WO2007121853A2

WO2007121853A2 - Lightening and/or colouring agents comprising n,n'-oxalyldiazoles and/or oximidyldiazoles

Info

Publication number: WO2007121853A2
Application number: PCT/EP2007/003163
Authority: WO
Inventors: Horst Höffkes; Denise Fuhr; Wibke Gross; Doris Oberkobusch; Georg KNÜBEL
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2006-04-20
Filing date: 2007-04-10
Publication date: 2007-11-01
Also published as: DE102006018778A1; WO2007121853A3

Abstract

The invention relates to high-performance and low irritant agents for lightening and/or colouring keratin fibres, in particular human hair. Said agents contain, in relation to their weight, 0,001 to 15 wt.% of one or more N,N'-oxalyldiazoles and/or oximidyldiazoles and, preferably, in addition to, 0,001 to 5 wt.% of one or more oxidation dye precursors and/or direct dyes.

Description

"Lightening and / or coloring agents with N, N ^{'-Oxalyldiazolen} and / or Oximidyldiazolen"

The present invention relates to means for dyeing and / or whitening keratinic fibers, i. Agent for use on keratin fibers, in particular human hair, and their use.

The change in shape and color of the hair is an important area of modern cosmetics dar. Thus, the appearance of the hair can be adapted to both current fashion trends and the individual desires of each person. In this case, permanent wave and other hair-changing methods can be used almost independently of the type of hair to be treated. In contrast, dyeing and bleaching processes are limited to certain initial hair colors. The basics of the bleaching processes are known to those skilled in the art and may be described in relevant monographs, e.g. by Kh. Schrader, Basics and Formulations of Cosmetics, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Umbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, be read.

At the same time, however, there is often the desire to change the hair color and to achieve a brightening of the hair to be dyed together with the hair coloring.

Conventional hair dyes usually consist of at least one developer and at least one coupler substance and possibly even contain direct dyes as Nuanceure. Coupler and developer components are also referred to as oxidation dye precursors.

Before being applied to human hair, hair dyeing and / or lightening agents are mixed in solid or pasty form with dilute aqueous hydrogen peroxide solution. This mixture is then applied to the hair and rinsed again after a certain exposure time. The duration of exposure to the hair to achieve complete coloration or brightening is between about 30 and 40 minutes. It is obvious that there is a need among users of these hair dyes or bleaching agents to reduce this exposure time.

Neither the pasty nor the powdered dyeing and / or bleaching agents that are on the market today can be considered optimal. While the dyeing and / or bleaching effect on the hair may be said to be tailored to consumer needs, there are still a number of disadvantages and problems both in the manufacture and handling of these agents.

Thus, coloration and bleaching processes on keratinic fibers usually proceed at alkaline pH values, in particular between 9.0 and 10.5. These pH values are necessary to ensure an opening of the outer cuticle (cuticle) and to allow a penetration of the active species (dye precursors and / or hydrogen peroxide) into the hair. The alkalizing agent used is usually ammonia, which however has the disadvantage of intense odor and possible irritation for the users.

In market products, for example, aminomethylpropanol or monoethanolamine are used as alternative alkalizing agents to ammonia. However, since they often lag behind ammonia in their performance, they are usually used in admixture with ammonia. But even here, the performance of the ammonia is impaired, especially with regard to the parameters gray covering, whitening performance and color result.

There is therefore still a need for active ingredients or active substance combinations for brightening and coloring agents with reduced ammonia content. In particular, in ammonia-reduced or even -free dye and / or hydrogen peroxide-containing formulations, a performance comparable to conventional ammonia-based compositions should be achieved.

It has now been found that azole derivatives of oxalic acid and / or imidoxalic acid can be incorporated with particular advantage into hair dyeing and lightening agents and lead to an increase in the performance of these agents.

In a first embodiment, the present invention relates to agents for dyeing and / or lightening keratin fibers, in particular human hair, containing - based on its weight -

0.001 to 15 wt .-% of one or more N, N ^{'-Oxalyldiazole} and / or

Oximidyldiazole. Keratin fibers mean furs, wool, feathers and in particular human hair. Although the compositions according to the invention are primarily suitable for dyeing and / or whitening keratin fibers, in principle, there is nothing to prevent their use in other fields as well.

The agents according to the invention comprise as essential ingredient at least one azole derivative of oxalic acid and / or imidoxalic acid, ie at least one compound of the type BC (O) -C (O) -B and / or of type BC (NR ¹ ) -C (NR ¹ ) B in which B is an azole radical, for example pyrrole and / or pyrazole and / or imidazole and / or 1, 2,3-triazole and / or 1, 2,4-triazole and / or 1, 2,3, 4-tetrazole.

Preferred agents for dyeing and / or lightening keratin fibers are characterized in that they contain one or more N, N ^{'-Oxalyldiazole} and / or Oximidyldiazole of formula (I)

contain, in which

A is O or NR1,

B is an optionally substituted, N-linked radical from the group pyrrole, pyrazole, imidazole, 1, 2,3-triazole, 1, 2,4-triazole, 1, 2,3,4-tetrazole,

R ¹ represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted (CrC ₆₎ alkyl group or an optionally substituted (C _r _C6) alkylene group,

According to the invention are preferably used accordingly

N, N ^{'-Oxalyl-di-pyrroles,} in which the pyrrole ring may be optionally substituted:

N, N ^{'-Oximidyl-di-pyrroles,} in which the pyrrole ring may be optionally substituted and R ¹ is as defined above:

N, N ^{'-Oxalyl-di-pyrazoles,} in which the pyrazole ring may be optionally substituted:

N, N ^{'-Oximidyl-di-pyrazoles,} in which the pyrazole ring may be optionally substituted and R ¹ is as defined above:

N, N ^'-Oxalyl-di- imidazoles in which the imidazole ring may be optionally substituted:

N, N ^{'-Oximidyl-di-lmdidazole} in which the imidazole ring may be optionally substituted and R ¹ is as defined above:

N, N ^'-Oxalyl-di- (1, 2,3-triazoles) wherein the triazole ring may be optionally substituted:

N, N ^{'-Oximidyl-di-} (1, 2,3-triazoles) wherein the triazole ring may be optionally substituted and R ¹ is as defined above:

NN ^{'-Oxalyl-di-O} ^ .ΦTriazole), where the triazole ring may be optionally substituted:

N, N ^{'-Oximidyl-di-} (1, 2,4-triazoles) wherein the triazole ring may be optionally substituted and R ¹ is as defined above:

NN ^' -oxalyl-dKI ^ .S ^ -tetrazoles) in which the tetrazole ring may optionally be substituted:

N, N'-oximidyl-di- (1,2,3,4-tetrazoles) in which the tetrazole ring may optionally be substituted and R ^{1 is} as defined above:

According to the invention, particularly preferred compositions for dyeing and / or lightening keratin fibers containing one or more N, N ^{'-Oxalyldiazole} and / or Oximldyldiazole of formula (II)

wherein

X ¹ , X ² and X ³ are each independently CR ¹ or NA is O or N R1,

R ¹ independently represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted (Ci-C ₆₎ alkyl group, or an optionally substituted (C _r _C6) alkylene group,

R ² represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted (C _r C ₆ ) alkyl group, or an optionally substituted (C ₁ -C ₆ ) -alkylene group, wherein the R ¹ at X ³ together with R ^{2 represents} an optionally aromatic or heteroaromatic ring can form.

Among these compounds of the formula (II), some are particularly preferred. Accordingly, particularly preferred composition of the invention for dyeing and / or lightening keratin fibers, characterized in that it comprises one or more N, N ^{'-Oxalyldiazole} of the formulas (IIa) and / or (IIb) and / or (Mc) and / or (Hd ) and / or (he)

wherein R ^{1 is in} each case -H, -CH ₃ , -CH ₂ CH ₃ , - (CH) ₂ -CH ₃ , -CH (CH ₃ ) _2l - (CH ₂ ) ₃ CH ₃ , - (CHz) ₄ CH ₃ , - (CH ₂ ) ₅ CH ₃ .

Explicitly, in particular, let us mention representatives in which R ^{1 is} -H, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl or n-hexyl. Here are preferred means for Dyeing and / or lightening keratin fibers, characterized in that it comprises one or more N, N ^{'-Oxalyldiazole} from the group

and or

contain.

Preferably, the azole derivative (s) of the oxalic or oxalic acid are used within narrower ranges. Here, agents according to the invention for dyeing and / or lightening keratin fibers preferred that the or the N, N ^{'-Oxalyldiazol} (s) in amounts of 0.1 to 12.5 wt .-%, preferably from 0.25 to 10 Wt .-%, particularly preferably from 0.5 to 7.5 wt .-% and in particular from 1 to 5 wt .-%, each based on the total agent 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 serve not (only) a lightening, but also or exclusively a color change of the keratin fibers treated with them. Agents which simultaneously have a coloring and lightening effect are also referred to as lightening colorants.

Preferred agents for dyeing and / or lightening keratinic fibers according to the invention are characterized in that they additionally contain, based on their weight, from 0.001 to 5% by weight of one or more oxidation dye precursors and / or direct dyes.

