivat in hair dyes in combination with at least one amino acid or an oligopeptide. The amino acid is advantageous an α-amino acid; all particularly preferred α-amino acids Arginine, ornithine, lysine, serine and histidine, especially arginine.

Particularly according to the invention preferred means of dyeing and / or lightening keratinic fibers are characterized that she contain at least one coupler component as oxidation dye precursor, preferred coupler components being selected from resorcinol, 2-methylresorcinol, 5-methyl-resorcinol, 2,5-dimethylresorcinol, 4-chlororesorcinol, resorcinol monomethyl ether, 5-aminophenol, 5-amino-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 3-Amino-4-chloro-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-amino-2,4-dichlorophenol, 2,4-diaminophenoxyethanol, 2-amino-4- (2'-hydroxyethyl) amino-anisolsulfat, 1,3-bis (2,4-diaminophenoxy) propane, 2-amino-3-hydroxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-phenyl-3-methylpyrazol-5-one, 2,6-bis - [(2'-hydroxyethyl) amino] -toluene, 4-hydroxyindole, 6-hydroxyindole, 6-hydroxybenzomorpholine.

Preferably become coupler and developer components in a certain ratio to each other used. Here are oxidation colorants according to the invention preferably, the coupler component (s) in an amount of 0.01 to 20 wt .-%, preferably from 0.5 to 5 wt .-%, and the developer component (s) in from 0.01 to 20% by weight, preferably from 0.5 to 5% by weight, each based on the total oxidation colorant included.

Additionally, the colorants may contain one or more substantive dyes for shade. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, triphenylmethane dyes, acid dyes, basic dyes, preferably from the group of the international trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 1, 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, Acid Red 92, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Disperse Red 17, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol , 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-di nitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2-Ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, Picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene, 3- (2 ', 6'- Diaminopyridyl-3'-azo) pyridine; 2 - ((4- (ethyl (2-hydroxyethyl) amino) -2-methylphenyl) azo) -5-nitro-1,3-thiazole; N, N-di (2-hydroxyethyl) -3-methyl-4 - ((4-nitrophenyl) azo) -aniline; 3-diethylamino-7- (4-dimethylaminophenylaz0) -5-phenyl-phenazinium chloride; 4- (2-thiazolylazo) resorcinol; 4 - (((4-phenylamino) azo) benzosulfonic acid, sodium salt, 1 - ((3-aminopropyl) amino) -9,10-anthracenedione, 3 ', 3'',4,5,5', 5 '', 6,7-octabromophenolsulfonephthalein; 1 - ((4-amino-3,5-dimethylphenyl) - (2,6-dichlorophenyl) methylene) -3,5-dimethyl-4-imino-2,5-cyclohexadiene-phosphoric acid (1 : |) (Basic Blue 77); 3 ', 3'',5', 5 '' - Tetrabrom-m-kre solsulfonphthalein; 2,4-dinitro-l-naphthol-7-sulfonic acid disodium salt; 4- [2'-hydroxy-1'-naphthyl) azo] benzenesulfonic acid sodium salt; 3 ', 6'-dihydroxy-2', 41 | 51 | 71-tetraiodospiro [isobenzo-furan-1 (3H), g1 (9H) -xanthenl-3-one disodium salt; 6-hydroxy-5 - ((2-methoxy-5-methyl-4-sulfophenyl) azo) -2-naphthalene-sulfonic acid disodium salt; 2,4-dinitro-Inaphthol sodium salt; 2 ', 4', 5 ', 7'-tetrabromo-4151617-tetrachloro-3'16'-dihydroxy-spiro [isobenzofuran-l (3H), 9' [9H] xanthene] -3-one disodium salt; 4- (2-hydroxy-l-naphthylazo) -3-methyl-benzolsulfonsäurenatriumsalz; Basic Orange 31, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic, Brown 16, Basic Brown 17, Natural Brown 7, Basic Green 1, Basic Red 2, Basic Red 12 Basic Red 22, Basic Red 51, Basic Red 76, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 10, Basic Violet 14, Basic Yellow 57, Basic Yellow 87, Basic Red 46.

According to the invention preferred Dyeing agent and / or lightening keratinic fibers are characterized that she contain at least one substantive dye that is selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group of international Names or trade names of known dyes 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, Acid Black 52, Basic Yellow 87, Basic Orange 31 and Basic Red 51 known compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) -aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2-Ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

• (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• (b) aromatischen 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 Heterozyklus 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.

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

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

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 trademark Arianor® ^®, are also very particularly preferred cationic substantive dyes according to the invention.

The agents according to the invention according to this embodiment contain the substantive dyes preferably in an amount from 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 hair colorants according to the invention 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 ", published from 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.

A coloring Keratinic fibers can also be made by means of dyes which in an oxidatively catalyzed reaction of C, H-acidic compounds be formed with reactive carbonyl compounds.

• A Verbindungen, die eine reaktive Carbonylgruppe enthalten mit Komponente
• B Verbindungen, ausgewählt aus (a) CH-aciden Verbindungen, (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen, (c) Aminosäuren, (d) aus 2 bis 9 Aminosäuren aufgebauten Oligopeptiden.

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

• A compounds containing a reactive carbonyl group with component
• B Compounds selected from (a) CH-acidic compounds, (b) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (c) amino acids, (d) from 2 up to 9 amino acids oligopeptides.

• a) Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Kondensationsverbindung
• b) von Alkoholen unter Bildung von Acetaten oder Ketalen als Kondensationsverbindung
• c) von Wasser unter Bildung von Hydraten als Additionsverbindung.

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

• a) amines and derivatives thereof to form imines or oximes as a condensation compound
• b) of alcohols to form acetates or ketals as a condensation compound
• c) of water to form hydrates as addition compound.

Component A is preferably selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4, 6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4- Dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4 , 4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1-hydroxy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7- Trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone,
Vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxy benzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxybenzaldehyde 2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy 4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3 Ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6- Dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-T trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2, 4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino 2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy- 1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimeth oxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2-methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3- methoxy-cinnamic aldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylamino benzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9- carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline ( Fischer's aldehyde or tribasic aldehyde),
2-indolealdehyde, 3-indolealdehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ', 3 ', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine , 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, chromon-3-aldehyde, 3- (5 'Nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein and imidazole-2-aldehyde,
1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- (2'-pyridoyl) acetophenone and 2- (3'-pyridoyl) acetophenone,
Benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4-diethylaminobenzylideneacetone, 3 Benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2-Benzylidene-cyclohexanone, 2- (4'-hydroxybenzylidene) cyclohexanone, 2- (4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3- (4'-dimethylaminobenzylidene) -1, 3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxy-3 -methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene) - cyclopentanone, 2- (4'-dimethyl aminobenzylidene) -cyclopentanone,
5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3, 4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl ) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal,
6- (4-Dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5 -dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6 - (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3,5- dien-2-one,
5- (4-Dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy 3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3 nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-ni trobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2- Nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9- Methyl 3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1,4, 9-trimethyl-3-carbazolaldehyd,
4-Formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1 benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1 methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8- Formyl 1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-Formyl-1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-1-allylquinolinium, 6-formyl-1-allylquinolinium, 7-formyl-1 allyl-quinolinium and 8-formyl-1-allyl-quinolinium, 5-acetyl-1-methyl-quinolinium, 6-acetyl-1-methyl-quinolinium, 7-acetyl-1-methyl-quinolinium, 8-acetyl-1-methylchloro nolinium, 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium, 6-acetyl 1-benzylquinolinium, 7-acetyl-1-benzylquinolinium, 8-acetyl-1-benzylquinolinium, 5-acetyl-1-allylquinolinium, 6-acetyl-1-allylquinolinium, 7-acetyl-1-allylquinolinium and 8 Acetyl-1-allyl quinolinium, 9-formyl-10-methylacridinium, 4- (2'-formylvinyl) -1-methylpyridinium, 1,3-dimethyl-2- (4'-formylphenyl) benzimidazolium, 1, 3-Dimethyl-2- (4'-formylphenyl) imidazolium, 2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium, 2- (4'-methyl) Formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5 '-Formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formyl-1-naphthyl) -3-methylbenzothiazolium, 5-chloro -2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3 , 5-dimethylbenzothiazolium benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate,
Isatin, 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5- Carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures of the above compounds.

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• • R^1*, R^2* und R^3* stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Dialkylaminogruppe, eine Di(C₂-C₆-hydroxyalkyl)aminogruppe, eine Di(C₁-C₆-alkoxy-C₁-C₆-alkyl)aminoguppe, eine C₁-C₆-Hydroxyalkyloxygruppe, eine Sulfonylgruppe, eine Carboxygruppe, eine Sulfonsäuregruppe, eine Sulfonamidogruppe, eine Sulfonamidgruppe, eine Carbamoylgruppe, eine C₂-C₆-Acylgruppe oder eine Nitrogruppe,
• • Z' steht für eine direkte Bindung oder eine Vinylengruppe,
• • R^4* und R^5* stehen für ein Wasserstoffatom oder bilden gemeinsam, zusammen mit dem Restmolekül einen 5- oder 6-gliederigen aromatischen oder aliphatischen Ring.

Benzaldehyde, cinnamic aldehyde and naphthaldehyde and their derivatives, in particular having one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl compound in the agents according to the invention. Again, the compounds according to formula (Ca-1) are preferred,

wherein

• R ^{1 *} , R ^{2 *} and R ^{3 *} independently of one another represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkyl group, a hydroxy group, a C ₁ -C ₆ -alkoxy group, a C ₁ -C ₆ - Dialkylamino group, di (C ₂ -C ₆ hydroxyalkyl) amino group, di (C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl) amino group, C ₁ -C ₆ hydroxyalkyloxy group, sulfonyl group, carboxy group , a sulfonic acid group, a sulfonamido group, a sulfonamide group, a carbamoyl group, a C ₂ -C ₆ acyl group or a nitro group,
• Z 'is a direct bond or a vinylene group,
• • R ^{4 *} and R ^{5 *} represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

The derivatives of the benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component C are particularly preferably selected from certain aldehydes. Preferred herein are agents which additionally contain at least one reactive carbonyl compound selected from the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-metho xybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl 4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2- Ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxybenzaldehyde 2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy-4- hydroxy-benzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxy-benzaldehyde, 2-ethoxy-4-hydroxy-benzaldehyde, 3-ethoxy 4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenza ldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2, 3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2, 4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3-methoxy- benzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde 2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2, 3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydrox benzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3 Chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4- Dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1 naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 5- Hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehy d, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro 4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4- (1-imidazolyl) benzaldehyde and piperonal.

According to the invention preferred Agents are characterized in that they act as hair dyes formulated, based on their weight 0.01 to 20 wt .-%, preferably 0.05 to 15 wt .-%, particularly preferably 0.1 to 12.5 Wt .-% and in particular 0.2 to 10 wt .-% of one or more reactive Carbonyl compound (s) included.

When CH-Acids are generally considered to be compounds which a hydrogen atom bonded to an aliphatic carbon atom carry, due to electron-withdrawing substituents one Activation of the corresponding carbon-hydrogen bond causes becomes. According to the invention, CH-acidic compounds also include enamines. by alkaline treatment of quaternized N-heterocycles with a conjugated to quaternary nitrogen CH-acid Alkyl group arise.

The CH-acidic compounds of component B are preferably selected from the group consisting of 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1,4-dimethylchinolinium iodide, 1,2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-indoxylacetate, 2-coumaranone, 5- Hydroxy-2-cumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenyl-pyrazolin-5-one, indan-1,2-dione, indan-1,3-dione, indan-1-one, Benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5-dimethylcyclohexane-1,3-dione, 2H -1,4-benzoxazin-4H-3-one, 3-ethyl-2-me ethyl benzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl-4-methylquinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,2,3-trimethylquinoxaluminum iodide, 3-ethyl-2-methyl-benzoxazolium-p- toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl-4-methyl-quinolinium p-toluenesulfonate, 1-ethyl-2-methylquinolinium p-toluenesulfonate, and 1,2,3-trimethylquinoxaluminum p-toluene sulfonate.

