DE102009045575A1 - Agent, useful for dyeing and optionally bleaching keratin fibers, preferably human hair, comprises at least one new or known (1H-benzotriazol-5-yl)-phenyl-diazene compound - Google Patents

Abstract

Agent (A) comprises at least one (1H-benzotriazol-5-yl)-phenyl-diazene compound (I). Agent (A) comprises at least one (1H-benzotriazol-5-yl)-phenyl-diazene compound of formula (I). R1 : H, 1-6C alkyl (optionally carrying a substituent containing at least one nitrogen atom and optionally a positive charge), 2-6C alkenyl, 2-6C monohydroxyalkyl, 2-6C polyhydroxyalkyl, 1-6C alkoxy-2-6C alkyl or di(1-6C alkyl)amino-2-6C alkyl; either R2, R3 : H, 1-6C alkyl (optionally carrying a substituent containing at least one nitrogen atom and optionally a positive charge), 2-6C alkenyl, 2-6C monohydroxyalkyl, 2-6C polyhydroxyalkyl, 1-6C alkoxy, halo, carboxyl, nitrile, carbamoyl, sulfonamido, carboxamido, 1-6C alkyloxycarbonyl, sulfonic acid, OH, amino, mono-(1-6C alkyl)amino or di(1-6C alkyl)amino; or R2R3 : six-membered aromatic, carbocyclic or fused heterocyclic ring (optionally carrying further substituents); K1 : OR5 or -NR6R7; and R5-R7 : H, 1-6C alkyl (optionally carrying a substituent containing at least one nitrogen atom and optionally a positive charge), 2-6C alkenyl, 2-6C hydroxyalkyl, 1-6C alkoxy-2-6C alkyl or di-(1-6C alkyl) amino-2-6C alkyl. Independent claims are included for: (1) (1H-benzotriazol-5-yl)-phenyl-diazene compound (I) (where K1 is -NR6R7, and with the proviso that least one of R1, R2, R3, R5, R6 and/or R7 comprises a cationic charge); and (2) a method of dyeing and optionally bleaching keratin fibers, preferably human hair, comprising optionally applying a pretreatment agent M1 to the fiber; applying an agent M2 on the fiber, optionally adding an agent M3 to the agent M2 before the application; rinsing the agent M2 from the fiber after a period of 5-30 minutes; and after the treatment, optionally applying a post-treatment agent M4 to the fiber and rinsing from them after a contact time of a few minutes, where at least one of the agents M1, M2 or M3 is the agent (A). [Image].

Description

The The invention relates to dyeing agents and optionally simultaneous lightening of keratinous fibers, in particular human hair containing specific benzotriazole azo dyes, some of these dyes themselves, the use of these substantive Dyes for dyeing hair and a method for Dyeing of keratinous fibers, especially human Hair.

For the dyeing of keratinous fibers generally occurs either direct dyes or oxidation dyes, the by oxidative coupling of one or more developer components with one another or with one or more coupler components, for use. Coupler and developer components are also known as oxidation dye precursors designated.

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

Specific Representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxamido-4-amino-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 4,5-diamino-1- (2-hydroxyethyl) pyrazole.

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

Although intensive dyeings with good fastness properties can be obtained with oxidation dyes, the development of the color is generally carried out under the influence of oxidizing agents such. H ₂ O ₂ , which in some cases may result in damage to the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes sensitize people with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage lies in the fact that the dyes often have only insufficient fastness properties.

The object of the present invention is to provide novel substantive dyes which are outstandingly suitable for use in hair dyeing and are distinguished by good fastness properties, such as, for example, light fastness, rubfastness and washfastness as well as perspiration and cold wave fastness. In the case of simultaneous use with oxidation dyes and / or oxidants direct drawers should have sufficient stability against H ₂ O ₂ and not lose their positive fastness and dyeing properties. In addition, the colorants must have no or only a very low sensitizing potential and may under no circumstances be mutagenic. In addition, as bright and intense colors as possible should be achieved.