The agents of the invention are preferably colorants, i. Means for changing the color of keratinic fibers. Among them, particularly the so-called oxidation colorants are preferable. Oxidation colorants according to the invention contain at least one coupler and at least one developer component. Coupler and developer components are also referred to as oxidation dye precursors. In addition, the oxidation colorants according to the invention may also contain substantive dyes as nuances. According to preferred means for dyeing and / or lightening keratinischer fibers are therefore characterized in that they contain at least one oxidation dye precursor of the developer type and / or coupler type.

The developer components are usually primary aromatic amines with a further, located in the para or ortho position free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone 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, hydroxypyrimidine 2 ₁ 4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used.

Suitable coupler substances are in particular 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- Methyl resorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylaminopyridine and 3,5-diamino-2,6-dimethoxypyridine.

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 analog dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups.

In a first preferred embodiment, the colorant further contains at least one developer component. The developer components are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-amino pyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its Derivatives used.

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, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy ( C _r to C ₄₎ alkyl group a 4'-aminophenyl, or C ₁ - to C ₄ alkyl radical substituted with a nitrogenous group, a phenyl group or a 4'-aminophenyl radical; G ² represents a hydrogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy (C _r to C ₄₎ alkyl radical or a C ₁ - to C ₄ alkyl radical substituted with a nitrogenous 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 - bis C ₄ -hydroxyalkyl radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to C ₄ -

Acetylaminoalkoxy radical, a C ₁ - to C ₄ -mesylaminoalkoxy radical or a C ₁ - to C ₄ -

Carbamoylaminoalkoxyrest;

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are especially the amino groups, C ₁ - to C ₄ monoalkylamino, C ₁ - to C ₄ dialkylamino, C ₁ - to C ₄ -Trialkylamrnoniumgruppen, C ₁ - to C ₄ - Monohydroxyalkylaminogruppen, Imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-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-acetyla Minoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts. Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.

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

Among the binuclear developer components which can be used in the 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 represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen , Sulfur or nitrogen atoms may be interrupted or terminated and may optionally be substituted by one or more hydroxyl or C ₁ - to C ₈ -alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -hydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that the compounds of the formula (E2) contain only one bridge Y per molecule and the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred dinuclear developing agents of the formula (E2) are in particular: N, N'-bis- (β-hydroxyethyl-N, N'-bis-1'-aminophenyl O-S, S-diamino-propane, -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 acceptable salts.

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

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a Cp 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, C ₁ to C ₄ aminoalkyl, Hy (C ₁ to C ₄ ) alkylamino, C ₁ to C ₄ hydroxyalkoxy, C ₁ to C C ₄ -hydroxyalkyl- (C ₁ -C ₄ ) -aminoalkyl radical or a (di-C ₁ -C ₄ -alkylamino) - (C ₁ -C ₄ ) -alkyl radical, 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 _r to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ -cyanoalkyl radical,

G ¹⁵ is hydrogen, a d- to C ₄ alkyl, C ₁ - to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ is hydrogen or a halogen atom.

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

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

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

Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Further, the developer component may be selected from heterocyclic developer components, such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts. Preferred pyridine derivatives are in particular the compounds 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxypyridine, 2- (β-methoxyethyl ) amino-3-amino-6-methoxypyridine 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 _I 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3 - (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1 - isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-

Triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

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

in which:

D- to C ₄ alkyl radical, an aryl radical, a hydroxyalkyl radical to C _4, a C ₂ - - G ^17, G ^18, G ¹⁹ and G ²⁰ are independently a hydrogen atom, a C ₁ to C ₄ - Polyhydroxyalkylrest a (d- to C ₄ J-AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ - aminoalkyl radical which may optionally be protected by an acetyl-ureide or a sulfonyl radical, a (d- to C ₄₎ alkylamino (Cr to _C4) alkyl, a di-J (C ₁ - to C ₄₎ alkyl] - (Cr to _C4) aminoalkyl radical, wherein the dialkyl residues 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 independently of one another are a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C _r - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a cis-bis C ₄ -Aminoalkylrest, a (C ₁ - to CO-alkylamino-fCr to C ₄ ) alkyl, a di-KC ₁ - to C ₄ ) alkyl] - (C ₁ - to C ₄ ) aminoalkyl radical, wherein the dialkyl Radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, a C ₁ - to C _4- alkyl or di- (C ₁ - to C ₄ -hydroxyalkyl) amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0, if p + q equals 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ bel keep the positions (2,3); (5,6); (6,7); (3,5) or (3,7); wweennnn pp ++ qq gglleeiicchh 11 iisstt ,, nn ddeenn WWeerrtt 11 hhaatt ,, and dd the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the

Group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);

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

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

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

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

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

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

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

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

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

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

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

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

5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1, 5-a] -pyrimidine; and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

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

Particularly preferred oxidation colorants according to the invention are characterized in that the developer component is selected from 3-methyl-1,4-diaminobenzene, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 2- (2,5-diaminophenoxy) ethanol , N, N-bis (2'-hydroxyethyl) -1, 4-diaminobenzene, 3-methyl-4-aminophenol and 2-methylamino-4-aminophenol, p-phenylenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine , N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino propan-2-ol, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-fluorophenol, 4-amino-2-aminomethylphenol, 4-amino-2- ((diethylamino) methyl) phenol, o-aminophenol, 2-amino-4-methylphenol, 2-amino-5-methylphenol, 2-amino-4-chlorophenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-tr iaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, 1- (2'-hydroxy-5'-aminobenzyl) -imidazolidin-2-one, 4,5-diamino-1 (2'-hydroxyethyl) pyrazole and Λ / - (4-amino-3-methylphenyl) -Λ / - [3- (1H -imidazol-1-yl) propyl] amine trihydrochloride.

Preferred agents according to the invention contain as oxidation dye precursor at least one developer component, 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] -propan-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 of the invention may further contain at least one coupler component.

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

Coupler components preferred according to the invention are m-aminophenol and its derivatives, such as, for example, 5-amino-2-methylphenol, N-

Cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5- Amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-

Hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol, 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-bis

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 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 preferred coupler components according to the invention 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.

As precursors of naturally-analogous dyes such indoles and indolines are preferably used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

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 CVC ^ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C 1 -C ₄ -alkyl group, and R ⁵ is one of the groups mentioned under R ⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline,

N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.

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

(Illb) in the independently

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, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,

R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,

R ⁴ is hydrogen, a Ci-C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -AIk ^ gOiPPe, and

R ⁵ is one of the groups mentioned under R ⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid. Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

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

The indoline and indole derivatives can be used in the colorants used in the process according to the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for. As the hydrochlorides, sulfates and hydrobromides are used. The indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment, it may be preferred according to the invention to use the indoline or indole derivative in hair dyes in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; Very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.

Particularly preferred oxidation colorants according to the invention are characterized in that the coupler component is selected from m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives, preferred agents being resorcinol, 3-amino-2-methylamino-6-methoxypyridine, 3-amino-6-methylphenol, 3-amino-2-hydroxypyridine, 1, 3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 5-methyl-resorcinol, 2.5 Dimethyl resorcinol and 4-chlororesorcinol 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine, 2 - ({3 - [(2- Hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3- [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenyl amine and / or 2 - [(3-morpholin-4-yl-phenyl) -amino] -ethanol dihydrochloride.

Agents preferred according to the invention for dyeing and / or lightening keratinic fibers are characterized in that they contain at least one coupler component as the oxidation dye precursor, preferred coupler components being selected from Resorcinol, 2-methylresorcinol, 5-methylresorcinol, 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.

Preferably, coupler and developer components are used in a particular ratio to each other. Here, oxidation colorants of the present invention containing the coupler component (s) in an amount of 0.01 to 20 wt%, preferably 0.5 to 5 wt%, and the developer component (n) in an amount of 0, are preferable. 01 to 20 wt .-%, preferably from 0.5 to 5 wt .-%, 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 1,1,4-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-hydroxybenzyl 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-methylpheny1) azo) -5-nitro-1,3-thiazole; N, N-di (2-hydroxyethyl) -3-methyl-4 - ((4-nitrophenyl) azo) aniline; 3-diethylamino-7- (4-dimethylaminophenylazo) -5-phenyl-phenazinium chloride; 4- (2-thiazolylazo) resorcinol, 4 - (((4-

Phenylamino) azo) benzenesulfonic acid, sodium salt; 1 - ((3-aminopropyl) amino) -9, IO-anthracenedione; 3 ', 3 ", 4,5,5', 5", 6,7-Octabromphenolsulfonphtalein; 1 - ((4-Amino-3,5-dimethylpheny1) - (2,6-dichlorophenyl) methylene) -3.5 -dimethyl-4-imino-2,5-cyclohexadiene-phosphoric acid (1: 1) (Basic Blue 77); 3 ', 3 ", 5', 5"-tetrabromo-m-cresolsulfonephthalein; 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt; 4- [2'-hydroxy-1'-naphthyl) azo] - benzenesulfonic acid sodium salt; 3 ', 6'-dihydroxy-2', 41151171-tetraiodospiro- [isobenzo-furan-1 (3H), g1 (9H) -xanthenl-3-one disodium salt; 6-hydroxy-5 - ((2-methoxy-5-methyl-4-sulfophenyl) azo) -2-naphthalenesulfonic acid disodium salt; 2,4-dinitro-inaphthol sodium salt; 2 ', 4 ^l , 5', 7'-tetrabromo-4151617-tetrachloro-3'16'-dihydroxy-

Spiro [isobenzofuran-I (3H), 9 '[9H] xanthene] -3-one disodium salt; 4- (2-hydroxy-1-naphthylazo) -3-methyl-benzenesulfonic acid sodium salt; 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.