in der R6 für eine Hydroxy- oder eine Aminogruppe, die durch C1-4-Alkyl, Cl.4-Hydroxyalkyl- oder C1-4-Alkoxy-C1-4-alkyl substituiert sein kann, steht, R7, R'', R9, R'O und RI' für Wasserstoff, eine Hydroxy- oder eine Aminogruppe, die durch eine Cl-4-Alkyl-, Cl-4-Hydroxyalkyl, Cl-4-Aminoalkyl- oder Cl-4-Alkoxy- C1-4-alkylgruppe sub-stituiert sein kann, für eine Carbon- doer Sulfonsäuregruppe stehen, und Z für eine direkte Bindung, eine gesättigte oder ungesättigte, ggf. durch Hydroxygruppen substituierte Kohlenstoffkette mit 1 bis 4 Kohlenstoffatomen, eine Carbonyl-, Sulfonyl- oder Iminogruppe, ein Sauerstoff- oder Schwefelatom, oder eine Gruppe mit der Formel 111 Q-(CH2-p-CH2-Q')1 > (111) in der P eine direkte Bindung, eine CH2- oder CHOH-Gruppe bedeutet, Q und Q' unabhängig voneinander für ein Sauerstoffatom, eine NR 12 – Gruppe, worin R 12 Wasserstoff, eine Cl-, -Alkyl-, oder Hydroxy-C 1-4-alkylgruppe bedeutet, die Gruppe 0-(CH2)p-NH oder NH-(CH2)p, -0, worin p und p' 2 oder 3 sind, stehen und o eine Zahl von 1 bis 4 bedeutet, wie beispielsweise 4,4'- Diaminostilben, 4,4'-Diaminostilben-2,2'-disulfonsäure-mono- oder -di-Na-Salz, 4-Amino-4'-dimethylaminostilben, 4,4'-Diaminodiphenylmethan, -sulfid,
-sulfoxid, -amin, 4,4'-Diaminodiphenyiamin-2-sulfonsäure, 4,4'-Diaminobenzophenon, -diphenylether, 3,3',4,4'-Tetraaminodiphenyl, 3,3',4,4'-Tetraamino-benzophenon, 1,3-Bis-(2,4-diaminophenoxy)-propan, 1,8-Bis-(2,5-diaminophenoxy)-3,6-dioxaoctan, 1,3-Bis-(4-aminophenylamino)-propan,-2-propanoi, 1,3-Bis-[N-(4-aminophenyl)-2-hydroxyethyla-mino]-2-propanol, N,N-Bis-[2-(4-aminophenoxy)-ethyl]-methylamin, N-Phenyl-1,4-phenylendiamin.Suitable compounds having primary or secondary amino group as component B are, for example, primary aromatic amines such as N, N-dimethyl, N, N-diethyl, N- (2-hydroxyethyl) -N-ethyl, N, N-bis ( 2-hydroxyethyl) -, N- (2-methoxyethyl), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4 -morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenoi, 2-hydroxymethyl-4-aminophenoi, o-, p-phenylenediamine, o-toluenediamine, 2,5-diaminotoluene, -phenot , - phenethole, 4-amino-3-methylphenoi, 2- (2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanoi, 2- (2,5-diaminophenoxy) ethanol, 4-methylamino, 3 -Amino-4- (2'-hydroxyethyloxy) -, 3,4-methylenediamino, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro, 4-methylamino, 2-methyl-5-amino , 3-methyl-4-amino, 2-methyl-5- (2-hydroxyethylamino) -, 6-methyl-3-amino-2-chloro, 2-methyl-5-amino-4-chloro, 3 , 4-methylenedioxy, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl, 4-amino-2-hydroxymethylphenol, 1,3-diamino-2,4 -dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicyacetic acid, 3 Amino-4-hydroxy, 4-amino-3-hydroxybenzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6- Amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5- Aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, penta-aminobenzene, hexa-aminobenzene, 2,4,6-triaminoresorcinol, 4,5 Di-amino-catechol, 4,6-diaminopyrogaliol, 3,5-diamino-4-hydroxy-catechol, aromatic anilines or phenols with another aromatic radical as shown in the formula below

in the R6 stands for a hydroxy or an amino group which may be substituted by C1-4-alkyl, Cl.4-hydroxyalkyl or C1-4-alkoxy-C1-4-alkyl, R7, R ", R9 , R'O and RI 'are hydrogen, a hydroxy or an amino group represented by a Cl-4-alkyl, Cl-4-hydroxyalkyl, Cl-4-aminoalkyl or Cl-4-alkoxy-C1-4- alkyl substituent group, Z is a direct bond, a saturated or unsaturated, optionally substituted by hydroxy groups carbon chain having 1 to 4 carbon atoms, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group of the formula III Q- (CH 2 -p-CH 2 -Q ') 1> (III) in which P is a direct bond, a CH 2 or CHOH group, Q and Q' are independently for an oxygen atom, an NR 12 group in which R 12 is hydrogen, a Cl, alkyl, or hydroxyC 1-4 alkyl group, the group 0- (CH 2) p -NH or NH- (CH 2) p, -O, wherein p and p '2 od he is 3, stand and o is a number from 1 to 4, such as 4,4'-diaminostilbene, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 4- Amino-4'-dimethylaminostilbene, 4,4'-diaminodiphenylmethane, sulfide,
sulfoxide, amine, 4,4'-diaminodiphenyiamine-2-sulfonic acid, 4,4'-diaminobenzophenone, diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetraamino benzophenone, 1,3-bis- (2,4-diaminophenoxy) -propane, 1,8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane, 1,3-bis (4-aminophenylamino) propane, 2-propanoi, 1,3-bis [N- (4-aminophenyl) -2-hydroxyethyl-amino] -2-propanol, N, N-bis [2- (4-aminophenoxy) -ethyl ] -methylamine, N-phenyl-1,4-phenylenediamine.

The the aforementioned compounds both in free form and in the form of their physiologically acceptable Salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid, can be used.

Suitable nitrogen-containing heterocyclic compounds are, for example, 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino 5-amino, 2-methylamino-3-amino-6-methoxy, 2,3-diamino-6-methoxy, 2,6-dimethoxy-3,5-dia-mino-, 2,4,5 Triamino, 2,6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino, 4,5,6-triamino, 4-hydroxy-2,5,6-triamino , 2-hydroxy-4,5,6-triamino, 2,4,5,6-tetraamino, 2-methylamino-4,5,6-triamino, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methyl-pyrimidine, 3,5-diaminopyrazole, 1,2,4-triazole, 3-amino, 3-amino-5-hydroxypyrazole, 2-, 3-, 8- Aminoquinoline, 4-amino-chinaidine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-aminobenzimidazole, benzothiazole, 2,5-dihydroxy-4-morpholinoan-lin and indoles and indolines, and their physiologically acceptable salts. Preferred examples of indole or indoline derivatives 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. Further preferred are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5 , 6-dihydroxyindoline-2-carboxylic acid. 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline. The abovementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, for example as salts of inorganic acids, such as hydrochloric or sulfuric acid.

When amino acids All come naturally occurring and synthetic (alpha-amino acids in question, e.g. Hydrolysis of plant or animal proteins, e.g. collagen, Keratin, casein, elastin, soy protein, wheat gluten or almond protein, accessible Amino acids. It can both acidic and alkaline amino acids are used become. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), Ornithine, lysine and tryptophan. But you can also use other amino acids be such. 6-aminocaproic acid.

The Oligopeptides can of course occurring or synthetic oligopeptides, but also those in polypeptide or protein hydrolysates contained oligopeptides, provided they have a for the Application in the colorants according to the invention sufficient water solubility feature. As examples, e.g. Glutathione or in the hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or to name almond protein-containing oligopeptides. Prefers is the use together with compounds with primary or secondary Amino group or with aromatic hydroxy compounds.

suitable Aromatic hydroxy compounds are e.g. 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, catechol, Hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy, 3-dimethylamino, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, - phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, acetophenone, 2-, 4-chlororesorcinol, 1-naphthol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid ,

When CH-active compounds can 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium p-toluoisulfonate, are mentioned by way of example, 1,2,3,3-tetramethyl-3H-indolium methanesulfonate, Fischer's base (1,3,3-trimethyl-2-methylenindoline), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl-2-quinaldinium iodide, 1-methyl-2-quinaldinium iodide barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxyl acetate, Coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

worin

• • R⁸ und R⁹ stehen unabhängig voneinander für eine lineare oder cyclische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-C₁-C₆-alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₁-C₆-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,
• • R¹⁰ und R^{1 2} stehen unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe, wobei mindestens einer der Reste R¹⁰ und R^{1 2} eine C₁-C₆-Alkylgruppe bedeutet,
• • R¹¹ steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Hydroxyalkoxygruppe, eine Gruppe R^IIIR^IVN-(CH₂)_q-, worin R^III und R^IV stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe und q steht für eine Zahl 1, 2, 3, 4, 5 oder 6, wobei der Rest R¹¹ zusammen mit einem der Reste R¹⁰ oder R^{1 2} einen 5- oder 6-gliedrigen aromatischen Ring bilden kann, der gegebenenfalls mit einem Halogenatom, einer C₁-C₆-Alkylgruppe, einer C₁-C₆-Hydroxyalkylgruppe, einer C₂-C₆-Polyhydroxyalkylgruppe, einer C₁-C₆-Alkoxygruppe, einer C₁-C₆-Hydroxyalkoxygruppe, einer Nitrogruppe, einer Hydroxygruppe, einer Gruppe R^VR^VIN-(CH₂)_s-, worin R^V und R^VI stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe und s steht für eine Zahl 0, 1, 2, 3, 4, 5 oder 6 substituiert sein kann,
• • R^{1 3} und R^{1 4} bilden entweder zusammen mit dem Stickstoffatom einen gesättigten oder ungesättigten 5- oder 6-gliedrigen Ring oder stehen unabhängig voneinander für eine (C₁-C₆)-Alkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine Arylgruppe, eine Aryl-(C₁-C₆)-alkylgruppe, eine (C₂-C₆)-Hydroxyalkylgruppe, eine (C₂-C₆)-Polyhydroxyalkylgruppe oder eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁-C₆)-Alkylgruppe, eine (C₁-C₆)-Alkenylgruppe oder eine Aryl-C₁-C₆-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6, und
• • R^{1 5} ein Wasserstoffatom, eine (C₁-C₆)-Alkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine Arylgruppe, eine Aryl-(C₁-C₆)-alkylgruppe, eine (C₂-C₆)-Hydroxyalkylgruppe, eine (C₂-C₆)-Polyhydroxyalkylgruppe oder eine Gruppe R^IIIR^IVN-(CH₂)_n-, worin R^III und R^IV stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁-C₆)-Alkylgruppe, eine (C₁-C₆)-Alkenylgruppe oder eine Aryl-C₁-C₆-alkylgruppe, wobei R^III und R^IV gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und n steht für eine Zahl 2, 3, 4, 5 oder 6
• • Y steht für ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe NR^VII worin R^VII steht für ein Wasserstoffatom, eine Arylgruppe, eine Heteroarylgruppe, eine C₁-C₆-Alkylgruppe oder eine C₁-C₆-Arylalkylgruppe,
• • X^– steht für ein physiologisch verträgliches Anion,
• • Het steht für einen gegebenenfalls substituierten Heteroaromaten,
• • X¹ steht für eine direkte Bindung oder eine Carbonylgruppe.

The CH-acidic compounds are preferably selected from the formulas (II) and / or (III) and / or (IV)

wherein

• R ⁸ and R ⁹ independently of one another represent a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-C ₁ -C ₆ - alkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl group, a group R ^I R ^II N- (CH ₂ ) _m in which R ^I and R ^II independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group, where R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
• • R ¹⁰ and R ^{1 2} are each independently a hydrogen atom or a C ₁ -C ₆ alkyl group, wherein at least one of the radicals R ¹⁰ and R ^{1 2} is a C ₁ -C ₆ alkyl group,
• R ¹¹ is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ -Hydroxyalkoxygruppe, a group R ^III R ^IV N- (CH ₂ ) _q -, wherein R ^III and R ^IV independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group or a Aryl-C ₁ -C ₆ -alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ¹¹ together with one of the radicals R ¹⁰ or R ^{1 2 is} a 5- or 6-membered may form an aromatic ring optionally substituted with a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ -hydroxyalkoxy, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH ₂ ) _s -, wherein R ^V and R ^VI independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ - C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,
• R ^{1 3} and R ^{1 4} either together with the nitrogen atom form a saturated or unsaturated 5- or 6-membered ring or independently of one another represent a (C ₁ -C ₆ ) -alkyl group, a (C ₂ -C ₆ ) - Alkenyl group, an aryl group, an aryl (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) hydroxyalkyl group, a (C ₂ -C ₆ ) polyhydroxyalkyl group or a group R ^I R ^II N- (CH ₂ ) _m -, in which R ^I and R ^II independently of one another represent a hydrogen atom, a (C ₁ -C ₆ ) -alkyl group, a (C ₁ -C ₆ ) -alkenyl group or an aryl-C ₁ -C ₆ -alkyl group where R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, and
• R ^{1 5 represents} a hydrogen atom, a (C ₁ -C ₆ ) -alkyl group, a (C ₂ -C ₆ ) -alkenyl group, an aryl group, an aryl (C ₁ -C ₆ ) -alkyl group, a (C ₂ -) C ₆ ) -hydroxyalkyl group, a (C ₂ -C ₆ ) -polyhydroxyalkyl group or a group R ^III R ^IV N- (CH ₂ ) _n -, in which R ^III and R ^IV independently of one another represent a hydrogen atom, a (C ₁ - C ₆ ) alkyl group, a (C ₁ -C ₆ ) alkenyl group or an aryl C ₁ -C ₆ alkyl group, wherein R ^III and R ^IV together with the nitrogen atom form a 5-, 6- or 7-membered ring can and n stands for a number 2, 3, 4, 5 or 6
• Y is an oxygen atom, a sulfur atom or a group NR ^VII in which R ^VII represents a hydrogen atom, an aryl group, a heteroaryl group, a C ₁ -C ₆ -alkyl group or a C ₁ -C ₆ -arylalkyl group,
• • X ^- is a physiologically acceptable anion,
• Het is an optionally substituted heteroaromatic,
• • X ¹ represents a direct bond or a carbonyl group.

With the same effect the compounds of formula II are their enamine forms. It will here explicitly the document WO-A1-2004 / 022016, to the full extent Reference is made.

At least one group R ¹⁰ or R ^{1 2} according to formula II is necessarily a C ₁ -C ₆ alkyl group. This alkyl group preferably carries at least two hydrogen atoms on its alpha carbon atom. Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, neo-pentyl, n-hexyl group. Most preferably, R ¹⁰ and R ^{1 2} are each independently hydrogen or a methyl group, wherein at least one group R ¹⁰ or R ^{1 2} is a methyl group.

In a preferred embodiment Y stands for an oxygen or sulfur atom, more preferably an oxygen atom.