Agents preferred according to the invention for dyeing and / or brightening keratinic fibers are characterized in that they contain at least one substantive dye selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group known by the international names or trade names Dye 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 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 as well as 1 , 4-diamino-2-nitrobenzene, 2-amino-4-n itrophenol, 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 their derivatives Salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

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

(a) cationic triphenylmethane dyes such as Basic Blue 7,

Basic Blue 26, Basic Violet 2 and Basic Violet 14, (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as

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

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

CH ₃ SO ₄ ^'

Cf

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c). The cationic substantive dyes 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 preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the total colorant.

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

It is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, further components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

With regard to the dyes which can be used in the hair-dyeing and tinting compositions according to the invention, reference is expressly made to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250, direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the series "Dermatology" (Editor: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials", Issued by the European Community, available in disk form from the Federal Association of German industrial and commercial enterprises for pharmaceuticals, health products and personal care registered association, Mannheim, reference is made.

Staining of keratinic fibers can also be accomplished by dyes formed in an oxidatively catalyzed reaction of C, H-acidic compounds with reactive carbonyl compounds.

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) oligopeptides constructed from 2 to 9 amino acids.

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

Component A is preferably selected from the group formed from acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3 Hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-dihydroxyacetophenone 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-hydroxybenzophenone 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-dimethyl-benzaldehyde, 4-hydroxy-2,6-dimethyl-benzaldehyde, 4-hydroxy-3,5-dimethoxy-benzaldehyde, 4-hydroxy-3,5-dimethyl-benzaldehyde, 3,5-diethoxy 4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 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-trimethoxybenzaldeh yd, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3- Dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2, 3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino 2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxybenzaldehyde 1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1 -naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2-methoxycinnamaldehyde, 4-methoxycinnamaldehyde , 4-hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 4-dimethylamino-cinnamic aldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino cinnamaldehyde, 4-dibutylaminobenzaldehyde, 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-1 H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene -1, 3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde),

2-indolaldehyde, 3-indolaldehyde, 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, chromone-3-aldehyde, 3- (5'-nitro-2'-furyl) -acrolein, 3- (2'-Furyl) -acrolein and imidazole-2-aldehyde, 1, 3-diacetylbenzene, 1, 4-diacetylbenzene, 1, 3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) - acetophenone, 2- (2'-furoyl) acetophenone, 2- (2'-pyridoyl) acetophenone and 2- (3'-pyridoyl) acetophenone,

Benzylideneacetone, 4-hydroxybenzylideneacetone, 2-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-benzylidenecyclohexanone, 2- (4 '-Hydroxybenzylidene) cyclohexanone, 2- (4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3- ( 4'-dimethylaminobenzylidene) -1, 3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2 - (4'-hydroxy-3-methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidenecyclopentanone , 2 '- (4-hydroxybenzylidene) -cyclopene tanon, 2- (4'-dimethylaminobenzylidene) 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-diene-2-one,

5- (4-Dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy -3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3 nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde , 4,5-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 l-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-methyl-quinolinium, 4-acetyl-1-one methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8- Formyl-i-methylquinolinium, 5-formyl-i-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-Formyl-i-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-i-allylquinolinium, 6-formyl-i-allylquinolinium, 7-formyl-1 allyl-quinolinium and 8-formyl-i-allyl-quinolinium, 5-acetyl-1-methyl-quinolinium, 6-acetyl-1-methyl-quinolinium, 7-acetyl-1-methyl-quinolinium, 8-ace tyl-i-methylquinolinium, 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 - allyl-quinolinium and 8-acetyl-1-allyl-quinolinium, 9-formyl-10-methyl-acridinium, 4- (2'-formyl-vinyl) -1-methyl-pyridinium, 1, 3-dimethyl-2- (4'-formyl-phenyl) benzimidazolium, 1,3-dimethyl-2- (4'-formylphenyl) imidazolium, 2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3 -methylbenzothiazolium, 2- (4'-formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'- furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formyl-1 -naphthyl) -3-methylbenzothiazolium, 5-chloro-2- (4'-formylphenyl) -3-methylb enzothiazolium, 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.

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,

in which

R ^{1 *} , R ^{2 *} and R ^{3 *} independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkyl group, a hydroxy group, a C _r C ₆ -alkoxy group, a C ₁ -C ₆ -dialkylamino group, a di (C ₂ -C ₆ hydroxyalkyl) amino group, a di (Ci-C ₆ -alkoxy-CrC ₆ - alkyl) aminoguppe, a Ci-C _δ -Hydroxyalkyloxygruppe, a sulfonyl group, a 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-methoxybenzaldehyde, 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-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde hyd, 4-hydroxy-2,6-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-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-methyl-benzaldehyde, 2,4-dihydroxy-3-methoxybenzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 2,4-dihydroxy-6-methoxybenzaldehyde, 2,5- Dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-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-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethyl-aminobenzaldehyde, 4-dieth ylaminobenzaldehyde, 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-nitrobenzaldehyde, 2-hydroxy-3- nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldeh yd, 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.

Agents preferred according to the invention are characterized in that they are formulated as hair colorants, based on their weight 0.01 to 20 wt .-%, preferably 0.05 to 15% by weight, particularly preferably 0.1 to 12.5 wt .-% and in particular 0.2 to 10 wt .-% of one or more reactive carbonyl compound (s). As CH-acidic compounds are generally considered to carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents activation of the corresponding carbon-hydrogen bond is effected. According to the invention, CH-acidic compounds also include enamines which are formed by alkaline treatment of quaternized N-heterocycles with a CH-acidic alkyl group in conjugation with the quaternary nitrogen.

The CH-acidic compounds of component B are preferably selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methylnaphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1, 4-dimethylquinolinium iodide, 1, 2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-indoxylatoacetate, 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 on, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5-dimethyl lcyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methylbenzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl-4-methyl- quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1, 2,3-trimethylquinoxaluminum iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl 4-methylquinolinium p-toluenesulfonate, 1-ethyl-2-methylquinolinium p-toluenesulfonate, and 1,2,3-trimethylquinoxaluminum p-toluenesulfonate.

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 ₁ 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) -ethanoi, 2,4-diaminophenoxyethanoi, 2- (2,5-diaminophenoxy) ethanol, 4-methylamino, 3 -Amino-4- (2 ¹ -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-hydroxymethyl lphenol, 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-aminosalicic acid, 3-amino-4-hydroxy, 4-amino-3-hydroxy benzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-A-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, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobrencatechol, 4,6-diaminopyrogaliol, 3,5-diamino-4 - Hydroxybrenzcatechin, aromatic anilines or phenols with another aromatic radical, as shown in the following formula

in the R ^{6 represents} a hydroxy or an amino group represented by C _1-4 -alkyl,

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 is} hydrogen, a hydroxy or an amino group, which is substituted by a C _1-4 -alkyl group, or C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl; , C _1-4 -hydroxyalkyl, C- _M -aminoalkyl- or

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 with the following formula

-Q '- (CH ₂ -Q-CH ₂ -Q ") _O -

in which Q is a direct bond, a CH ₂ or CHOH group, Q and Q 'independently represent an oxygen atom, an NR ¹² group, wherein R ^{12 is} hydrogen, a CI-, -alkyl-, or hydroxy-C _1-4 alkyl group, the group -O- (CH ₂ ) _p -NH- or -NH- (CH ₂ ) _p -O-, wherein p and p 'are 2 or 3, and o is a number of 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'-tetraaminobenzophenone, 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-hydroxyethylamino] -2-propanol, N, N-bis- [2- (2- 4-aminophenoxy) ethyl] methylamine, N-phenyl-1, 4-phenylenediamine. The abovementioned compounds can be used 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.

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-diamino, 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-triamino-1} 6 ₁ 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-morpholinoaniline and Indoles and indolines, and their physiologically acceptable salts, be. 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 aforementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, for. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid, are used.

Preferred amino acids are all naturally occurring and synthetic (alpha-amino acids, eg the amino acids obtainable by hydrolysis from vegetable or animal proteins, eg collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan, but other amino acids can also be used, such as 6-aminocaproic acid.

The oligopeptides may be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolysates, provided that they have sufficient water solubility for use in the colorants according to the invention. Examples are, for example, glutathione or the oligopeptides contained in the hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Preferred is the use together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds. Suitable aromatic hydroxy compounds are, for example, 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, 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.