The radical R ⁸ is preferably selected from a (C ₁ -C ₆ ) -alkyl group (particularly preferably a methyl group), a C ₂ -C ₆ -alkenyl group (in particular an allyl group), a hydroxy- (Cz- to C ₆ ) - alkyl group, especially a 2-hydroxyethyl group, or an optionally substituted benzyl group.

R ¹¹ is preferably a hydrogen atom.

Particularly preferably, the radicals R ⁹ , R ¹⁰ and R ^{12 are} a methyl group, the radical R ^{11 is} a hydrogen atom, Y is an oxygen or sulfur atom and the radical R ⁸ is selected from a (C ₁ -C ₆ ) - Alkyl group (particularly preferably a methyl group), a C ₂ -C ₆ alkenyl group (in particular an allyl group), a hydroxy (C ₂ - to C ₆ ) alkyl group, in particular a 2-hydroxyethyl group, or an optionally substituted benzyl group.

Preferably, the compounds according to formula II are selected from one or more compounds of the group of salts with physiologically compatible counterion X ^- , which is formed from salts of
1,2-dihydro-1,3,4,6 tetramethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidiniums,
1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3,4-trimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and
1,2-dihydro-3,4-dimethyl-2-thioxo-chinazoliniums.

Very particularly preferred agents according to the invention are characterized in that they are as CH-acidic compound
Salts of 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium,
Salts of 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium,
Salts of 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium,
Salts of 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium,
Salts of 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium, 2- (cyanomethyl) benzimidazole,
4,5-dihydro-4-imino-2- (1-piperidinyl) thiazole and / or its hydrochloride,
4,5-dihydro-4-imino-2- (4-morpholinyl) thiazole and / or its hydrochloride,
4,5-dihydro-4-imino-2- (1-pyrrolidinyl) thiazole and / or its hydrochloride
contain.

X ^- in formula (II) and in the above lists is preferably halide, benzenesulfonate, p-toluenesulfonate, C ₁ -C ₄ -alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogensulfate, tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. The anions chloride, bromide, iodide, hydrogensulfate or p-toluenesulfonate are particularly preferably used as X ^- .

worin

• • R^{1 6} und R¹⁷ stehen unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, ein Halogenatom, eine Nitrogruppe, eine lineare oder zyklische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Cyanmethylgruppe, eine Cyanmethylcarbonylgruppe, eine gegebenenfalls substituierte Heteroarylguppe, eine Aryl-C₁-C₆-alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Alkoxycarbonylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, eine C₁-C₆-Sulfoalkylgruppe, eine C₁-C₆-Carboxyalkylgruppe, eine Gruppe R^VIIIR^IXN-(CH₂)_m-, worin R^VIII und R^IX stehen unabhängig voneinander für ein Wasserstoffatom, eine lineare oder zyklische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₄-alkylgruppe, wobei R^VIII und R^IX gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 0, 1, 2, 3 oder 4, wobei R^{1 6} und/oder R¹⁷ einen an den Ring des Restmoleküls ankondensierten, gegebenenfalls substituierten aromatischen oder heteroaromatischen, 5- oder 6-Ring bilden können
• • X² und X³ stehen unabhängig voneinander für ein Stickstoffatom oder eine Gruppe CR^{1 5}, wobei R^{1 5} steht für ein Wasserstoffatom, eine Hydroxygruppe, ein Halogenatom, eine Nitrogruppe, eine lineare oder zyklische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Cyanmethylgruppe, eine Cyanmethylcarbonylgruppe, eine gegebenenfalls substituierte Heteroarylguppe, eine Aryl-C₁-C₆-alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Alkoxycarbonylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, eine C₁-C₆-Sulfoalkylgruppe, eine C₁-C₆-Carboxyalkylgruppe und eine Gruppe R^XR^XIN-(CH₂)_n-, worin R^X und R^XI stehen unabhängig voneinander für ein Wasserstoffatom, eine lineare oder zyklische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₄-alkylgruppe, wobei R^X und R^XI gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und n steht für eine Zahl 0, 1, 2, 3 oder 4, wobei mindestens einer der Substituenten X² und X³ zusammen mit dem Restmolekül einen ankondensierten gegebenenfalls substituierten aromatischen 5- oder 6-Ring bilden kann,
• • X⁴ steht für ein Sauerstoffatom, ein Schwefelatom, einer Vinylengruppe oder eine Gruppe N-H, wobei die beiden letztgenannten Gruppen unabhängig voneinander gegebenenfalls mit einer linearen oder zyklischen C₁-C₆-Alkylgruppe, einer C₂-C₆-Alkenylgruppe, einer gegebenenfalls substituierten Arylgruppe, einer gegebenenfalls substituierten Heteroarylguppe, einer Aryl-C₁-C₆-alkylgruppe, einer C₂-C₆-Hydroxyalkylgruppe, einer C₂-C₆-Polyhydroxyalkylgruppe, einer C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, einer C₁-C₆-Sulfoalkylgruppe, einer C₁-C₆-Carboxyalkylgruppe, einer Gruppe R^XIIR^XIIIN-(CH₂)_p steht, worin R^XII und R^XIII stehen unabhängig voneinander für ein Wasserstoffatom, eine lineare oder zyklische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₄-alkylgruppe, wobei R^XII und R^XIII gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und p steht für eine Zahl 0, 1, 2, 3 oder 4, substituiert sein können, mit der Maßgabe, daß, wenn X⁴ für eine Vinylengruppe steht, mindestens eine der Gruppen X² oder X³ ein Stickstoffatom bedeutet.

The radical Het according to formula (III) preferably represents the molecule fragment of the formula (V),

wherein

• R ^{1 6} and R ¹⁷ are each independently hydrogen, hydroxy, halogen, nitro, C ₁ -C ₆ linear or cyclic, C ₂ -C ₆ alkenyl, optionally substituted aryl, one Cyanomethyl group, a cyanomethylcarbonyl group, an optionally substituted heteroaryl group, an arylC ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy group, a C C ₁ -C ₆ -alkoxycarbonyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, a C ₁ -C ₆ -sulfoalkyl group, a C ₁ -C ₆ -carboxyalkyl group, a group R ^VIII R ^IX N- (CH ₂ ) _m -, wherein R ^VIII and R ^IX independently of one another represent a hydrogen atom, a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₄ -alkyl group, wherein R ^VIII and R ^IX together with the nitrogen atom is a 5-, 6- or 7-membered ring and m is a number 0, 1, 2, 3 or 4, wherein R ^{1 6} and / or R ^{17 form} a fused to the ring of the remainder of the molecule, optionally substituted aromatic or heteroaromatic, 5- or 6-ring can
• X ² and X ³ independently of one another represent a nitrogen atom or a group CR ^{1 5} , where R ^{1 5} a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, a cyanomethyl group, a cyanomethylcarbonyl group, an optionally substituted heteroaryl group, an aryl-C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy group, a C ₁ -C ₆ -alkoxycarbonyl group, a C ₁ C ₆ alkoxy C ₂ -C ₆ alkyl group, a C ₁ -C ₆ sulfoalkyl group, a C ₁ -C ₆ carboxyalkyl group and a group R ^X R ^XI N- (CH ₂ ) _n -, wherein R ^X and R ^XI independently represent a hydrogen atom, a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₄ -alkyl group in which R ^X and R ^XI together with the nitrogen atom can form a 5-, 6- or 7-membered ring and n stands for a number 0, 1, 2, 3 or 4, wherein at least one of the substituents X ² and X ³ together with the remainder of the molecule can form a fused optionally substituted aromatic 5- or 6-membered ring,
• X ⁴ represents an oxygen atom, a sulfur atom, a vinylene group or a group NH, the last two groups independently of one another optionally with a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ alkyl group, a C ₁ -C ₆ sulfoalkyl, a C ₁ -C ₆ carboxyalkyl, a group R ^XII R ^XIII N- (CH _{2) p,} wherein R ^XII and R ^XIII are independently a hydrogen atom, a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₄ -alkyl group, wherein R ^XII and R ^XIII together with the Nitrogen atom can form a 5-, 6- or 7-membered ring and p is one 0, 1, 2, 3 or 4, with the proviso that when X ^{4 is} a vinylene group, at least one of X ² or X ^{3 represents} a nitrogen atom.

The bond of the heterocyclic ring according to formula (V) to the molecule fragment -X ¹ -CH ₂ -C≡N to give the compound according to formula (III) according to the invention takes place at the ring of the heterocycle and replaces a hydrogen atom bound to this ring. Consequently, it is imperative that the substituents R ^{1 6} , R ¹⁷ , X ² , X ³ and X ⁴ must be chosen such that at least one of these substituents allows a corresponding bond formation. Consequently, it is compulsory that at least one of R ^{1 6} or R ^{17 form} the bond to the molecular fragment -X ¹ -CH ₂ -C≡N when X ^{4 is} an oxygen atom or a sulfur atom and X ² and X ^{3 represent} a nitrogen atom ,

The radical Het according to formula (III) is particularly preferably derived from the heteroaromatics furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, pyridine, pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2 , 4-triazine, 1,3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, indole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, acridine, benzoquinoline, benzoisoquinoline, benzothiazole , Phenazine, benzocinnoline, benzoquinazoline, benzoquinoxaline, phenoxazine, phenothiazine, nephthyridine, phenanthroline, indolizine, quinolizine, carboline, purine, pteridine and coumarin, wherein the aforementioned heteroaromatic compounds having at least one group selected from a halogen atom, a nitro group, a thio group, a thio - (C ₁ -C ₆ ) -alkyl group, a heteroaryl group, an aryl group, a (C ₁ -C ₆ ) -alkyl group, a (C ₁ -C ₆ ) -alkoxy group, a hydroxy group, a (C ₂ -C ₆ ) -Hydroxyalkylgru ppe, a (C ₂ -C ₆ ) -polyhydroxyalkyl group, a (C ₁ -C ₆ ) -alkoxyl (C ₁ -C ₆ ) -alkyl group, an aryl (C ₁ -C ₆ ) -alkyl group, an amino group, a (C ₁ -C ₆ ) monoalkylamino group, a (C ₁ -C ₆ ) dialkylamino group, a dialkylaminoalkyl group- (CH ₂ ) _n -NR'R '', wherein n is an integer of 2 and 6, and R ' and R "independently represent a linear or branched alkyl group, which may optionally together form a ring, may be substituted.

Preferably are the compounds according to formula (III) selected from the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 2- (5-methyl-2-trifluoromethyl-3-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5-fluoro-2-thenoyl) -acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl) -acetonitrile, 2- (1,2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1H-benzimidazol-2-ylacetonitrile, 1H-benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indol-3-oyl) -acetonitrile, 2- (2-methylindol-3-oyl) -acetonitrile, 8-cyanoacetyl-7-methoxy-4-methyl coumarin, 2- (2-Isopropyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (2-phenyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (quinoxalin-2-yl) -acetonitrile, 2- (cumarone-2-yl) -acetonitrile, 6,7-dichloro-5- (cyanoacetyl) -2,3-dihydro-1-benzofuran-2-carboxylic acid tert-butyl ester, -acetonitrile 2- (6-hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) and 2- (1-phenyl-1,4-dihydrothiochromeno [4,3-c] pyrazol-3-oyl) -acetonitrile. Especially 1 H-benzimidazol-2-ylacetonitrile [2- (cyanomethyl) benzimidazole] is preferred.

According to the invention preferred Agents are characterized in that they act as hair dyes formulated, based on their weight 0.01 to 20 wt .-%, preferably 0.05 to 15 wt .-%, particularly preferably 0.1 to 12.5 Wt .-% and in particular 0.2 to 10 wt .-% of one or more CH-acidic Compounds).

The agents according to the invention optionally contain ammonia (calculated as 100% NH ₃ ), the amount of which is limited to a maximum of 3% by weight, based on the total agent or in the case of multicomponent agents, based on the ready-to-use mixture. Preferred agents or application mixtures according to the invention contain at most 1.8% by weight of ammonia, more preferably at most 1.5% by weight of ammonia, even more preferably not more than 1.25% by weight of ammonia, particularly preferably not more than 1.0% by weight. -% ammonia and in particular at most 0.5 wt .-% ammonia. In a further preferred embodiment of the present invention, the agents are ammonia-free.

enthalten, worin
R¹ steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe oder eine (C₁-C₆)-Alkylgruppe,
R² steht für ein Wasserstoffatom, eine Carboxaldehydgruppe, eine (C₁-C₆)-Alkylgruppe oder eine Nitrogruppe,
R³ steht für ein Wasserstoffatom, eine Carboxy-(C₁-C₆)-alkylgruppe, eine Amino-(C₁-C₆)-alkylgruppe, eine Carboxylgruppe, eine Carboxaldehydgruppe, eine (C₁-C₆)-Alkylgruppe, eine Nitrogruppe, eine 2-Amino-3-hydroxypropylgruppe oder eine Gruppe -CH₂-CH(NH₂)-COOH,
R⁴ steht für ein Wasserstoffatom, eine Carboxaldehydgruppe oder eine Carboxylgruppe.As a further ingredient, the agents according to the invention may with particular preference contain one or more imidazole compounds. Agents which are particularly preferred according to the invention for dyeing and / or lightening keratinic fibers are characterized in that they contain, based on their weight, 1 to 20% by weight of at least one imidazole compound of the formula (II) and / or their physiologically acceptable salts

contain, in which
R ¹ represents a hydrogen atom, an optionally substituted aryl group or a (C ₁ -C ₆ ) -alkyl group,
R ² represents a hydrogen atom, a carboxaldehyde group, a (C ₁ -C ₆ ) -alkyl group or a nitro group,
R ³ represents a hydrogen atom, a carboxy (C ₁ -C ₆ ) -alkyl group, an amino (C ₁ -C ₆ ) -alkyl group, a carboxyl group, a carboxaldehyde group, a (C ₁ -C ₆ ) -alkyl group, a nitro group, a 2-amino-3-hydroxypropyl group or a group -CH ₂ -CH (NH ₂ ) -COOH,
R ⁴ represents a hydrogen atom, a carboxaldehyde group or a carboxyl group.

Preferably the imidazole compound (s) of the formula (II) become / become within used in narrower ranges. Here are means according to the invention to dye and / or lightening keratinic fibers which are at least an imidazole compound according to formula (II) and / or physiologically acceptable salts thereof in amounts of From 2 to 15% by weight, preferably from 2.5 to 12.5% by weight, especially preferably from 3 to 10% by weight and in particular from 4 to 8% by weight contain.

Prefers the imidazole compounds according to formula (II) are selected from at least one representative from a group that is formed from histamine, D-histidine, L-histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, imidazole, imidazole-4-acetic acid, imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazole-2-carboxaldehyde, Imidazole-4-carboxaldehyde, imidazole-5-carboxaldehyde, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole-5-carboxaldehyde, N-methylimidazole-2-carboxaldehyde, 4-methylimidazole, 2-methylimidazole, N-methylimidazole, N- (4-aminophenyl) -imidazole, as well as the physiologically acceptable Salts of the aforementioned compounds. Particularly according to the invention imidazole is preferably used. Accordingly, according to the invention are preferred Means characterized in that the imidazole compound of the formula (II) and / or the physiologically acceptable salts thereof are / are selected from histamine, D-histidine, L-histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, Imidazole, imidazole-4-acetic acid, Imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazole-2-carboxaldehyde, Imidazole-4-carboxaldehyde, imidazole-5-carboxaldehyde, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole-5-carboxaldehyde, N-methylimidazole-2-carboxaldehyde, 4-methylimidazole, 2-methylimidazole, N-methylimidazole, N- (4-aminophenyl) -imidazole, as well as the physiologically acceptable Salts of the aforementioned compounds.

As already mentioned, can the agents according to the invention also directly before the application of two or more separately packaged Preparations are prepared. This is particularly suitable to separate incompatible ingredients to a premature one To avoid reaction.

A common way is therefore to use an agent A according to the invention directly before use an oxidizer preparation B to an application mixture to mix.

One Another object of the present invention is therefore an agent to dye and / or lightening keratinic fibers, especially human Hair, which immediately before applying to the hair from a flowable preparation A, an oxidizing agent preparation B containing at least one oxidizing agent, selected from hydrogen peroxide and its addition compounds to solid Carrier and a preparation C, which are mixed together to form a dyeing and / or whitening formulation, wherein the composition A and / or C is a composition according to the invention or the composition A oxidation dye precursor (s) and the composition C ester and / or anhydride (s) (or vice versa).

The Mixture of preparations A, B and C before use leads to a Application mixture, the esters and / or anhydride (s) and preferably Contains oxidation dye precursor (s). Preferred application mixtures suffice about that beyond the first embodiment of the present invention, i. particularly preferred means of second embodiment are so made up and / or are in such a relationship with each other mixed that the Application mixture The stated amounts of ester (s) and / or anhydride (s) contains.

An oxidizer formulation B contains at least one oxidizer selected from hydrogen peroxide and its attachment compounds to solid supports. As the oxidant of the present invention, hydrogen peroxide itself is preferably used. The hydrogen peroxide is used as a solution or in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide, used.

Very particularly preferred according to the invention are aqueous hydrogen peroxide solutions. The concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6-12% solutions in water are used. According to preferred means for dyeing and / or lightening keratinischer fibers are characterized in that the oxidizing agent preparation B - based on their weight - 0.5 to 10 wt .-%, preferably 0.75 to 9.0 wt .-%, particularly preferably 1 to 8.0 wt .-%, more preferably 1.25 to 7.0 wt .-% and in particular 1.5 to 6.0 wt .-% hydrogen peroxide (calculated as 100% H ₂ O ₂ ).

The Oxidizer formulation B is preferably an aqueous, flowable oxidizer formulation. Accordingly, preferred means for dyeing and / or Whitening keratinic fibers, characterized in that the flowable oxidizing agent preparation B - related on her weight - 40 to 90% by weight, preferably 50 to 85% by weight, more preferably 55 to 80 wt .-%, more preferably 60 to 77.5 wt .-% and in particular 65 to 75 wt .-% water.

Based on the application mixture, agents according to the invention for dyeing and / or lightening keratinic fibers are preferred, which contain 0.5 to 15% by weight, preferably 1 to 12.5% by weight, particularly preferably 2.5 to 10% by weight. and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H ₂ O ₂ ) included.

Preferably becomes the flowable oxidizer formulation B an emulsifier or a surfactant added, wherein surface-active Depending on the field of application substances are known as surfactants or as emulsifiers and anionic, cationic, zwitterionic, ampholytic and nonionic surfactants and emulsifiers. These substances are described in detail below.

The choice of this further peroxo compound is subject in principle to no restrictions, and conventional peroxo compounds known to the person skilled in the art are, for example, ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, ammonium persulfate, potassium persulfate, sodium persulfate, percarbonates, such as magnesium percarbonate. Peroxides such as barium peroxide and also perborates, urea peroxide and melamine peroxide are among these peroxo compounds which can also be used in combination.Partoxysulfates are particularly preferred according to the invention, especially combinations of at least two peroxydisulfates. or lightening keratinic fibers which additionally contain 0.01 to 2% by weight of at least one solid peroxy compound selected from ammonium, alkali metal alkaline and alkaline earth metal persulphates, peroxymonosulphates and peroxydisulphates, preferred agents containing peroxydisulfates, which are preferably selected from sodium peroxydisulfate and / or potassium peroxodisulfate and / or ammonium peroxydisulfate and particularly preferred agents containing at least two different peroxidisulfates.

Farther Particular preference is given to persulfates, in particular as Caro's Salt designated mixture of potassium peroxosulphate, potassium hydrogen sulfate and potassium sulfate.

There the "boosters" are hydrolytically light It is preferred to decompose these of the oxidizing agent preparation or the application mixture only immediately before application.

As an additional alkalizing agent, the compositions according to the invention may comprise at least one compound of amino acids and / or oligopeptides, these in each case having at least two amino groups and at least one -COOH or -SO ₃ H group and their 2.5% solution in water in each case has a pH of greater than 9.0.

preferred Alkalizing agents are aminocarboxylic acids, in particular α-aminocarboxylic acids and omega-aminocarboxylic acids. Under the α-aminocarboxylic acids are again lysine and especially arginine particularly preferred.

said amino acids can the agents according to the invention preferably added in free form. In a number of cases but it is also possible the amino acids in salt form. Preferred salts are then the compounds with hydrohalic acids, in particular the hydrochlorides and hydrobromides.

Farther can the amino acids also used in the form of oligopeptides and protein hydrolysates if it is certain that the required quantities the invention used amino acids contained therein. In this context, the revelation DE-OS 22 15 303, to which reference is expressly made.

One Particularly preferred alkalizing agent is arginine.

According to the invention preferred Means are characterized in that they additionally - 0.05 to 5 wt .-%, preferably 0.1 to 2.5 wt .-%, particularly preferably 0.15 to 1 wt .-% and in particular 0.2 to 0.5% by weight of amino acid (s), preferably (an) amino acid (s) from the group glycine and / or alanine and / or valine and / or lysine and / or leucine and / or threonine and / or serine.

The Anhydrous according to the invention Compositions can additionally at least one further bleach booster, other than inorganic Persalts is different, included.

When bleach booster can Compounds which, under perhydrolysis conditions, are aliphatic peroxycarboxylic acids preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups wear. Preference is given to polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In order to further increase the lightening power, anhydrous compositions according to the invention may additionally contain as bleaching boosters at least one optionally hydrated SiO ₂ compound. Although even small amounts of the optionally hydrated SiO ₂ compounds increase the lightening power, it may be preferred according to the invention, the optionally hydrated SiO ₂ compounds in amounts of 0.05 wt .-% to 15 wt .-%, particularly preferably in amounts of 0.15 wt .-% to 10 wt .-% and most preferably in amounts of 0.2 wt .-% to 5 wt .-%, each based on the anhydrous composition of the invention to use. The amounts given in each case the content of the SiO ₂ compounds (without their water content) in the funds again.

With regard to the optionally hydrated SiO ₂ compounds, the present invention is subject in principle no restrictions. Preference is given to silicic acids, their oligomers and polymers and their salts. Preferred salts are the alkali salts, especially the potassium and sodium salts. The sodium salts are very particularly preferred.

The optionally hydrated SiO ₂ compounds can be present in various forms. According to the invention, the SiO ₂ compounds are preferably used in the form of silica gels (silica gel) or particularly preferably as water glass. These SiO ₂ compounds may be partially present in aqueous solution.

Very particularly preferred according to the invention are water glasses which are formed from a silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m (K ₂ O) _p , where n is a positive rational number and m and p are each independently one positive rational number or 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1.

Next the components described by the molecular formula may glasses of water in small quantities still other additives, such as Phosphates or magnesium salts.

According to the invention particularly preferred water glasses are sold among others by Henkel under the names Ferrosil® ^® 119, soda water glass 40/42, Portil ^® A, Portil ^® AW and Portil ^® W and by Akzo under the name Britesil® ^® C20.

Preferred agents are characterized in that they additionally contain 0.05 to 15 wt .-%, particularly preferably 0.15 to 10 wt .-% and in particular 0.2 to 5 wt .-% of at least one optionally hydrated SiO ₂ compound Preferred agents include water glasses formed from a silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m (K ₂ O) _p , where n is a positive rational number and m and p are independently one positive rational number or 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1.

• i. Carbonate und/oder
• ii. Monoalkylcarbonate (Kohlensäuremonoester) und/oder
• iii. Kohlensäuremonoamide und/oder
• iv. Silylcarbonate und/oder
• v. Silylcarbamate.

In addition to the ingredients mentioned, the use of carbonates and carbonate analogues in the compositions according to the invention has proven to be preferred. According to preferred means for dyeing and / or lightening keratinischer fibers additionally contain 0.1 to 25 wt.%, Preferably 0.5 to 20 wt.%, Particularly preferably 1 to 15 wt.% And in particular 1.5 to 10 wt.% at least one substance from the groups of

• i. Carbonates and / or
• ii. Monoalkyl carbonates (carbonic acid monoesters) and / or
• iii. Carbonic acid monoamides and / or
• iv. Silyl carbonates and / or
• v. Silylcarbamate.

When Carbonates are especially ammonium, alkali metal and Alkaline earth metal carbonates and bicarbonates. Especially preferred are, for example, sodium bicarbonate, ammonium bicarbonate, Sodium carbonate, ammonium carbonate and ammonium carbamate.

In addition to Carbonates or in their place may agents of the invention preferably also at least one carbonic acid monoester and / or at least a carbonic acid monoamide contain. These substances are described in detail below.

Agents preferred according to the invention are characterized in that they contain at least one carbonic acid monoester of the formula (III) ROC (O) -OH (III) in which R represents a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (III), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sul Fonsäuregruppen or halogens come into question. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. R is particularly preferably a C _1-6 - Alkyl group. Examples of C ₁ -C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Particularly according to the invention preferred agents are characterized in that the remainder R is selected in formula (III) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-But- as well Hydroxymethyl and hydroxyethyl residues.

As an alternative to the carbonic acid monoester or in conjunction with it, the compositions according to the invention may contain carbonic acid monoamides. Here, preferred agents according to the invention are characterized in that they contain at least one carbonic acid monoamide of the formula (IV) R-NH-C (O) -OH (IV) in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (IV), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably, R is a C _1-6 alkyl group. Examples of C ₁ -C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Particularly according to the invention preferred agents are characterized in that the remainder R is selected in formula (IV) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl as well Hydroxymethyl and hydroxyethyl residues.

The Acid H atom of carbonic acid monoester or monoamides may also be present in neutralized form, i. it can According to the invention also salts of carbonic acid monoesters or carbonic acid monoamides be used. Here, agents according to the invention are preferred which the Kohlensäuremonoester or the carbonic acid monoamide in completely or partially neutralized form, preferably in the form its alkali metal, ammonium, alkaline earth metal or aluminum salt and especially in the form of its sodium salt.

Independently of, whether the agents according to the invention one or more carbonic acid monoesters and / or one or more carbonic acid monoamides included are means of the invention preferably, the or the carbonic acid monoesters and / or carbonic acid monoamides in amounts of from 0.1 to 20% by weight, preferably from 0.5 to 18% by weight, particularly preferably from 2 to 15% by weight and in particular from 5 to 12% by weight, based in each case on the total agent.

In addition to Carbonates and / or carbonic acid monoesters and / or carbonic acid monoamides or in their place the agents according to the invention preferably also at least one silyl carbonate and / or at least contain a silyl carbamate. These substances will be below described in detail.

enthalten, in der die Reste R¹, R² und R³ unabhängig voneinander für ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine Trialkylsilylgruppe, vorzugsweise eine Trimethylsilylgruppe oder für eine substituierte oder unsubstiuierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus oder für ein Halogen, eine substituierte oder unsubstituierte Hydroxy-, Oxo-, Amino-, Iminogruppen stehen und der Rest R⁴ für eine chemische Bindung zum Si-Atom oder zu einem der Reste R¹, R² oder R³, ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine substituierte oder unsubstituierte Silyl- oder Aluminylgruppe oder für eine substituierte oder unsubstiuierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus steht.Agents preferred according to the invention are characterized in that they contain at least one silyl carbonate of the formula (V)

in which the radicals R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a trialkylsilyl group, preferably a trimethylsilyl group or a substituent tuierte or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino, imino groups and the radical R ^{4 is} a chemical bond to the Si atom or to one of the radicals R ¹ , R ² or R ³ , a hydrogen atom, a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted silyl or alumino group or a substituted or unsubstituted aryl group or a substituted or unsubstituted Heterocycle stands.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (V) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among these, the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred agents according to the invention are characterized in that the radicals R ¹ , R ² and R ³ in formula (V) are selected from methyl, ethyl, n Propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ in the abovementioned formula (VII) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.