As CH-active compounds there can be exemplified 1, 2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium-p-toluoisulfonate, 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-indoxylacetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

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

wherein

R ⁸ and R ⁹ are independently a linear or cyclic Ci-C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-C _r C ₆ alkyl group, a C _r C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C _T -Cβ alkoxy-CrCβ-alkyl group, a group R ¹ R ¹¹ N- (CH ₂ JM, wherein R ¹ and R ¹ 'are independently of one another for a hydrogen atom, a

a C _r C ₄ -hydroxyalkyl group or an aryl-CτC ₆ -alkyl group, wherein R ¹ and R ¹¹ 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 ¹² independently represent a hydrogen atom or a C ₁ -C ₆ - alkyl group, wherein at least one of the radicals R ¹⁰ and R ¹² is a C _r C ₆ alkyl group,

R ¹¹ represents a hydrogen atom, a CrC ₆ alkyl group, a CrCβ-hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a CτC ₆ alkoxy group, a C ₁ -C ₆ - hydroxyalkoxy group, a group R "'R ^lv N - (CH ₂ ) q-, wherein R ¹ "and R ^IV independently represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl-d-Ce-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 ^{12 can form} a 5- or 6-membered aromatic ring which is optionally substituted by 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 -Ce hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH ₂ ) _S -, wherein R ^V and R ^VI are each independently a hydrogen atom, a CrC ₆ alkyl group, a C ₁ -C ₆ - hydroxyalkyl group or an Ar ^ -C C ₁ -C ₆ -alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,

R ¹³ and R ¹⁴ either form membered 6 together with the nitrogen atom form a saturated or unsaturated 5- or ring or independently represent a (C ₁ - C ₆₎ alkyl group, a (C ₂ -C ₆₎ alkenyl group, a 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 ¹ R ¹¹ N- (CH ₂ J _m in which R ¹ and R ¹¹ independently of one another represent a hydrogen atom, a (C 1 -C 4 -alkyl group, a C 1 -C 4 -alkenyl group or an arylCrCβ-alkyl group, where R 'and R ¹¹ together with the nitrogen atom form a 5-, Can form a 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, and

R ^{15 is} a hydrogen atom, a (C _r C ₆ ) alkyl group, a (C ₂ -C ₆ ) alkenyl group, an aryl group, an aryl (C _r C ₆ ) alkyl group, a (C ₂ -C ₆ ) - Hydroxyalkyl group, a (C ₂ -C ₆ ) - polyhydroxyalkyl group or a group R "'R ^lv N- (CH ₂ ) _n -, wherein R ¹ " and R ^IV independently of one another represent a hydrogen atom, a (Ci-C ₆ ) -Alkyl group, a (Ci-C ₆ ) - alkenyl group or an aryl-CrC ₆ -alkyl group, wherein R ¹ "and R ^ιv together with the nitrogen atom can form a 5-, 6- or 7-membered ring and n is one Number 2, 3, 4, 5 or 6

Y represents an oxygen atom, a sulfur atom or a group NR ^V ", in which R ^v " represents a hydrogen atom, an aryl group, a heteroaryl group, a C _r C ₆ -alkyl group or a d-Ce-arylalkyl group,

X ^" stands for a physiologically compatible anion,

Het is an optionally substituted heteroaromatic,

X ¹ represents a direct bond or a carbonyl group. Equivalent to the compounds of formula IV are their enamine forms. Reference is here made expressly to the document WO-A1-2004 / 022016, to which reference is made in full.

At least one group R ¹⁰ or R ¹² according to formula IV 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 ¹² are each independently hydrogen or a methyl group, wherein at least one group R ¹⁰ or R ^{12 is} a methyl group.

In a preferred embodiment of the formula (IV), Y is an oxygen atom or a sulfur atom, particularly preferably an oxygen atom.

The radical R ⁸ of the formula (IV) is preferably selected from a (C _r _C6) -Alkylgmppe (particularly preferably a methyl group), a C ₂ -C ₆ alkenyl group (particularly an allyl group), a hydroxy (C ₂ - to C ₆ ) alkyl group, in particular a 2-hydroxyethyl group, or an optionally substituted benzyl group.

R ¹¹ according to formula (IV) is preferably a hydrogen atom.

Particularly preferably, the radicals R ⁹ , R ¹⁰ and R ^{12 of} the formula (IV) 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 (CrC ₆ ) Alkyl group (particularly preferably a methyl group), a C ₂ -C ₆ alkenyl group (especially an allyl group), a hydroxy (C ₂ to C ₆ ) alkyl group, especially a 2-hydroxyethyl group, or an optionally substituted benzyl group.

Preferably, the compounds according to formula IV are selected from one or more

Compounds of the group of salts with physiologically acceptable counterion X ^' , which is formed from salts of the

1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidinium, 1, 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidinium,

1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium,

1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinone,

1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidiniums,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1, 3,4-trimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium,

1 _{l of} 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidinium _I

1, 2-dihydro-1, 3-diphenyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and

1, 2-dihydro-3,4-dimethyl-2-thioxo-quinazolinium.

Very particularly preferred agents according to the invention are characterized in that they are used as

CH-acidic compound

Salts of i-dihydro-i .SAδ-tetramethyl ^ -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 the 1-allyl-1 ^ -dihydro-SAδ-trimethyl ^ -oxopyrimidiniums,

Salts of 1 _{l of} 2-dihydro-1- (2-hydroxyethyl) -3,4 _{l of} 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.

X ^' in formula (IV) and in the above lists is preferably halide, benzenesulfonate, p-toluenesulfonate,

Trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogen sulfate, tetrafluoroborate, hexafluorophosphate or Tetrachlorozinkat. The anions chloride, bromide, iodide, hydrogen sulfate or p-toluenesulfonate are particularly preferably used as X ". The radical Het according to formula (V) is preferably the molecule fragment of the formula (VII)

wherein

R ¹⁶ and R ¹⁷ independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic C _r C ₆ alkyl group, a C ₂ - C ₆ alkenyl group, an optionally substituted aryl group, a cyanomethyl group a cyanomethylcarbonyl, an optionally substituted heteroaryl group, an aryl-alkyl group -C _6, a Ci-Ce-hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a -C ₆ alkoxy group, a -C ₆ alkoxycarbonyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ - alkyl group, a -C ₆ sulfoalkyl, a C _r C ₆ carboxyalkyl group, a group R ^v "'R ^lx N- (CH ₂₎ _m -, _wor i _n R ^VI" _unc J R ^IX independently of one another represent a hydrogen atom, a linear or cyclic C _r C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₄ -alkyl group, where R ^vι "and R ^ιx together with the nitrogen atom form a 5-, 6- or 7-membered ring can and m is a number O ₁ 1, 2, 3 or 4, wherein R ¹⁶ and / or R ^{17 can form} a fused to the ring of the remainder of the molecule, optionally substituted aromatic or heteroaromatic, 5- or 6-ring

X ² and X ³ independently of one another represent a nitrogen atom or a group CR ¹⁵ , where R ¹⁵ is a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic C _r 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 arylC _r C ₆ alkyl group, a CτC ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ - C ₆ alkoxy group, a Ci-C ₆ alkoxycarbonyl group, a Ci-C ₆ -alkoxy-C ₂ -C ₆ alkyl group, a -C ₆ sulfoalkyl, a -C ₆ carboxyalkyl group and a group R ^X R ^XI N- (CH ₂₎ _n -, wherein R ^x and R ^xι independently represent a hydrogen atom, a linear or cyclic Ci-C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₁ -C ₆ - hydroxyalkyl group or a Aryl-C _r C ₄ alkyl group, wherein R ^x and R ^xι together mi t is the nitrogen atom can form a 5-, 6- or 7-membered ring and n is 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 a fused optionally substituted can form aromatic 5- or 6-ring, • X ⁴ is an oxygen atom, a sulfur atom, a vinyl group or a group N-H, where the last two groups independently optionally _δ having a linear or cyclic CrC alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted Aryl group, an optionally substituted heteroaryl group, an aryl-CrCβ-alkyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ - polyhydroxyalkyl, a CrC ₆ alkoxy-C ₂ -C ₆ alkyl group, a Ci-Ce -Sulfoalkylgruppe, a C _r C ₆ -Carboxyalkylgruppe, a group R ^X "R ^XI " N- (CH ₂ ) _P -, wherein R ^x "and R ^xι " independently represent a hydrogen atom, a linear or cyclic C ₁ -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, a CrCβ-hydroxyalkyl group or an ArVl-C ₁ -C ₄ - alkyl group, wherein R ^x "and R ^xι " together with the nitrogen atom, a 5-, 6- or Can form a 7-membered ring and p stands for a number 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 (VII) to the molecule fragment -X ¹ -CH ₂ -C≡N to give the compound according to formula (V) 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 ¹⁶ , 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 ¹⁶ or R ^{17 forms} 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 (V) 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 ThJo - (C ₁ -C ₆ ) alkyl group, a heteroaryl group, an aryl group, a (CrCβJ alkyl group, a (C ₁ -C ₆ ) alkoxy group, a hydroxy group, a (C ₂ -C ₆ ) hydroxyalkyl group pe, a (C ₂ -C ₆ ) polyhydroxyalkyl group, a (C ₁ -C ₆ ) alkoxyl (C ₁ -C ₆ ) alkyl group, an aryl (C _r C ₆ ) alkyl group, an amino group, a (C 1 -C 4 -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, the compounds according to formula (V) are 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-Dimethylpyrrole-3-oyl) -acetonitrile, 2- (1, 2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1 H-benzimidazol-2-ylacetonitrile, 1 / - / - benzothiazole -2-ylacetonitrile, 2- (pyrid-2-yl) acetone itril, 2,6-bis (cyanomethyl) pyridine, 2- (indole-3-oyl) -acetonitrile, 2- (2-methylindole) 3-oyl) -acetonitrile, 8-cyanoacetyl-7-methoxy-4-methylcoumarin, 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-car tert-butyl ester, 2- (6-hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile and 2- (1-phenyl-1,4-dihydrothiochromeno) -. S -pypyrazole-S -oyO-acetonitrile. Particularly preferred is 1 / - / - benzimidazol-2-ylacetonitrile [2- (cyanomethyl) benzimidazole].