The acidic H atom of the silyl carbonate (R ⁴ = -H in formula V) can also be present in neutralized form, ie according to the invention it is also possible to use salts of silyl carbonates. Here, agents according to the invention are preferred which comprise at least one silyl carbonate in completely or partially neutralized form, preferably in the form of its alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt.

In addition to the silyl carbonates or in their place, the agents of the invention Silylcarbamate included.

enthalten, in der enthält, in der die Reste R¹, R² und R³ unabhängig voneinander für ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine Trialkylsilylgruppe, vorzugsweise eine Trimethylsilylgruppe oder für eine substituierte oder unsubstiuierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus oder für ein Halogen, eine substituierte oder unsubstituierte Hydroxy-, Oxo-, Aminogruppen stehen und die Rest R⁴ und R⁵ unabhängig voneinander für eine chemische Bindung zum Si-Atom oder zu einem der Reste R¹, R² oder R³, ein Wasserstoffatom, einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest oder für eine substituierte oder unsubstituierte Silyl- oder Aluminylgruppe oder für eine substituierte oder unsubstiuierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus stehen.Agents preferred according to the invention are characterized in that they contain a silyl carbamate of the formula VI)

containing, in which the radicals R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or for a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino groups and the radicals R ⁴ and R ⁵ independently of one another for a chemical bond to the Si atom or to a the radicals R ¹ , R ² or R ³ , a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted silyl or alumino group or a substituted or unsubstituted aryl group or a s substituted or unsubstituted heterocycle.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (VI) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among these, the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred agents according to the invention are characterized in that the radicals R ¹ , R ² and R ³ in formula (VI) are selected from methyl, ethyl, n Propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ and R ⁵ in the abovementioned formula (VI) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.

Regardless of whether the compositions according to the invention contain one or more silyl carbonates and / or one or more silyl carbamates, agents according to the invention are preferred which contain the silyl carbonate (s) and / or silyl carbamate (s) in amounts of from 0.1 to 25% by weight %, preferably from 0.5 to 20% by weight, be especially preferably from 1 to 15% by weight and in particular from 1.5 to 10% by weight, in each case based on the total agent.

The agents according to the invention preferably have a pH of 5.0 to 9.0, preferably from 5.5 to 8.0, more preferably from 6.0 to 7.7, more preferably from 6.2 to 7.2 and especially from 6.5 to 6.8.

The dyeing and / or lightening agents according to the invention may additionally comprise at least one cyanate of the formula M ⁺ [OCN] ^- in which M ⁺ for K ⁺ , Na ⁺ , Li ⁺ or NH ₄ ⁺ or 1/2 Ca ²⁺ , 1/2 Mg ²⁺ or 1/2 Zn ²⁺ and / or at least one compound of the formula H ₂ NC (O) -L, in which L stands for a group displaceable by the anion ^- OOH, enthaften.

• – 0,05 bis 5 Gew.-% mindestens eines Cyanats der Formel M⁺ [OCN]^– in der M⁺ für K⁺, Na⁺, Li⁺ oder NH₄ ⁺ oder 1/2 Ca²⁺, 1/2 Mg²⁺ oder 1/2 Zn²⁺ steht und/oder
• – 0,05 bis 5 Gew.-% mindestens einer Verbindung der Formel H₂N-C(O)-L in der L für eine durch das Anion ^–OOH verdrängbare Gruppe steht.

According to preferred means for dyeing and / or brightening keratinic fibers therefore also contain

• 0.05 to 5% by weight of at least one cyanate of the formula M ⁺ [OCN] ^- in which M ^{+ stands} for K ⁺ , Na ⁺ , Li ⁺ or NH ₄ ⁺ or 1/2 Ca ²⁺ , 1/2 Mg ²⁺ or 1/2 Zn ²⁺ and / or
• 0.05 to 5% by weight of at least one compound of the formula H ₂ NC (O) -L in which L stands for a group displaceable by the anion ^- OOH.

As cyanates according to the invention potassium cyanate, KOCN, and / or sodium cyanate, NaOCN, and / or lithium cyanate, LIOCN, and / or ammonium cyanate, NH ₄ OCN, and / or calcium cyanate, Ca (OCN) ₂ , and / or magnesium cyanate, Mg (OCN ) ₂ , and / or zinc cyanate, Zn (OCN) ₂ .

According to the invention preferred Agents are characterized by being 0.075 to 4% by weight, preferably 0.1 to 2.5 wt .-% and in particular 0.2 to 1 wt .-% sodium cyanate and / or potassium cyanate and / or ammonium cyanate, wherein sodium cyanate is particularly preferred.

und M für -H, Na, K, NH4 steht, Q ausgewählt ist aus den aus tertiären Aminen gebildeten quartären Ammoniumresten, Heteroarylresten oder nicht-aromatischen Heterocyclen und R¹ für -H, -CH₃, -CH₂CH₃, -(CH₂)₂CH₃, -CH(CH₃)₂ oder eine andere Alkylgruppe steht.Instead of cyanates or in combination with them, compounds of the formula H ₂ NC (O) -L in which L is a group displaceable by the anion ^- OOH may also be present in the agents according to the invention. According to the invention, preferred agents for dyeing and / or lightening keratinic fibers are characterized in that they contain from 0.075 to 4% by weight, preferably from 0.1 to 3.5% by weight and in particular from 0.2 to 3% by weight, at least a compound of the formula H ₂ NC (O) -L in which L is selected from -S-CH ₂ -COOH, -S- (CN ₂ ) ₃ SO ₃ H, -S- (CH ₂ ) ₂ -NH ₂ , -OCH ₃ , -O- (C ₆ H ₄ ) -SO ₃ M, -Q ⁺ , -NH-OH, -OC (O) -R ¹ , -OC (O) -H, -O-CH (OH) ₂ , -SO ₃ M, -PH (O) OH, -P (O) (OH) ₂ , - (NH-glucosamine) _n , -NH-C (O) -NH ₂ , -NH-NH ₂ , -NH-CN, -P (OH) (O) -C (O) NH ₂ , -SCN, -OCN, -SC (NH) NH ₂ ,

and M is -H, Na, K, NH4, Q is selected from quaternary ammonium radicals, heteroaryl radicals or non-aromatic heterocycles formed from tertiary amines and R ^{1 is} -H, -CH ₃ , -CH ₂ CH ₃ , - ( CH ₂ ) ₂ CH ₃ , -CH (CH ₃ ) ₂ or another alkyl group.

• – H₂N-C(O)-S-CH₂-COOH
• – H₂N-C(O)-S-(CN₂)₂-NH₂
• – H₂N-C(O)-S-(CH₂)₃SO₃Na
• – H₂N-C(O)-S-(CH₂)₃SO₃K
• – H₂N-C(O)-S-(CH₂)₃SO₃NH₄
• – H₂N-C(O)-SO₃H
• – H₂N-C(O)-SO₃Na
• – H₂N-C(O)-SO₃K
• – H₂N-C(O)-SO₃NH₄
• – H₂N-C(O)-O-(C₆H₄)-SO₃H
• – H₂N-C(O)-O-(C₆H₄)-SO₃Na
• – H₂N-C(O)-O-(C₆H₄)-SO₃K
• – H₂N-C(O)-O-(C₆H₄)-SO₃NH₄
• – H₂N-C(O)-O-C(O)-H
• – H₂N-C(O)-O-C(O)-CH₃
• – H₂N-C(O)-O-C(O)-CH₂CH₃
• – H₂N-C(O)-O-C(O)-(CH₂)₂CH₃
• – H₂N-C(O)-O-C(O)-CH(CH₃)₂
• – H₂N-C(O)-OCH₃
• – H₂N-C(O)-NH-OH
• – H₂N-C(O)-O-CH(OH)₂
• – H₂N-C(O)-PH(O)OH
• – H₂N-C(O)-P(O)(OH)₂
• – H₂N-C(O)-NH-C(O)-NH₂
• – H₂N-C(O)-NH-NH₂
• – H₂N-C(O)-NH-CN
• – H₂N-C(O)-P(OH)(O)-C(O)NH₂
• – H₂N-C(O)-SCN
• – H₂N-C(O)-OCN
• – H₂N-C(O)-S-C(NH)NH₂
• – H₂N-C(O)-N(CH₃)₃ ⁺Cl^–
• – H₂N-C(O)-N(CH₂CH₃)₃ ⁺Cl^–
• – H₂N-C(O)-N((CH₂)₂CH₃)₃+ Cl^–
• – H₂N-C(O)-N(CH(CH₃)₂)₃ ⁺Cl^–
• – H₂N-C(O)-N(C₆H₅)₃ ⁺Cl^–
• – H₂N-C(O)-N(CH₂-Ph)₃ ⁺Cl^–
• – H₂N-C(O)-N(CH₃)₃ ⁺Br^–
• – H₂N-C(O)-N(CH₂CH₃)₃ ⁺Br^–
• – H₂N-C(O)-N((CH₂)₂CH₃)₃ ⁺Br^–
• – H₂N-C(O)-N(CH(CH₃)₂)₃ ⁺Br^–
• – H₂N-C(O)-N(C₆H₅)₃ ⁺Br^–
• – H₂N-C(O)-N(CH₂-Ph)₃ ⁺Br^–
• – H₂N-C(O)-N(CH₃)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N(CH₂CH₃)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N((CH₂)₂CH₃)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N(CH(CH₃)₂)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N(C₆H₅)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N(CH₂-Ph)₃ ⁺H₃C-OSO₃ ^–
• – H₂N-C(O)-N(CH₃)₃ ⁺H₃C-CH₂-OSO₃ ^–
• – H₂N-C(O)-N(CH₂CH₃)₃ ⁺H₃C-CH₂-OSO₃ ^–
• – H₂N-C(O)-N((CH₂)₂CH₃)₃ ⁺H₃C-CN₂-OSO₃ ^–
• – H₂N-C(O)-N(CH(CH₃)₂)₃ ⁺H₃C-CH₂-OSO₃ ^–
• – H₂N-C(O)-N(C₆H₅)₃ ⁺H₃C-CH₂-OSO₃ ^–
• – H₂N-C(O)-N(CH₂-Ph)₃ ⁺H₃C-CN₂-OSO₃ ^–

Particularly preferred agents according to the invention contain from 0.075 to 4% by weight, preferably from 0.1 to 3.5% by weight and in particular from 0.2 to 3% by weight of at least one of the compounds listed below:

• - H ₂ NC (O) -S-CH ₂ -COOH
• - H ₂ NC (O) -S- (CN ₂ ) ₂ -NH ₂
• - H ₂ NC (O) -S- (CH ₂ ) ₃ SO ₃ Na
• - H ₂ NC (O) -S- (CH ₂ ) ₃ SO ₃ K
• - H ₂ NC (O) -S- (CH ₂ ) ₃ SO ₃ NH ₄
• - H ₂ NC (O) -SO ₃ H
• - H ₂ NC (O) -SO ₃ Na
• - H ₂ NC (O) -SO ₃ K
• - H ₂ NC (O) -SO ₃ NH ₄
• - H ₂ NC (O) -O- (C ₆ H ₄ ) -SO ₃ H
• - H ₂ NC (O) -O- (C ₆ H ₄ ) -SO ₃ Na
• - H ₂ NC (O) -O- (C ₆ H ₄ ) -SO ₃ K
• - H ₂ NC (O) -O- (C ₆ H ₄ ) -SO ₃ NH ₄
• - H ₂ NC (O) -OC (O) -H
• - H ₂ NC (O) -OC (O) -CH ₃
• - H ₂ NC (O) -OC (O) -CH ₂ CH ₃
• - H ₂ NC (O) -OC (O) - (CH ₂ ) ₂ CH ₃
• - H ₂ NC (O) -OC (O) -CH (CH ₃ ) ₂
• - H ₂ NC (O) -OCH ₃
• - H ₂ NC (O) -NH-OH
• - H ₂ NC (O) -O-CH (OH) ₂
• - H ₂ NC (O) -PH (O) OH
• - H ₂ NC (O) -P (O) (OH) ₂
• - H ₂ NC (O) -NH-C (O) -NH ₂
• - H ₂ NC (O) -NH-NH ₂
• - H ₂ NC (O) -NH-CN
• - H ₂ NC (O) -P (OH) (O) -C (O) NH ₂
• - H ₂ NC (O) -SCN
• - H ₂ NC (O) -OCN
• - H ₂ NC (O) -SC (NH) NH ₂
• H ₂ NC (O) -N (CH ₃ ) ₃ ⁺ Cl ^-
• H ₂ NC (O) -N (CH ₂ CH ₃ ) ₃ ⁺ Cl ^-
• - H ₂ NC (O) -N ((CH ₂ ) ₂ CH ₃ ) ₃ + Cl ^-
• H ₂ NC (O) -N (CH (CH ₃ ) ₂ ) ₃ ⁺ Cl ^-
• H ₂ NC (O) -N (C ₆ H ₅ ) ₃ ⁺ Cl ^-
• H ₂ NC (O) -N (CH ₂ -Ph) ₃ ⁺ Cl ^-
• - H ₂ NC (O) -N (CH ₃ ) ₃ ⁺ Br ^-
• - H ₂ NC (O) -N (CH ₂ CH ₃ ) ₃ ⁺ Br ^-
• - H ₂ NC (O) -N ((CH ₂ ) ₂ CH ₃ ) ₃ ⁺ Br ^-
• - H ₂ NC (O) -N (CH (CH ₃ ) ₂ ) ₃ ⁺ Br ^-
• - H ₂ NC (O) -N (C ₆ H ₅ ) ₃ ⁺ Br ^-
• - H ₂ NC (O) -N (CH ₂ -Ph) ₃ ⁺ Br ^-
• H ₂ NC (O) -N (CH ₃ ) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N (CH ₂ CH ₃ ) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N ((CH ₂ ) ₂ CH ₃ ) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N (CH (CH ₃ ) ₂ ) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N (C ₆ H ₅ ) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N (CH ₂ -Ph) ₃ ⁺ H ₃ C-OSO ₃ ^-
• H ₂ NC (O) -N (CH ₃ ) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^-
• H ₂ NC (O) -N (CH ₂ CH ₃ ) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^-
• - H ₂ NC (O) -N ((CH ₂ ) ₂ CH ₃ ) ₃ ⁺ H ₃ C-CN ₂ -OSO ₃ ^-
• H ₂ NC (O) -N (CH (CH ₃ ) ₂ ) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^-
• H ₂ NC (O) -N (C ₆ H ₅ ) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^-
• H ₂ NC (O) -N (CH ₂ -Ph) ₃ ⁺ H ₃ C-CN ₂ -OSO ₃ ^-

Farther it has proved to be advantageous if the dyeing and / or Brightening agents contain non-ionic surfactants.

there are such surface-active Substances having an HLB of 5.0 and greater are preferred. For the definition the HLB value becomes explicit on the designs in Hugo Janistyn, Handbuch der Kosmetika und Riechstoffe, III. Tape: The body care products, 2nd edition, dr. Alfred Huthig Verlag Heidelberg, 1973, pages 68-78 and Hugo Janistyn, paperback the modern perfumery and Cosmetics, 4th Edition, Scientific Publishing Company M.B.H. Stuttgart, 1974, pages 466-474, and the original works cited therein Referenced.

Particularly preferred nonionic surfactants are because of the ease of processing substances that are commercially available as solids or liquids in pure form. The definition of purity in this context does not refer to chemically pure compounds. Much In particular, when it comes to natural-based products, mixtures of different homologs may be used, for example, with different alkyl chain lengths, such as those obtained with natural fat and oil-based products. Even with alkoxylated products, mixtures of different degrees of alkoxylation are usually present. The term purity in this context refers rather to the fact that the chosen substances should preferably be free from solvents, stabilizers and other impurities.

• – alkoxylierte Fettalkohole mit 8 bis 22, insbesondere 10 bis 16, Kohlenstoffatomen in der Fettalkylgruppe und 1 bis 30, insbesondere 1 bis 15, Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Fettalkylgruppen sind beispielsweise Lauryl-, Myristyl-, Cetyl-, aber auch Stearyl-, Isostearyl- und Oleylgruppen. Besonders bevorzugte Verbindungen dieser Klasse sind beispielsweise Laurylalkohol mit 2 bis 4 Ethylenoxid-Einheiten, Oleyl- und Cetylalkohol mit jeweils 5 bis 10 Ethylenoxideinheiten, Cetyl- und Stearylalkohol sowie deren Mischungen mit 10 bis 30 Ethylenoxideinheiten sowie das Handelsprodukt Aethoxal^®B (Henkel), ein Laurylalkohol mit jeweils 5 Ethylenoxid- und Propylenoxideinheiten. Neben den üblichen alkoxylierten Fettalkoholen können auch sogenannte „endgruppenverschlossene" Verbindungen erfindungsgemäß eingesetzt werden. Bei diesen Verbindungen weist die Alkoxygruppe am Ende keine OH-Gruppe auf, sondern ist in Form eines Ethers, insbesondere eines C1-C4-Alkyl-Ethers, „verschlossen". Ein Beispiel für eine solche Verbindung ist das Handelsprodukt Dehypon^®LT 054, ein C_12-18-Fettalkoholol + 4,5 Ethylenoxid-butylether.
• – alkoxylierte Fettsäuren mit 8 bis 22, insbesondere 10 bis 16, Kohlenstoffatomen in der Fettsäuregruppe und 1 bis 30, insbesondere 1 bis 15, Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Fettsäuren sind beispielsweise Laurin-, Myristin-, Palmitin-, Stearin-, Isostearin- und Ölsäure.
• – alkoxylierte, bevorzugt propoxylierte und insbesondere ethoxylierte, Mono-, Di- und Triglyceride. Beispiele für bevorzugte Verbindungen sind Glycerinmonolaurat + 20 Ethylenoxid und Glycerinmonostearat + 20 Ethylenoxid.
• – Polyglycerinester und alkoxylierte Polyglycerinester. Bevorzugte Verbindungen dieser Klasse sind beispielsweise Poly(3)glycerindiisostearat (Handelsprodukt: Lameform^®TGI (Henkel)) und Poly(2)glycerinpolyhydroxystearat (Handelsprodukt: Dehymuls^®PGPH (Henkel)).
• – Sorbitan-Fettsäureester und alkoxylierte Sorbitan-Fettsäureester wie beispielsweise Sorbitanmonolaurat und Sorbitanmonolaurat + 20 Ethylenoxid (EO).
• – Alkylphenole und Alkylphenolalkoxylate mit 6 bis 21, insbesondere 6 bis 15, Kohlenstoffatomen in der Alkylkette und 0 bis 30 Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Vertreter dieser Klasse sind beipielsweise Nonylphenol + 4 EO, Nonylphenol + 9 EO, Octylphenol + 3 EO und Octylphenol + 8 EO.

Preferred nonionic surfactants are

• - Alkoxylated fatty alcohols having 8 to 22, in particular 10 to 16, carbon atoms in the fatty alkyl group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty alkyl groups are, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl groups. Particularly preferred compounds of this class are, for example, lauryl alcohol with 2 to 4 ethylene oxide units, oleyl and cetyl alcohol with 5 to 10 ethylene oxide, cetyl alcohol and stearyl alcohol and mixtures thereof with 10 to 30 ethylene oxide units and the commercial product Aethoxal ^® B (Henkel), Lauryl alcohol with 5 ethylene oxide and 3 propylene oxide units. In addition to the usual alkoxylated fatty alcohols, it is also possible to use so-called "end-capped" compounds according to the invention In these compounds, the alkoxy group has no OH group at the end but is "closed" in the form of an ether, in particular a C 1 -C 4 -alkyl ether. , An example of such a compound is the commercially available product ^® Dehypon LT 054, a C _12-18 -Fettalkoholol + 4.5 ethylene oxide-butyl ether.
• - alkoxylated fatty acids having 8 to 22, in particular 10 to 16, carbon atoms in the fatty acid group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty acids are, for example, lauric, myristic, palmitic, stearic, isostearic and oleic acids.
• - alkoxylated, preferably propoxylated and especially ethoxylated, mono-, di- and triglycerides. Examples of preferred compounds are glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide.
• Polyglycerol esters and alkoxylated polyglycerol esters. Preferred compounds of this class are for example poly (3) glycerol diisostearate (commercial product: Lameform ^® TGI (Henkel)) and poly (2) glycerinpolyhydroxystearat (commercial product: Dehymuls ^® PGPH (Henkel)).
• Sorbitan fatty acid esters and alkoxylated sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monolaurate + 20 ethylene oxide (EO).
• - Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15, carbon atoms in the alkyl chain and 0 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 4 EO, nonylphenol + 9 EO, octylphenol + 3 EO and octylphenol + 8 EO.

Especially preferred classes of nonionic surfactants the alkoxylated fatty alcohols, the alkoxylated fatty acids as well the alkylphenols and alkylphenol alkoxylates.

When Particularly advantageous agents according to the invention have proven, the nonionic surfactants Substances in quantities of 1 - 5 Wt .-% included.

Farther can the dyeing and / or Lightening agent all known in such preparations active, additive and auxiliaries. In many cases, the funds contain at least a surfactant, where 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, cationic or nonionic surfactants. Anionic surfactants can do this be particularly preferred.

Preferred anionic surfactants are alkyl sulfates, ether carboxylic acid salts having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule such as C _{1 2} H ₂₅ - (C ₂ H ₄ O) ₆ -CH ₂ -COONa and in particular salts of saturated and especially unsaturated C8-C22 carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.

These anionic surfactants should preferably be in solid, in particular powder form available. Very particularly preferred are at room temperature solid soaps, in particular sodium stearate. These are preferred in amounts of 5 to 20 wt .-%, in particular 10 to 15 wt .-%, before.

When Nonionic surfactants are particularly suitable C8-C22 alkyl mono- and oligoglycosides and their ethoxylated analogs. Especially the non-ethoxylated compounds have been found to be particularly suitable.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and
Trialkylmethylammonium chlorides, eg cetyltrimethylammonium chloride,
Stearyltrimethylammonium chloride, distearyldimethylammonium chloride,
Lauryldimethylammoniumchlorid, Lauryldimethylbenzylammoniumchlorid and
Tricetylmethylammonium chloride. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

Alkylamidoamines, in particular fatty acid amidoamines, such as the ^{stearylamidopropyldimethylamine} obtainable under the name Tego ^Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as the Distearoylethylhydroxyethylammoniummethosulfat available in a blend with Cetearylalkohle under the name Dehyquart® ^® F 75 miles.

at the compounds used as surfactants with alkyl groups each are uniform substances. However, it is usually preferred in the preparation of these substances of native vegetable or animal raw materials, so that you substance mixtures obtained with different, depending on the raw material alkyl chain lengths.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether und andere, als Feststoff stabile bzw. im Handel erhältliche Verbindungen,
• – zwitterionische und amphotere Polymere, die als Feststoffe stabil bzw. bevorzugt als Handelsprodukte erhältlich sind,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren und Vinylacetat/Crotonsäure-Copolymere, sofern diese als Feststoffe stabil bzw. bevorzugt im Handel erhältlich sind,
• – 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 Glucose, Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline, sowie Silikonöle
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Farbstoffe zum Einfärben der Zubereitungen,
• – Wirkstoffe wie Panthenol, Pantothensäure, Allantoin, Pyrrolidoncarbonsäuren und deren Salze,
• – Cholesterin,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs, Paraffine, Fettalkohole und Fettsäureester,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,

Other active ingredients, auxiliaries and additives are, for example

• 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 and other solid-stable or commercially available compounds,
• Zwitterionic and amphoteric polymers, which are stable as solids or preferably available as commercial products,
• Anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids and vinyl acetate / crotonic acid copolymers, if these are stable or preferably commercially available as solids,
• Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives such as methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol,
• - structurants such as glucose, maleic acid and lactic acid,
• Hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, and silicone oils
• 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,
• Dyes for coloring the preparations,
• - active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts,
• - cholesterol,
• Fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• Fatty acid alkanolamides,
• - complexing agents such as EDTA, NTA and phosphonic acids,
• - swelling and penetrating substances such as carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

The Selection of these other substances will be the skilled person according to the desired Meet properties of the agents.

When further ingredient can the compositions of the invention at least one ammonium compound from the group ammonium chloride, Ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate in an amount of 0.5 to 10, preferably 1 to 5 wt .-%, based on contain the total composition of the agent.

• – 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/Methyl-methacrylat/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.Butyl-acrylamid-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-1-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,

enthaltenFurthermore, the dyeing and / or brightening agents according to the invention may contain 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, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• Anionic polymers, for example polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives such as methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as 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

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

The agents according to the invention can the ingredients in a suitable aqueous, alcoholic or aqueous-alcoholic carrier contain. For the purpose of hair coloring are such carriers For example, 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 possible, one powdery or also tablet-shaped To provide formulation, which is for coloring and / or brightening agents is preferred.

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.

preferred inventive agent are characterized in that they additionally a non-aqueous solvent contain, with particularly preferred compositions according to the invention the solvent in a concentration of 0.1-30 Weight percent, preferably in a concentration of 1-20 weight percent, completely more preferably in a concentration of 2-10% by weight, respectively based on the agent included.

In furthermore preferred agents according to the invention is the solvent selected from ethanol, n-propanol, Isoropanol, n-butanol, propylene glycol, n-butylene glycol, glycerol, Diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, Phenoxyethanol and benzyl alcohol and their mixtures.

Of the pH value of the agents according to the invention can by suitable ingredients such as Acidifizierungsmittel or Alkalizing agent can be adjusted in a wide range.

A oxidative staining The fibers may be in the presence of oxidation dye precursors in principle done with atmospheric oxygen. However, preference is given to a chemical Oxidizing agent used, especially if in addition to the staining a Whitening effect on human hair is desired. This whitening effect can be independent from the staining method required be. The presence of oxidation dye precursors is accordingly no mandatory requirement for an employment of oxidizing agents in the agents according to the invention. 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 ³⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

• – 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 which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg

• Pyranose oxidase and 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.

at An application of oxidants becomes the actual colorant expediently immediately before use by mixing the preparation of the Oxidizing agent with the preparation containing the compounds of formula I and optionally dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. Particularly preferred is the application of Hair Dye in a slightly alkaline environment. The application temperatures can in a range between 15 and 40 ° C. After an exposure time of 5 to 45 minutes will be 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 may be an agent of the invention optionally with additional Dye precursors but also without prior mixing with the Oxidation component to be applied to the hair. After a Einwirkdauer of 20 to 30 minutes will then - if necessary after a 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.