Agents preferred according to the invention are characterized in that they are formulated as hair colorants, based on their weight 0.01 to 20 wt .-%, preferably 0.05 to 15% by weight, particularly preferably 0.1 to 12.5 wt .-% and in particular 0.2 to 10 wt .-% of one or more CH-acidic compound (s) included.

As a further ingredient, the agents according to the invention may with particular preference contain one or more imidazole compounds. Particularly preferred agents according to the invention are characterized in that they additionally contain 0.1 to 15 wt .-%, preferably 0.5 to 12.5 wt .-%, particularly preferably 1 to 10 wt .-% and in particular 3 to 8 wt. -% of at least one imidazole compound according to formula (VIII) and / or physiologically acceptable salts thereof

contain, in which

R ¹ represents a hydrogen atom, an optionally substituted aryl group or a (d-CeJ-alkyl group, R ² is a hydrogen atom, a carboxaldehyde group, a (dC ₆ ) alkyl group or a nitro group,

R ³ represents a hydrogen atom, a carboxy (CrC ₆ ) alkyl group, an AmJnO (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 formula (VIII) are / are used within narrower ranges. Here, agents according to the invention are preferred which contain at least one imidazole compound of the formula (VIII) and / or their physiologically tolerable salts in amounts of from 0.5 to 15% by weight, preferably from 2.5 to 12.5% by weight, especially preferably from 3 to 10 wt .-% and in particular from 4 to 8 wt .-%.

Preferably, the imidazole compounds according to formula VIII are selected from at least one member of a group which 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, and the physiologically acceptable salts of the aforementioned compounds. Imidazole is particularly preferably used according to the invention. Accordingly, preferred agents according to the invention are characterized in that the imidazole compound according to formula (VIII) and / or its physiologically acceptable salts is / 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, and the physiologically acceptable salts of the aforementioned 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 not more than 1, 8% by weight of ammonia, more preferably not more than 1, 5 wt .-% ammonia, even more preferably not more than 1, 25 wt .-% ammonia, more preferably at most 1, 0 wt. -% ammonia and in particular not more than 0.5% by weight of ammonia. In a further preferred embodiment of the present invention, the agents are ammonia-free.

As already mentioned, the compositions according to the invention can also be prepared directly before use from two or more separately packaged preparations. This is particularly useful for the separation of incompatible ingredients to avoid premature reaction.

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

Another object of the present invention is therefore an agent for dyeing and / or whitening keratinic fibers, in particular human hair, which immediately before application to the hair from a flowable preparation A, an oxidizing agent preparation B containing at least one oxidizing agent selected from hydrogen peroxide and whose addition compounds are obtained on solid carriers and a preparation C, which are mixed together to a dyeing and / or Aufhellansatz, wherein the composition A and / or C is a composition of the invention, or the composition A oxidation dye precursor (s) and the composition C Azole derivative (s) of oxalic acid and / or imidoxalic acid (or vice versa).

The mixture of formulations A, B and C prior to use results in an application mixture containing azole derivative (s) of oxalic acid and / or imidoxalic acid and preferably oxidation dye precursor (s). Moreover, preferred application mixtures satisfy the first embodiment of the present invention, i. particularly preferred agents of the second embodiment are so formulated and / or are mixed together in such a ratio that the application mixture contains said quantities of azole derivative (s) of oxalic acid and / or imidoxalic acid.

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 to 12 percent 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 ) contains.

The oxidizer formulation B is preferably an aqueous, flowable oxidizer formulation. Accordingly, preferred agents for dyeing and / or lightening keratinic fibers according to the invention are characterized in that the flowable oxidizing agent preparation B - based on their weight - 40 to 90 wt .-%, preferably 50 to 85 wt .-%, particularly 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 or based on one-component agent, agents according to the invention which are 0.5 to 15 wt.%, Preferably 1 to 12.5 wt.%, Particularly preferably 2.5 to 10 wt.% And in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H ₂ O ₂ ) included.

Preferably, an emulsifier or a surfactant is added to the flowable oxidizing agent preparation B, wherein surface-active substances are referred to as surfactants or as emulsifiers, depending on the field of application, and are selected from 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 customary 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. Among these peroxo compounds, which can also be used in combination, the inorganic compounds are preferred according to the invention. in particular combinations of at least two peroxide isulfates. Here, agents according to the invention for dyeing and / or lightening keratinic fibers are preferred, which additionally contain 0.01 to 2% by weight of at least one solid peroxo compound selected from ammonium, alkali metal and alkaline earth metal persulphates, peroxomonosulphates and peroxydisulfates, 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.

Particular preference is furthermore given to persulfates, in particular the mixture of potassium peroxosulfate, potassium hydrogen sulfate and potassium sulfate, referred to as Caro's salt.

In the case of multicomponent agents, preferably, the flowable oxidizer composition B additionally contains at least one peroxy compound, which is preferably selected from ammonium and alkali metal persulfates and peroxydisulfates, preferred agents containing at least 2 different peroxydisulfates.

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 H group and having their 2,5-

% solution in water in each case has a pH greater than 9.0.

Preferred alkalizing agents are aminocarboxylic acids, in particular α-aminocarboxylic acids and omega-aminocarboxylic acids. Among the α-aminocarboxylic acids lysine and especially arginine are again particularly preferred.

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

Furthermore, the amino acids can also be used in the form of oligopeptides and protein hydrolysates if it is ensured that the required amounts of the amino acids used according to the invention are contained therein. In this context, reference is made to the disclosure of DE-OS 22 15 303, to which reference is expressly made.

A particularly preferred alkalizing agent is arginine. Agents preferred according to the invention are characterized in that they additionally contain from 0.05 to 5% by weight, preferably from 0.1 to 2.5% by weight, particularly preferably from 0.15 to 1% by weight and in particular 0.2 to 0.5 wt .-% amino acid (s), preferably (one) 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 compositions of the present invention may additionally contain at least one other bleaching enhancer other than the inorganic persalts.

As bleach amplifiers, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylene diamines, 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, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran.

To further increase the lightening power, anhydrous compositions according to the invention may additionally comprise, as bleach 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 quantities 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 in principle subject to 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.

In addition to the components described by the empirical formula, the water glasses in small amounts may contain 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.

Agents preferred according to the invention are characterized in that they additionally contain 0.05 to 15% by weight, more preferably 0.15 to 10% by weight and in particular 0.2 to 5% by weight 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.

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

Carbonates and / or

Monoalkyl carbonates (carbonic acid monoesters) and / or

Carbonic acid monoamides and / or Silyl carbonates and / or silyl carbamates.

Particularly suitable carbonates are ammonium, alkali metal and alkaline earth metal carbonates and bicarbonates. For example, sodium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate and ammonium carbamate are particularly preferred.

In addition to or in place of carbonates, the compositions according to the invention may preferably also contain at least one carbonic acid monoester and / or at least one carbonic acid monoamide. 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 (IX)

R-O-C (O) -O-H (IX)

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 (IX), 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. R is particularly preferably _-6 alkyl group is a C. 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 preferred agents according to the invention are characterized in that the radical R in formula (IX) is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl as well as hydroxymethyl and hydroxyethyl radicals.

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 (X) R-NH-C (O) -OH (X)

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 (X), 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 Cvβ-alkyl group. Examples of CrC 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 preferred agents according to the invention are characterized in that the radical R in formula (X) is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl as well as hydroxymethyl and hydroxyethyl radicals.

The acidic H atom of the carbonic acid monoester or monoamide may also be in neutralized form, i. salts of carbonic acid monoesters or carbonic acid monoamides can also be used according to the invention. Here, agents according to the invention are preferred which contain the carbonic acid monoester or the carbonic acid monoamide 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.