For the application the agents according to the invention on the hair, the dyeing and / or lightening agent mixed with a hydrogen peroxide solution immediately before application. The concentration of this hydrogen peroxide solution is on the one hand by the legal requirements and on the other hand of the desired Effect determined; usually 6- to 12-percent solutions in Water used. The proportions of dyeing and / or lightening agent and hydrogen peroxide solution are usually in the Range 1: 1 to 1: 2, with an excess of hydrogen peroxide solution in particular then chosen if not too pronounced Blondierwirkung desired is.

In addition, the agents according to the invention contain additional ingredients. A use of certain metal ions For example, or complexes may be preferred to be intense colorations to obtain. Here, agents according to the invention are preferred which additionally contain Cu, Fe, Mn, Ru ions or complexes of these ions.

Preferred agents according to the invention for dyeing and / or lightening keratinic fibers additionally contain Cu, Fe, Mn, Co, Ce, V, Ru ions or complexes of these ions, preferred agents being from 0.0001 to 2.5% by weight .-%, preferably 0.001 to 1 wt .-% of at least one compound from the group copper chloride (CuCl ₂ ), copper sulfate (CuSO ₄ ), iron (II) sulfate, manganese (II) sulfate, manganese (II) chloride, cobalt ( II) chloride, cerium sulfate, cerium chloride, vanadium sulfate, manganese dioxide (MnO ₂ ).

According to the invention preferred is also the use of so-called complexing agents. Complex images are Substances that can complex metal ions. Preferred complexing agents are so-called chelate complexing agents, ie substances with metal ions form cyclic compounds, wherein a single ligand more than occupy a coordination site on a central atom, i. at least "bidentate". In this case Thus, normally stretched compounds by complexation on a Ion closed to rings. The number of bound ligands depends on the coordination number of the central ion.

common and in the context of the present invention, preferred chelate complex images Examples are polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), Nitrilotriacetic acid (NTA) and hydroxyethanediphosphonic acids or their alkali metal salts. Also complexing polymers, ie polymers, either in the main chain itself or sideways too carry functional groups which can act as ligands and with suitable metal atoms usually reacting to form chelate complexes are used according to the invention. The polymer-bound ligands of the resulting metal complexes can with only one macromolecule or belong to different polymer chains. The latter leads to Crosslinking of the material, unless the complexing polymers already above covalent bonds were crosslinked.

complexing Groups (ligands) more common complexing polymers are iminodiacetic acid, hydroxyquinoline, thiourea, Guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and crown ether residues with z. T. very specific. Activities towards ions different metals. Many base polymers are also commercially available important complexing polymers are polystyrene, polyacrylates, Polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethylenimines. Also natural Polymers such as cellulose, starch or chitin are complexing polymers. In addition, these can provided by polymer-analogous transformations with other ligand functionalities become.

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine.

In the context of the present invention, it is particularly preferable to use one or more chelating agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di (β-hydroxyethyl) glycine, N- (1,2-dicarboxy 2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof,
• d) aminophosphonic acids, such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

When polycarboxylic a) in the context of this patent application also carboxylic acids Monocarbonsäuren- understood, in which the sum of carboxyl and contained in the molecule Hydroxyl groups is at least 5. Complexing agent from the Group of nitrogen-containing polycarboxylic acids, in particular EDTA, are prefers. In the invention required alkaline pH values of the treatment solutions are these complexing agents at least partially as anions. It does not matter if they are in the form of acids or in the form of salts. In case of use Salts are alkali, ammonium or alkylammonium salts, in particular Sodium salts, preferred.

As well As further preferred complexing agents are polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts and derivatives, in addition to cobuilder properties also have a bleach-stabilizing effect.

Further suitable complexing agents are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Another class of substances with complex-forming properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. You will be in front preferably in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. The complexing agent used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. These substances will be described below.

According to the invention preferred Chelating agents are phosphonates, preferably hydroxyalkane or aminoalkanephosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its Di- or tetrasodium salt and / or ethylenediamine tetramethylene phosphonate (EDTMP) or its hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta- or Octasodium.

• (a) Nitrilotriessigsäure (NTA),
• (b) Diethylenetriaminpentaesigsäure (DTPA),
• (c) Ethylendiamindibernsteinsäure (EDDS),
• (d) Ethylenediamindiglutarsäure (EDGA),
• (e) 2-Hydroxypropylendiamindibernsteinsäure (HPDS),
• (f) Glycinamid-N,N'-dibernsteinsäure (GADS),
• (g) Ethylendiamin-N-N'-diglutarsäure (EDDG),
• (h) 2-Hydroxypropylendiamin-N-N'-dibernsteinsäure (HPDDS),
• (i) Ethylendiamintetraessigsäure (EDTA),
• (j) Ethylendicysteinsäure (EDC),
• (k) Diaminoalkyldi(sulfobernsteinsäure) (DDS),
• (l) Ethylendiamine-N-N'-bis(ortho-hydroxyphenylesigsäure (EDDHA),
• (m) N-2-hydroxyethyl-N,N-diessigsäure,
• (n) Glyceryliminodiessigsäure,
• (o) Iminodiessigsäure-N-2-hydroxypropylsulfonsäure,
• (p) Asparaginsäure-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonsäure,
• (q) 8-Alanin-N,N'-diessigsäure,
• (r) Asparaginsäure-N,N'-diessigsäure,
• (s) Asparaginsäure-N-monoessigsäure,
• (t) Dipicolinsäure,
• (u) sowie deren Salze und/oder Derivate

Particularly preferred agents according to the invention contain one or more substances from the group

• (a) nitrilotriacetic acid (NTA),
• (b) diethylenetriaminepentaacetic acid (DTPA),
• (c) ethylenediamine disuccinic acid (EDDS),
• (d) ethylenediamine-diglutaric acid (EDGA),
• (e) 2-hydroxypropylenediamine disuccinic acid (HPDS),
• (f) glycinamide-N, N'-disuccinic acid (GADS),
• (g) ethylenediamine-N-N'-diglutaric acid (EDDG),
• (h) 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS),
• (i) ethylenediaminetetraacetic acid (EDTA),
• (j) ethylene dicysteic acid (EDC),
• (k) diaminoalkyldi (sulfosuccinic acid) (DDS),
• (l) ethylenediamine-N-N'-bis (ortho-hydroxyphenylacetic acid (EDDHA),
• (m) N-2-hydroxyethyl-N, N-diacetic acid,
• (n) glyceryliminodiacetic acid,
• (o) iminodiacetic acid N-2-hydroxypropylsulfonic acid,
• (p) aspartic acid-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonic acid,
• (q) 8-alanine-N, N'-diacetic acid,
• (r) aspartic acid-N, N'-diacetic acid,
• (s) aspartic acid N-monoacetic acid,
• (t) dipicolinic acid,
• (u) and their salts and / or derivatives

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine,

wobei bevorzugte Mittel Phosphonate, vorzugsweise Hydroxyalkan- bzw. Aminoalkanphosphonate und insbesondere 1-Hydroxyethan-1,1-diphosphonat (HEDP) bzw. dessen Di- oder Tetranatriumsalz und/oder Ethylendiamintetramethylenphosphonat (EDTMP) bzw. dessen Hexanatriumsalz und/oder Diethylentriaminpentamethylenphosphonat (DTPMP) bzw. dessen Hepta- oder Octanatriumsalz, enthalten.From the above-mentioned groups of substances, some representatives are particularly preferred in the context of the present invention. Particularly preferred according to the invention for dyeing and / or brightening keratinic fibers additionally contain one or more chelate complexing agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins,

preferred agents being phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and especially 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylene phosphonate (EDTMP) or its hexasodium salt and / or diethylene triamine pentamethylene phosphonate (DTPMP) or its hepta- or octa-sodium salt.

preferred inventive agent are formulated low in water or anhydrous. Particularly according to the invention preferred agents are characterized by being less as 5% by weight, preferably less than 2% by weight, more preferably less than 1% by weight and in particular less than 0.5% by weight of water contain, with preferred agents are anhydrous. The water content the means can be left For example, determine by titration Karl Fischer.

• – gewünschtenfalls ein Vorbehandlungsmittel M1 auf die Faser aufgebracht wird, dann
• – ein Mittel M2 auf der Faser zur Anwendung kommt, wobei gewünschtenfalls dem Mittel M2 vor der Anwendung ein weiteres Mittel M3 zugegeben wird,
• – dieses Mittel M2 nach einer Zeit von 5-30 Minuten von der Faser abgespült wird
• – und nach der Behandlung gegebenenfalls ein Nachbehandlungsmittel M4 auf die Faser aufgetragen und nach einer Einwirkzeit von einigen Minuten wieder abgespült wird,

wobei mindestens eines der Mittel M1, M2 oder M3 ein erfindungsgemäßes Mittel ist.A second object of the present invention is a process for whitening keratin fibers, in particular human hair, in which

• - If desired, a pretreatment agent M1 is applied to the fiber, then
• A means M2 is applied to the fiber, wherein, if desired, an additional agent M3 is added to the agent M2 before use,
• - This agent M2 is rinsed from the fiber after a time of 5-30 minutes
• - and after the treatment optionally a post-treatment agent M4 applied to the fiber and rinsed again after a contact time of a few minutes,

wherein at least one of the means M1, M2 or M3 is an agent according to the invention.

The agents according to the invention can Accordingly, as Einkomponentenmittel (coloring and brightening agent M2 or Aftertreatment agent M4), as a two-component agent (M2 + M3) or formulated as a three-component agent (M2 + M3 + M4) and accordingly be applied. Separation into multicomponent systems offers in particular where to expect incompatibilities of the ingredients or to be feared; the agent to be used in such systems by the consumer prepared directly before use by mixing the component.

One dyeing and whitening process wherein the whitening cream and the oxidizing agent first are present separately, is preferred. Another item The present invention therefore provides a method of dyeing and Lightening of human hair, in which a composition on an aqueous basis, containing hydrogen peroxide, with an agent according to the invention mixed into a homogeneous composition, and this on the Hair is applied.

In preferred processes of this type according to the invention, the aqueous composition contains from 1 to 20% by weight, preferably from 2 to 10% by weight and in particular from 3 to 6% by weight of hydrogen peroxide, calculated as 100% H _2, by weight O ₂ .

Further preferred method according to the invention of this type are characterized in that the composition is water-based, containing hydrogen peroxide, with an agent according to the invention in weight ratio 1: 5 to 10: 1, preferably 1: 2 to 5: 1 and especially 1: 2 to 2: 1 mixed to a homogeneous composition, and this on the hair is applied.

alternative can - like mentioned above - also a Three-component system used. Another item The present invention therefore provides a method of dyeing and Lightening of human hair, in which a composition on an aqueous basis, containing hydrogen peroxide, containing with another agent preferably at least one alkali donor and / or substantive Hair dye and / or at least one oxidation dye precursor, and an agent of the invention mixed into a homogeneous composition, and this on the Hair is applied.

Regarding further preferred embodiments the inventive method mutatis mutandis applies to the means of the invention said.

in der
X, Y, Z stehen unabhängig voneinander für ein Wasserstoffatom oder ein Halogenatom
R steht für eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte (C₁-C₆)-Alkylgruppe, oder eine gegebenenfalls substituierte (C₁-C₆)-Alkylengruppe, oder einen (C₁-C₆)Acylrest
in Mitteln zum Färben und/oder Aufhellen keratinischer Fasern.Another object of the present invention is the use of esters and / or anhydrides of the formula (I):

in the
X, Y, Z independently represent a hydrogen atom or a halogen atom
R is an optionally substituted aryl group or an optionally substituted (C ₁ -C ₆ ) -alkyl group, or an optionally substituted (C ₁ -C ₆ ) -alkylene group, or a (C ₁ -C ₆ ) acyl radical
in agents for dyeing and / or lightening keratinic fibers.

• i. Steigerung der Aufhell- bzw. Blondierleistung und/oder
• ii. Steigerung der Hautverträglichkeit von Aufhell- bzw. Blondiermitteln.

Particularly preferably, the use of the compounds serves to achieve certain advantageous effects. Preferred according to the invention are uses for

• i. Increase in the whitening or bleaching performance and / or
• ii. Increase the skin compatibility of brightening or bleaching agents.

With regard to preferred uses according to the invention, mutatis mutandis is the preferred executed.

Examples:

The Investigations were carried out in aqueous solutions carried out. strands from dark blond hair (codes: Kerling 2/0 or 7/0) of about 0.5 g weight were in beakers with the 15-fold amount of drug solution poured over and 30 minutes at Bleached at 32 ° C. The pH was adjusted to about 10.0 and 8.0, respectively.

The Hydrogen peroxide concentrations were 6.0%, respectively Concentrations of the 3 active ingredients (Aldrich) 5.0%. The solutions were additionally with 1.5% Turpinal (60% solution of hydroxyethanediphosphonic acid) and 0.1% dipicolinic acid stabilized.

Colorimetric results:

The Measurements show that even by the addition of the acetic acid derivatives to the hydrogen peroxide solutions an improvement in lightening is achieved.

Claims (22)

Agent for dyeing and / or whitening keratin fibers, in particular human hair, containing, by weight, from 0.001 to 15% by weight of at least one ester and / or anhydride of the formula (I):

in which X, Y, Z independently of one another represent a hydrogen atom or a halogen atom R stands for an optionally substituted aryl group or an optionally substituted (C ₁ -C ₆ ) -alkyl group or a hydroxyalkyl group or a polyhydroxyalkyl group or an optionally substituted (C ₁ -) C ₆ ) -alkylene group, or a (C ₁ -C ₆ ) acyl radical. Agent for dyeing and / or lightening keratinic fibers according to claim 1, characterized in that it contains one or more esters from the group - methyl acetate and / or - ethyl acetate and / or - monoiodoacetic acid methyl ester and / or - monobromoacetic acid methyl ester and / or - monochloroacetic acid methyl ester and / or - methyl monofluoroacetate and / or - methyl diiodoacetate and / or - methyl dibromoacetate and / or - dichloroacetate and / or - methyl difluoroacetate and / or - methyl tribromoacetate and / or - methyl trichloroacetate and / or - trifluoroacetate and / or - monoiodoacetic acid ethyl ester and / or Ethyl monobromoacetate and / or ethyl monochloroacetate and / or ethyl monofluoroacetate and / or di-ethyl acetate and / or ethyl dibromoacetate and / or dichloro ethyl acetate and / or - Difluoroessigsäureethylester and / or - Triiodessigsäureethylester and / or - Tribromessigsäureethylester and / or - trichloroacetic acid ethyl ester and / or - trifluoroacetic acid ethyl ester. Dyeing agent and / or lightening keratinic fibers according to one of claims 1 or 2, characterized in that it one or more anhydrides from the group Acetic anhydride and / or - Monoiodessigsäureanhydrid and or - Monobromacetic anhydride and or - monochloroacetic anhydride and or - Monofluoroacetic anhydride and or Diiodoacetic anhydride and or - dibromoacetic anhydride and or - Dichloroacetic anhydride and or - Difluoroacetic anhydride and or - Triiodoacetic anhydride and or - tribromoacetic anhydride and or - Trichloroacetic anhydride and or - trifluoroacetic anhydride and or - propionic acid-acetic anhydride and or - Butanoic acid-acetic anhydride and or - Acetic acid monoiodoacetic anhydride and or - Acetic acid monobromoacetic anhydride and or - Acetic acid monochloroacetic anhydride and or - Acetic acid monofluoroacetic anhydride and or - Acetic acid diiodoacetic anhydride and or - Acetic acid dibromoacetic anhydride and or - Acetic acid dichloroacetic anhydride and or - Acetic acid-difluoroacetic anhydride and or - Acetic acid triiodoacetic anhydride and or - Acetic acid tribromoacetic anhydride and or - Acetic acid trichloroacetic anhydride and or - Acetic acid trifluoroacetic anhydride and or Trichloroacetic acid monoiodoacetic anhydride and or Trichloroacetic acid monobromoacetic anhydride and or Trichloroacetic acid monochloroacetic anhydride and or Trichloroacetic acid monofluoroacetic anhydride and or Trichloroacetic diiodoacetic anhydride and or Trichloroacetic acid dibromoacetic anhydride and or - Trichloroacetic acid-dichloroacetic anhydride and or - trichloroacetic acid-difluoroacetic anhydride and or Trichloroacetic acid triiodoacetic anhydride and or Trichloroacetic acid tribromoacetic anhydride and or Trichloroacetic acid trifluoroacetic anhydride and or Trifluoroacetic acid monoiodoacetic anhydride and or Trifluoroacetic acid monobromoacetic anhydride and or - trifluoroacetic acid monochloroacetic anhydride and or - trifluoroacetic acid monofluoroacetic anhydride and or Trifluoroacetic acid diiodoacetic anhydride and or - Trifluoroacetic acid-dibromoacetic anhydride and or - trifluoroacetic acid-dichloroacetic anhydride and or - Trifluoroacetic acid-difluoroacetic anhydride and or Trifluoroacetic acid triiodoacetic anhydride and or Trifluoroacetic acid tribromoacetic anhydride and or Trifluoroacetic acid trichloroacetic anhydride contains. Dyeing agent and / or lightening keratinic fibers according to any one of claims 1 to 3, characterized in that it the ester (s) and / or anhydride (s) in amounts of 0.1 to 12.5% by weight, preferably from 0.25 to 10% by weight, especially preferably from 0.5 to 7.5% by weight and in particular from 1 to 5% by weight, each based on the total agent contains. Agent for dyeing and / or whitening keratinic fibers according to one of Claims 1 to 4, characterized in that it contains 0.5 to 15% by weight, preferably 1 to 12.5% by weight, more preferably 2.5 to 10 Wt .-% and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H ₂ O ₂ ) contains. Dyeing agent and / or lightening keratinic fibers according to any one of claims 1 to 5, characterized in that it additionally - related on his weight - 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes. Dyeing agent and / or lightening keratinic fibers according to any one of claims 1 to 6, characterized in that it as oxidation dye precursor at least one developer component contains preferred developer components being selected from p-phenylenediamine, p-toluenediamine ,, N, N-bis (2-hydroxyethyl) amino-p-phenylenediamine, 1,3-bis - [(2-hydroxyethyl-4'-aminophenyl) amino] propane-2-ol, 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane, 4-aminophenol, 4-amino-3-methylphenol, bis (5-amino-2-hydroxyphenyl) methane, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4,5-diamino-1- (2-hydroxyethyl) pyrazole. Dyeing agent and / or lightening keratinic fibers according to any one of claims 1 to 7, characterized in that it as oxidation dye precursor at least one coupler component contains preferred coupler components being selected from resorcinol, 2-methylresorcinol, 5-methyl-resorcinol, 2,5-dimethylresorcinol, 4-chlororesorcinol, resorcinol monomethyl ether, 5-aminophenol, 5-amino-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 3-amino-4-chloro-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-amino-2,4-dichlorophenol, 2,4-diaminophenoxyethanol, 2-amino-4- (2'-hydroxyethyl) amino-anisole sulfate, 1,3-bis (2,4-diaminophenoxy) propane, 2-amino-3-hydroxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-phenyl-3-methylpyrazol-5-one, 2,6-bis - [(2'-hydroxyethyl) amino] -toluene, 4-hydroxyindole, 6-hydroxyindole, 6-hydroxybenzomorpholine. Dyeing agent and / or lightening keratinic fibers according to any one of claims 1 to 8, characterized in that it contains at least one substantive dye that is selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group of international Names or trade names of known dyes 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, Acid Black 52, Basic Yellow 87, Basic Orange 31 and Basic Red 51 known compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) -aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-Amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. Agent for dyeing and / or lightening keratinic fibers according to one of claims 1 to 9, characterized in that it - based on its weight - 1 to 20 wt .-% of at least one imidazole compound of formula (II) and / or their physiologically acceptable salts

contains, in which R ¹ represents a hydrogen atom, an optionally substituted aryl group or a (C ₁ -C ₆ ) alkyl group, R ² represents a hydrogen atom, a carboxaldehyde group, a (C ₁ -C ₆ ) alkyl group or a nitro group, R ³ a hydrogen atom, a carboxy (C ₁ -C ₆ ) alkyl group, an amino (C ₁ -C ₆ ) alkyl group, a carboxyl group, a carboxaldehyde group, a (C ₁ -C ₆ ) alkyl group, a nitro group, a 2-amino-3-hydroxypropyl group or a group -CH ₂ -CH (NH ₂ ) -COOH, R ⁴ represents a hydrogen atom, a carboxaldehyde group or a carboxyl group. Dyeing agent and / or whitening keratinic fibers according to claim 10 characterized in that it at least one imidazole compound according to formula (II) and / or its physiologically acceptable salts in amounts of from 2 to 15% by weight, preferably from 2.5 to 12.5% by weight, particularly preferably from 3 to 10% by weight and in particular from 4 to 8 wt .-% contains. Dyeing agent and / or whitening keratinic fibers according to one of claims 10 or 11, characterized in that the Imidazole compound according to formula (II) and / or the physiologically acceptable salts thereof are / are selected from histamine, D-histidine, L-histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, imidazole, imidazole-4-acetic acid, imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, imidazole-2-carboxaldehyde, Imidazole-4-carboxaldehyde, imidazole-5-carboxaldehyde, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole-5-carboxaldehyde, N-methylimidazole-2-carboxaldehyde, 4-methylimidazole, 2-methylimidazole, N-methylimidazole, N- (4-aminophenyl) -imidazole, as well as the physiologically acceptable Salts of the aforementioned compounds. Dyeing agent and / or lightening keratinic fibers according to any one of claims 1 to 12 characterized in that it additionally 0.01 to 2% by weight of at least one solid peroxy compound which is selected from ammonium and alkali metal persulfates and peroxydisulfates contains preferred agents containing peroxydisulfates, preferably selected are from sodium peroxydisulfate and / or potassium peroxydisulfate and / or Ammonium peroxydisulfate and particularly preferred agents being at least contain two different Peroxidislfate. Dyeing agent and / or lightening keratinic fibers according to any one of claims 1 to 13, characterized in that it additionally 0.1 to 25 wt.%, Preferably 0.5 to 20 wt.%, Particularly preferably 1 to 15 wt.% And in particular 1.5 to 10 wt.% Of at least one Substance from the groups of i. Carbonates and / or ii. Monoalkyl carbonates (carbonic acid monoester) and or iii. Kohlensäuremonoamide and or iv. Silyl carbonates and / or v. Silylcarbamate contains. Agent for dyeing and / or lightening keratinic fibers according to any one of claims 1 to 14, characterized in that it additionally - 0.05 to 5 wt .-% of at least one cyanate of the formula M ⁺ [OCN] ^- in which M ^{+ stands} for K ⁺ , Na ⁺ , Li ⁺ or NH ₄ ⁺ or 1/2 Ca ²⁺ , 1/2 Mg ²⁺ or 1/2 Zn ²⁺ and / or - 0.05 to 5 wt. -% of at least one compound of the formula H ₂ NC (O) -L in which L is a group displaceable by the anion ^- OOH. Dyeing agent and / or lightening keratinic fibers according to claim 15, characterized characterized in that it 0.075 to 4 wt .-%, preferably 0.1 to 2.5 wt .-% and in particular 0.2 to 1% by weight of sodium cyanate and / or potassium cyanate and / or ammonium cyanate contains wherein sodium cyanate is particularly preferred. Agent for dyeing and / or whitening keratinic fibers according to one of claims 15 or 16, characterized in that it contains 0.075 to 4 wt.%, Preferably 0.1 to 3.5 wt.% And in particular 0.2 to 3 wt .-% of at least one compound of the formula H ₂ NC (O) -L in which L is selected from -S-CH ₂ -COOH, -S- (CH ₂ ) ₃ SO ₃ H, -S- (CH ₂ ) ₂ -NH ₂ , -OCH ₃ , -O- (C ₆ H ₄ ) -SO ₃ M, -Q ⁺ , -NH-OH, -OC (O) -R ¹ , -OC (O) -H, -O-CH (OH) ₂ , -SO ₃ M, -PH (O) OH, -P (O) (OH) ₂ , - (NH-glucosamine) _n , -NH-C (O) -NH ₂ , -NH-NH ₂ , -NH-CN, -P (OH) (O) -C (O) NH ₂ , -SCN, -OCN, -SC (NH) NH ₂ ,

and M is -H, Na, K, NH4, Q is selected from quaternary ammonium radicals, heteroaryl radicals or non-aromatic heterocycles formed from tertiary amines and R ^{1 is} -H, -CH ₃ , -CH ₂ CH ₃ , - ( CH ₂ ) ₂ CH ₃ , -CH (CH ₃ ) ₂ or another alkyl group. Agent for dyeing and / or lightening keratinic fibers according to one of Claims 1 to 17, characterized in that it additionally contains Cu, Fe, Mn, Co, Ce, V, Ru ions or complexes of these ions, preferred agents comprising from 0.0001 to 2.5% by weight, preferably from 0.001 to 1% by weight, of at least one compound selected from the group consisting of copper chloride (CuCl ₂ ), copper sulfate (CuSO ₄ ), iron (II) sulfate, manganese (II ) sulfate, manganese (II) chloride, cobalt (II) chloride, cerium sulfate, cerium chloride, vanadium sulfate, manganese dioxide (MnO ₂ ). Dyeing agent and / or lightening keratinic fibers according to any one of claims 1 to 18, characterized in that it additionally one or more chelating agents from the groups of (I) polycarboxylic in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, (Ii) nitrogenous mono- or polycarboxylic acids, (iii) geminal diphosphonic acids, (Iv) aminophosphonic, (V) phosphonopolycarboxylic, (Vi) cyclodextrins contains preferred agents include phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta- or octa sodium salt. Method for whitening keratin fibers, in particular human hair, characterized in that If desired, a pretreatment agent M1 is applied to the fiber, then - a medium M2 on the fiber is used, if desired the agent M2 before use another agent M3 added becomes, - this one Means M2 is rinsed off the fiber after 5-30 minutes - and after the treatment optionally an M4 after treatment Fiber applied and after a contact time of a few minutes rinsed off again becomes, wherein at least one of the means M1, M2 or M3 a Means according to one of the claims 1 to 18 is. Use of esters and / or anhydrides of the formula (I):

in which X, Y, Z independently of one another represent a hydrogen atom or a halogen atom R represents an optionally substituted aryl group or an optionally substituted (C ₁ -C ₆ ) -alkyl group, or an optionally substituted (C ₁ -C ₆ ) -alkylene group , or a (C ₁ -C ₆ ) acyl radical in agents for dyeing and / or whitening keratinic fibers. Use according to claim 21 for i. Increase in the whitening or bleaching performance and / or ii. Increase the skin compatibility of brightening or bleaching agents.