Regardless of whether the compositions according to the invention comprise one or more carbonic acid monoesters and / or one or more carbonic acid monoamides, agents according to the invention are preferred which contain the carbonic acid monoester and / or carbonic acid monoamides in amounts of from 0.1 to 20% by weight, preferably from 0 , 5 to 18 wt.%, Particularly preferably from 2 to 15 wt.% And in particular from 5 to 12 wt.%, Each based on the total agent.

In addition to or in place of carbonates and / or carbonic acid monoesters and / or carbonic acid monoamides, the compositions according to the invention may preferably also contain at least one silyl carbonate and / or at least one silyl carbamate. These substances are described in detail below. Agents preferred according to the invention are characterized in that they contain at least one silyl carbonate of the formula (XI)

R ²

R ¹ -Si-OC (O) -OR ⁴ (XI)

R ³

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 substituted 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 alumyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heter ocycle stands.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (XI) 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 (XI) are selected from methyl, ethyl, n Propyl, iso-propyl, n-butyl, iso-butyl, te / t-butyl, hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ in the abovementioned formula (XI) 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 XI) 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 silylcarbonates or in their place, the compositions of the invention may contain silyl carbamates.

Agents preferred according to the invention are characterized in that they contain a silyl carbamate of the formula XII)

R ²

R ¹ -Si-OC (O) -NR ⁴ R ⁵ (XII)

R ³

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 SiIyI 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 (XII) 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 (XII) 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 (XII) 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 wt.%, Particularly preferably from 1 to 15 wt.% And in particular from 1, 5 to 10 wt.%, Each based on the total agent included.

The agents according to the invention preferably have a pH of from 5.0 to 9.0, preferably from 5.5 to 8.0, particularly 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 brightening agents according to the invention may additionally comprise at least one cyanate of the formula M ⁺ [OCN] ^" in the M ⁺ for K ⁺ , Na ⁺ , Li ⁺ or NH ₄ ⁺ or V ₂ Ca ²⁺ , V ₂ Mg ²⁺ or V ₂ Zn ²⁺ and / or at least one compound of the formula H ₂ NC (O) -L, in which L is a group displaceable by the anion ^" OOH.

Therefore, preferred agents according to the invention additionally contain

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 V ₂ Ca ²⁺ , V ₂ Mg ²⁺ or V 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 stands for a group displaceable by the ^~ 00H anion.

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 .

Agents preferred according to the invention are characterized in that they contain 0.075 to 4% by weight, preferably 0.1 to 2.5% by weight and in particular 0.2 to 1% by weight of sodium cyanate and / or potassium cyanate and / or ammonium cyanate with sodium cyanate being particularly preferred.

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 ^~ 00H anion may also be present in the agents according to the invention. Here are preferred agents according to the invention characterized in that they are 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 J ₃ SO ₃ H, -S- (CH ₂ ) ₂ -NH _2l -OCH ₃ , -O- (C ₆ H ₄ ) -SO ₃ M, -Q ⁺ , -NH-OH, -O-C (O) -R ¹ , -O-C (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 , OONa

and M is -H, Na, K, NH 4, Q is selected from quaternary ammonium radicals, heteroaryl radicals or nonaromatic heterocycles formed from tertiary amines and R ^{1 is} --H, -CH ₃ , -CH ₂ CH ₃ , - ( CH ₂ J ₂ CH ₃ , -CH (CH ₃ ) ₂ or another alkyl group.

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- (CH ₂ ) ₂ -NH ₂

- H ₂ NC (O) -S- (CH ₂ J ₃ SO ₃ Na

- H ₂ NC (O) -S- (CH ₂ ) ₃ SO ₃ K

- H ₂ NC (O) -S- (CHz) 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 J-SO ₃ H

- H ₂ NC (O) -O- (C ₆ H ₄ J-SO ₃ Na

- H ₂ NC (O) -O- (C ₆ H ₄ ) -SO ₃ K

- H ₂ NC (O) -O- (C ₆ H ₄ J-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 J 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 ⁺ Cr H ₂ NC (O) -N (CH ₂ CHa) 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 Hs) 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 CHa) 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 Hs) ₃ ⁺ Br ^" H ₂ NC (O) -N (CH ₂ -Ph ) ₃ ⁺ Br ^" H ₂ NC (O) -N (CH ₃ J ₃ ⁺ H ₃ C-OSO ₃ ^" H ₂ NC (O) -N (CH ₂ CHa) 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 Hs) 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 (CHa) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^" H ₂ NC (O) -N (CH ₂ CHa) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^" H ₂ NC (O) -N ((CH ₂ ) ₂ CH ₃ ) ₃ ⁺ H ₃ C-CH 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 Hs) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^" H ₂ NC (O) -N (CH ₂ -Ph) ₃ ⁺ H ₃ C-CH ₂ -OSO ₃ ^" Furthermore, it has proved to be advantageous if the dyeing and / or brightening agents according to the invention contain nonionic surfactants. Such surfactants having an HLB of 5.0 and greater are preferred. For the definition of the HLB value, explicit reference is made to the statements in Hugo Janistyn, Handbuch der Kosmetika und Riechstoffe, III. Volume: The personal care products, 2nd edition, Dr. med. Alfred Hüthig Verlag Heidelberg, 1973, pages 68-78 and Hugo Janistyn, Paperback of modern perfumery and cosmetics, 4th edition, Scientific Verlagsgesellschaft mbH Stuttgart, 1974, pages 466-474, as well as the original works cited therein reference.

Particularly preferred non-ionic surface-active substances are substances that are commercially available as solids or liquids in pure form because of their ease of processing. The definition of purity in this context does not refer to chemically pure compounds. Rather, especially when it comes to natural-based products, mixtures of different homologs can be used, for example, with different alkyl chain lengths, such as those obtained with products based on natural fats and oils. 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.

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), a 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-i ₈ -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.

Particularly preferred classes of nonionic surfactants are the alkoxylated fatty alcohols, the alkoxylated fatty acids and the alkylphenols and alkylphenol alkoxylates.

Agents according to the invention which contain non-ionic surface-active substances in amounts of 1 to 5% by weight have proved to be particularly advantageous.

Furthermore, the dyeing and / or brightening agents according to the invention may contain all known in such preparations active ingredients, additives and excipients. In many cases, the agents contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, cationic or nonionic surfactants. Anionic surfactants may be very 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 ₁₂ 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 present in solid, in particular powder form. Very particular preference is given to solid soaps, especially sodium stearate, at room temperature. These are preferably present in amounts of from 5 to 20% by weight, in particular from 10 to 15% by weight.

Suitable nonionic surfactants are in particular C 8 -C 22 -alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated 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. Cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetylmethyl ammonium 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.

The compounds containing alkyl groups used as surfactants may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths. Other active ingredients, auxiliaries and additives are, for example

nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers,

Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes; cationic polymers such as quaternized cellulose ethers and other solid state compounds; zwitterionic and amphoteric polymers which are stable as solids

Commercial products are available, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids and

Vinyl acetate / crotonic acid copolymers, provided that they are stable as solids or preferably in

Trade are available,

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic,

Karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. Bentonite or fully synthetic hydrocolloids such as e.g. polyvinyl alcohol,

Structurants such as glucose, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg

Lecitin and cephalins, as well as 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,

Complexing agents such as EDTA, NTA and phosphonic acids,

Swelling and penetration substances such as carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, The choice of these other substances will be made by those skilled in the art according to the desired properties of the agents.

As a further constituent, the compositions according to the invention may contain at least one ammonium compound from the group of ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate in an amount of from 0.5 to 10, preferably from 1 to 5,% by weight, based on the total composition of the composition ,

Furthermore, the dyeing and / or brightening agents according to the invention may contain further active ingredients, auxiliaries and

Additives, such as nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl ammonium chloride copolymers, with 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-butylaminoethylmethacrylamide. Hydroxypropyl methacrylate copolymers, anionic polymers such as 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, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. Bentonite or fully synthetic hydrocolloids such as e.g. Polyvinyl alcohol, 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, dimethyl isosorbide and cyclodextrins, Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl 2-alkylimidazolinium methosulfate defoamers such as silicones, dyes for staining the agent,

Antidandruff active ingredients such as Piroctone Olamine, zinc Omadine and Climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,

Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and also bisabolol, vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, 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 agents 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,

Stabilizers for hydrogen peroxide and other oxidizing agents, propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

The compositions according to the invention may contain the ingredients in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. But it is also possible to provide a powdered or tablet-shaped formulation, which is preferred for dyeing and / or brightening agents.

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 -alkoxyethane, 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 agents according to the invention are characterized in that they additionally contain a nonaqueous solvent, particularly preferred compositions according to the invention the solvent in a concentration of 0.1 to 30 weight percent, preferably in a concentration of 1 to 20 weight percent, most preferably in a concentration of 2 to 10 weight percent, each based on the agent.

In further preferred agents according to the invention, the solvent is 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 mixtures thereof.

The pH of the compositions according to the invention can be adjusted within a wide range by suitable ingredients such as acidifying agent or alkalizing agent.

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

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

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

Suitable enzymes are e.g. Peroxidases that can significantly increase 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, e.g. Pyranose oxidase and e.g. D-glucose or galactose,

Glucose oxidase and D-glucose, glycerol oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts, - alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and its salts, tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, choline oxidase and choline, amino acid oxidase and amino acids. In an application of oxidants, the actual colorant is conveniently prepared immediately prior to use by mixing the preparation of the oxidizing agent with the preparation containing the compounds of formula I and optionally dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures can range between 15 and 40 ° C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.

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

For the application of the compositions of the invention on the hair dyeing and / or brightening agents are mixed immediately before application with a hydrogen peroxide solution. The concentration of this hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; As a rule, 6-12% solutions in water are 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 is particularly selected when no too pronounced Blondierwirkung is desired.

In addition, the compositions according to the invention may contain further ingredients. For example, use of certain metal ions or complexes may be preferred to obtain intense colorations. Agents according to the invention which additionally contain Cu, Fe, Mn, Ru ions or complexes of these ions are preferred here. Preferred agents according to the invention additionally comprise 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 from 0.001 to 1 % By weight of at least one compound 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 ) included.

Also preferred according to the invention is 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 which form cyclic compounds with metal ions, a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.

Customary and preferred chelate complex images in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and hydroxyethanediphosphonic acids or their alkali metal salts. Also, complex-forming polymers, ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms usually with the formation of chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complexing polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific. Activities towards ions of different metals. Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.

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.

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) ₁ 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 (methyl enphosphonic acid) or nitrilotri (methylenephosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and f) cyclodextrins.

For the purposes of this patent application, polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. In the case of the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred. Also to be mentioned as further preferred complexing polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.

Further suitable complexing agents are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

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 aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. 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.

Compounds which are preferred according to the invention are phosphonates, preferably hydroxyalkane or aminoalkane phosphonates 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 diethylene triamine pentamethylene phosphonate (DTPMP ) or its hepta- or octasodium salt.

From the above-mentioned groups of substances, some representatives are particularly preferred in the context of the present invention. 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) ₁

(h) 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS),

(i) ethylenediaminetetraacetic acid (EDTA),

(j) ethylene dicysteic acid (EDC),

(k) diaminoalkyl di (sulfosuccinic acid) (DDS),

(I) ethylenediamine-N-N'-bis (ortho-hydroxyphenylacetic acid (EDDHA),

(m) N-2-hydroxyethyl-N, N-diacetic acid,

(n) glyceryliminodiacetic acid,

(o) lminodiacetic 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

Agents preferred according to the invention are characterized in that they additionally comprise 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 diethylenetriaminepentamethylenephosphonate (DTPMP) or its hepta- or octasodium salt. Preferred agents according to the invention are formulated with little or no water. Particularly preferred agents according to the invention are characterized in that they contain less than 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, preferred agents being anhydrous. The water content of the agent can be determined, for example, by means of titration according to Karl Fischer.

A second object of the present invention is a process for whitening and / or dyeing keratin fibers, in particular human hair, characterized in that, if desired, a pretreatment agent M1 is applied to the fiber, then a means M2 is applied to the fiber, wherein if desired Agent M2 is added before use another agent M3, this agent M2 is rinsed from the fiber after a period of 5-30 minutes and after treatment optionally a post-treatment agent M4 applied to the fiber and rinsed 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 be formulated as single-component agents (dyeing and whitening agents M2 or aftertreatment agents M4), as two-component agents (M2 + M3) or as three-component agents (M2 + M3 + M4) and used accordingly. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or feared; the agent to be used in such systems is manufactured by the consumer just prior to use by mixing the component.

A dyeing and whitening process in which the whitening cream and the oxidizing agent are initially separate is preferred. A further subject of the present invention is therefore a process for dyeing and lightening human hair, in which an aqueous-based composition containing hydrogen peroxide is mixed with an agent according to the invention to form a homogeneous composition and applied to the hair.

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 O ₂ . Further preferred processes of this kind according to the invention are characterized in that the aqueous-based composition comprising hydrogen peroxide is mixed with an agent according to the invention in a weight ratio of 1: 5 to 10: 1, preferably 1: 2 to 5: 1 and in particular 1: 2 to 2: 1 mixed into a homogeneous composition, and this is applied to the hair.

Alternatively, as mentioned above, a three-component system may also be used. A further subject matter of the present invention is therefore a process for dyeing and lightening human hair which comprises an aqueous-based composition containing hydrogen peroxide with a further agent containing preferably at least one alkalinity donor and / or substantive hair dye and / or at least one oxidation dye precursor, and a composition according to the invention mixed to a homogeneous composition, and this is applied to the hair.

With regard to further preferred embodiments of the method according to the invention, mutatis mutandis the statements made concerning the agents according to the invention apply.

Another object of the present invention is the use of N, N ^{'-Oxalyldiazolen} and / or Oximidyldiazolen in agents for dyeing and / or lightening keratin fibers.

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

Increase in the whitening or bleaching performance and / or

Increase the skin compatibility of brightening or bleaching agents.

With regard to preferred uses according to the invention, the mutated mutandis applies to the preferred agents.

Examples:

The investigations were carried out in aqueous solutions. Strands of dark brown or 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 active ingredient solution and bleached for 30 minutes at 32 ° C. The pH was adjusted to about 10.0 and 8.0, respectively.

The concentrations of hydrogen peroxide each amounted to 6.0%, the concentrations of N ₁ N ^' - oxalyldiimidazole (Aldrich) 5.0%. The solutions were additionally stabilized with 1.5% turpinal (60% solution of hydroxyethanediphosphonic acid) and 0.1% dipicolinic acid.

Colorimetric results:

The measured values show that the whitening is achieved by the addition of N, N ^{'-Oxalyldiimidazol} to the hydrogen peroxide solutions improvement, although in all cases, despite the alkaline pH a significant gas evolution was observed. The improved lightening compared to the standards can not be explained by the release of (about 4%) imidazole in the hydrolysis or perhydrolysis of the oxalic acid diimidazolide, because the lightening is better than when using imidazole as activator.

recipes:

The following colorants were provided:

1. Coloring creams:

Adjust to pH 10.0 with ammonia solution (25%). Stenol ^® 1618 to C _16. ₁₈ fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis) Lorol ^® tech. C _{_2-18} fatty alcohol (INCI name: Coconut alcohol) (Cognis) Texapon ^® K 14 S 70 C Laurylmyristylethersulfat sodium salt (ca. 68% to 73% active substance content ^'; INCI name: Sodium Myreth Sulfate) (Cognis )

Akypo Soft 45 NV ^® lauryl alcohol 4.5 EO acid sodium salt (min. 21% active substance content; INCI name: Sodium Laureth-6 Carboxylate) (Chem-Y) Lamesoft ^® PO65 alkylpolyglucoside monoglyceride mixture (about 65-70 % solids; INCI name: Coco-Glucoside, Glyceryl Oleate, Aqua (Water)) (Cognis) Dehyton ^® CN, N-dimethyl-N- (C8-18-cocamidopropyl) ammoniumaceto- betaine (30% active substance; INCI Designation: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

Eumulgin ^® B 1 cetylstearyl alcohol with about 12 EO units (INCI name: Ceteareth-12) (Cognis) Eumulgin B2 ^® cetylstearyl alcohol with about 20 EO units (INCI name: Ceteareth-20) (Cognis) Polymer ^® W 37 197 about 20% by weight of active substance content in water; INCI name: Acrylamidopropyltrimonium Chloride / Acrylates Copolymer (Stockhausen)

Luviquat ^® Care Vinylimidazolium methosulfate-vinylpyrrolidone copolymer (20:80) (6-7% solids in water, INCI name: Polyquaternium-44) (BASF)

Polymer JR ^® 400 quaternized hydroxyethyl cellulose (INCI name: Polyquaternium-10) (Amerchol)

HC Red BN 4 [(3-hydroxypropyl) amino] -3-nitrophenol

Turpinal ^® SL 1-Hydroxyethane-1, 1-diphosphonic acid (about 58 - 61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia) 2nd developer emulsion:

Adjust to pH 4.0 with ammonia solution (25%)

Texapon NSO lauryl ether sulfate, sodium salt (about 27.5% active ingredient;

Name: Sodium Laureth Sulfate) (Cognis)

Dehyquart® ^® A trimethylhexadecylammonium (about 24 -26%

Active substance; INCI name: Aqua (Water), Cetrimonium Chloride (Cognis)

Eumulgin ^® B 1 Cetylstearylalkohol with about 12 EO units (INCI name:

Ceteareth-12) (Cognis) Eumulgin B2 ^® cetylstearyl alcohol with about 20 EO units (INCI name:

Ceteareth-20) (Cognis)

Turpinal ^® SL 1-hydroxyethane-1, 1-diphosphonic acid (about 58 - 61%

Active substance content; INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

Both dyeing creams were each mixed with the developer emulsion in a ratio of 1: 1 and dyed on the natural white hair for 30 minutes at 32 ° C. (Ratio of application mixture: hair = 4: 1). In the case of Formulation 1, a bright smoke-blue shade was created, in the case of Formulation 2 a brilliant, intense color red shade.

3. Anhydrous coloring paste:

Cetiof 868 ethylhexyl stearate (INCI name: Ethyl hexyl Stearate) (Cognis) Dehydol ^® LS 4 Ci ₂ - ₁₄ fatty alcohol with about 4 EO units (INCI name: Laureth-2) (Cognis Pulcra)

Aerosil ^® 200 silica (INCI name: Silica) (Degussa) Oxone ^® salt from 2KHSO ₅ KHSO ₄ K ₂ SO ₄

This paste was also mixed with the developer emulsion in the ratio 1: 1 and the pH adjusted to 10.5 with ammonia solution. On the natural white hair resulted in a dark reddish brown tone.

Claims

claims:

1. Means for dyeing and / or lightening keratin fibers, in particular human hair, containing - based on its weight -

0.001 to 15 wt .-% of one or more N, N ^{'-Oxalyldiazole} and / or Oximidyldiazole.

2. Agent for dyeing and / or lightening keratin fibers according to claim 1, characterized in that it comprises one or more N, N ^{'-Oxalyldiazole} and / or Oximidyldiazole of formula (I)

B B

(I), wherein A is O or NR1, B is an optionally substituted, N-linked radical from the group pyrrole, pyrazole, imidazole, 1, 2,3-triazole, 1, 2,4-triazole, 1 , 2,3,4-tetrazole,

R ¹ represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted (C _r C ₆ ) alkyl group, or an optionally substituted (C ₁ -C ₆ ) -alkylene group,

3. A composition for dyeing and / or lightening keratinic fibers according to one of claims 1 or 2, characterized in that one or more N, N ^' -oxalyldiazoles and / or oximidyldiazoles of the formula (II)

(II) contains, in which

X ¹ , X ² and X ³ are each independently CR ¹ or NA is O or NR 1,

R ¹ independently represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted (C 1 -C ₆ ) alkyl group, or an optionally substituted one

R ² represents a hydrogen atom, 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, wherein the R ¹ at X ³ together with R ^{2 represents} an optionally aromatic or heteroaromatic ring can form.

4. Agent for dyeing and / or lightening keratinous fibers according to any one of claims 1 to 3, characterized in that it contains one or more N, N ^{'-Oxalyldiazole} of the formulas (IIa) and / or (IIb) and / or (Hc) and / or (Md) and / or (he)

(Hc)

wherein R ^{1 is in} each case -H ₁ -CH ₃ , -CH ₂ CH ₃ , - (CH) ₂ -CH ₃ , -CH (CH ₃ ) ₂ , - (CH ₂ ) ₃ CH ₃ , - (CHz) ₄ CH ₃ , - (CH ₂ ) ₅ CH ₃ .

5. Agent for dyeing and / or lightening keratinous fibers according to any one of claims 1 to 4, characterized in that it comprises one or more N, N ^{'-Oxalyldiazole} from the group

and or

contains.

6. Agent for dyeing and / or lightening keratinic fibers according to one of claims 1 to

5, characterized in that it is particularly preferred that the or N, N ^{'-Oxalyldiazol} (s) in amounts of 0.1 to 12.5 wt .-%, preferably from 0.25 to 10 wt .-%, of 0.5 to 7.5 wt .-% and in particular from 1 to 5 wt .-%, each based on the total agent contains.

7. A means for dyeing and / or brightening keratinous fibers according to any one of claims 1 to

6, characterized in that it contains 0.5 to 15 wt .-%, preferably 1 to 12.5 wt .-%, particularly preferably 2.5 to 10 wt .-% and in particular 3 to 6 wt .-% hydrogen peroxide ( calculated as 100% H ₂ O ₂ ).

8. Composition for dyeing and / or lightening keratinic fibers according to one of claims 1 to

7, characterized in that it additionally contains - based on its weight - 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes.

9. Agent for dyeing and / or brightening keratinic fibers according to one of claims 1 to

8, characterized in that it contains as oxidation dye precursor at least one developer component, wherein 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] -propan-2-ol, 1, 10-bis (2', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane, 4- Aminophenol, A-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.

10. A composition for dyeing and / or lightening keratinic fibers according to any one of claims 1 to

9, characterized in that it contains as oxidation dye precursor at least one coupler component, preferred coupler components are 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 -Dichlorphenol, 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-methylpyrazole-5-one, 2,6-bis - [(2 ^'- hydroxyethyl) amino] toluene, 4-hydroxyindole, 6-hydroxyindole, 6-hydroxybenzomorpholine.

11. A composition for dyeing and / or brightening keratinic fibers according to one of claims 1 to

10, characterized in that it contains at least one substantive dye selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group of known under the international names or trade names dyes HC Yellow 2, HC Yellow 4, HC Acid Yellow 1, Acid Yellow 36, 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 ₁ Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1 Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, Acid Black 52, Basic Yellow 87, Basic Orange 31 and Basic Red 51 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) -a minophenol, 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.

12. A dyeing and / or brightening keratinous fiber according to any one of claims 1 to

11, characterized in that it - based on its weight - 1 to 20 wt .-% of at least one imidazole compound according to formula (VIII) and / or their physiologically acceptable salts

contains, in which

R ¹ represents a hydrogen atom, an optionally substituted aryl group or a (d-CeJ-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 _r C ₆ ) alkyl group, an amino (Ci-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.

13. A composition for dyeing and / or lightening keratinic fibers according to claim 12, characterized in that it comprises at least one imidazole compound according to formula (VIII) and / or physiologically acceptable salts thereof in amounts of 2 to 15 wt .-%, preferably of 2, 5 to 12.5 wt .-%, particularly preferably from 3 to 10 wt .-% and in particular from 4 to 8 wt .-%.

14. A composition for dyeing and / or lightening keratinic fibers according to any one of claims 12 or 13, characterized in that the imidazole compound according to formula (VIII) and / or physiologically acceptable salts thereof is / 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.

15. Composition for dyeing and / or lightening keratinic fibers according to one of claims 1 to

14, characterized in that it additionally contains 0.01 to 2% by weight of at least one solid peroxo compound selected from ammonium and alkali metal persulfates and peroxidisulfates, preferred agents containing peroxydisulfates, which are preferably selected from sodium peroxodisulfate and / or or potassium peroxydisulfate and / or ammonium peroxydisulfate and particularly preferred agents containing at least two different peroxide islfates.

16. A composition for dyeing and / or lightening keratinic fibers according to one of claims 1 to

15, characterized in that it additionally contains 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 the 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 contains.

17. A means for dyeing and / or whitening keratinous fibers according to one of claims 1 to 16, characterized in that it additionally

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 V ₂ Ca ²⁺ , Vi Mg ²⁺ or Vi 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.

18. A dyeing and / or whitening agent for keratinous fibers according to claim 17, characterized in that it contains from 0.075 to 4% by weight, preferably from 0.1 to 2.5% by weight and in particular from 0.2 to 1% by weight. Sodium cyanate and / or potassium cyanate and / or ammonium cyanate, with sodium cyanate being particularly preferred.

19. A dyeing and / or whitening agent for keratinous fibers according to any one of claims 17 or 18, characterized in that it is 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, wherein L is selected from -S-CH ₂ -COOH, -S- (CH ₂ J ₃ SO ₃ H, -S- (CH ₂ J ₂ -NH ₂ , -OCH ₃ , -O- (C ₆ H ₄ ) -SO ₃ M, -Q ⁺ , -NH-OH, -O-C (O) -R ¹ , -O-C (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 , Oona

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.

20. A dyeing and / or brightening keratinous fiber according to any one of claims 1 to 19, characterized in that it additionally contains Cu, Fe, Mn, Co, Ce, V, Ru ions or complexes of these ions in which preferred agents comprise 0.0001 to 2.5% by weight, preferably 0.001 to 1% by weight, of at least one compound from the group copper chloride (CuCl ₂ ), copper sulfate (CuSO ₄ ), iron (II) sulfate, manganese ( ll) sulfate, manganese (II) chloride, cobalt (II) chloride, cerium sulfate, cerium chloride, vanadium sulfate, manganese dioxide (MnO ₂ ).

21. A dyeing and / or whitening agent for keratinous fibers according to any one of claims 1 to 20, characterized in that it additionally comprises one or more chelate complexing agents from the groups of

(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 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 diethylenetriamine pentamethylene phosphonate (DTPMP) or its hepta- or octasodium salt.

22. A process for whitening keratin fibers, in particular human hair, characterized in that if desired, a pretreatment agent M1 is applied to the fiber, then a means M2 is applied to the fiber, where desired the

Agent M2 is added before use, a further agent M3, this agent M2 is rinsed from the fiber after a period of 5-30 minutes and after treatment optionally a post-treatment agent M4 on the

Fiber is applied and rinsed after a contact time of a few minutes, wherein at least one of the means M1, M2 or M3 is an agent according to any one of claims 1 to 19.

23. The use of N, N ^{'-Oxalyldiazolen} and / or Oximidyldiazolen in agents for dyeing and / or lightening keratin fibers.

24. Use according to claim 23 for i. Increase in the whitening or bleaching performance and / or ii. Increase the skin compatibility of brightening or bleaching agents.