It was surprisingly found that compounds of general formula (I) works very well as a direct trainer for the hair coloring are suitable. The obtained in colorations Nuances are extremely intense and lie in the orange and red area. The directors also deliver at the same time Application of oxidizing agents such as hydrogen peroxide or a Mixture of hydrogen peroxide and peroxydisulfates luminous nuances without attenuation of color intensity and color brilliance. In this way, the simultaneous lightening and coloring of hair possible, whereby even on dark hair one bright coloring can be achieved.

wobei

• – der Rest R1 steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, die gegebenenfalls einen Substituenten tragen kann, der mindestens ein Stickstoffatom und gegebenenfalls eine positive Ladung aufweist, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Monohydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe oder eine Di-(C₁-C₆-alkyl)amino-C₂-C₆-alkylgruppe,
• – die Reste R2 und R3 stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, die gegebenenfalls einen Substituenten tragen kann, der mindestens ein Stickstoffatom und gegebenenfalls eine positive Ladung aufweist, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Monohydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, ein Halogenatom, eine Carboxylgruppe, eine Nitrilgruppe, eine Carbamoylgruppe, eine Sulfonamidogruppe, eine Carboxamidogruppe, eine C₁-C₆-Alkyloxycarbonylguppe, eine Sulfonsäuregruppe, eine Hydroxygruppe, eine Aminogruppe, eine Mono-(C₁-C₆-alkyl)aminogruppe, eine Di-(C₁-C₆-alkyl)aminogruppe oder die beiden Reste R2 und R3 bilden gemeinsam einen 6-gliedrigen aromatischen, carbozyklischen oder heterozyklischen anellierten Ring, welcher gegebenenfalls weitere Substituenten tragen kann und
• – der Rest K steht für eine Gruppierung -OR5 oder eine Gruppierung -NR6R7, wobei die Reste R5 beziehungsweise R6 und R7 stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, die gegebenenfalls einen Substituenten tragen kann, der mindestens ein Stickstoffatom und gegebenenfalls eine positive Ladung aufweist, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Hydroyxalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe oder eine Di-(C₁-C₆-alkyl)amino-C₂-C₆-alkylgruppe.

The present invention relates, in a first embodiment, to agents for dyeing and, if appropriate, simultaneous lightening of keratin fibers, in particular human hair, comprising at least one compound of the formula (I):

in which

• - the radical R1 is a hydrogen atom, a C ₁ -C ₆ alkyl group which may optionally bear a substituent which has at least one nitrogen atom and optionally a positive charge, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy C ₂ -C ₆ alkyl group or a di (C ₁ -C ₆ alkyl) amino C ₂ -C ₆ - alkyl group,
• - The radicals R2 and R3 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group which may optionally bear a substituent which has at least one nitrogen atom and optionally a positive charge, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ monohydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C ₁ -C ₆ alkoxy, halogen, carboxyl, nitrile, carbamoyl, sulfonamido, carboxamido, C ₁ -C ₆ Alkyloxycarbonyl group, a sulfonic acid group, a hydroxy group, an amino group, a mono (C ₁ -C ₆ alkyl) amino group, a di (C ₁ -C ₆ alkyl) amino group or the two radicals R 2 and R 3 together form a 6 -membered aromatic, carbocyclic or heterocyclic fused ring, which may optionally bear further substituents, and
• The radical K is a grouping -OR5 or a grouping -NR6R7, where the radicals R5 or R6 and R7 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group which may optionally carry a substituent which is at least one A nitrogen atom and optionally a positive charge, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl, a C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkyl group or a di- (C ₁ - C ₆ alkyl) amino C ₂ -C ₆ alkyl group.

Under Keratin fibers are wool, furs, feathers and in particular to understand human hair. The invention Dyes can in principle but also for dyeing other natural fibers, such. As cotton, jute, sisal, linen or Silk, modified natural fibers, such as regenerated cellulose, Nitro, alkyl or hydroxyalkyl or acetyl cellulose used become.

Of the term used according to the invention "dyeing of keratin fibers "includes any form of color change the fibers. Includes in particular the terms tinting, Bleaching, oxidative staining, semipermanent staining, permanent staining and temporary staining included color changes. Explicitly included According to the invention, color changes, the have a lighter color result compared to the original color, such as bleaching.

Examples of (C ₁ to C ₆ ) -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals.

Examples of preferred (C ₂ to C ₆ ) alkenyl radicals are vinyl and allyl.

Further, as preferable examples of a (C ₁ to C ₆ ) monohydroxyalkyl group, there may be mentioned hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6 Be called hydroxyethyl group. A 2-hydroxyethyl group is particularly preferred.

Examples of a (C ₂ to C ₆ ) polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group.

Preferred (C ₁ to C ₆ ) alkoxy groups according to the invention are, for example, a methoxy or an ethoxy group.

The methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxybutyl and methoxyhexyl groups are examples of (C ₁ to C ₆ ) alkoxy (C ₂ to C ₆ ) alkyl groups according to the invention.

A preferred hydroxy (C ₁ -C ₆ ) alkoxy group is the 2-hydroxyethoxy group. Examples of halogen atoms are F, Cl, Br or I atoms, with Br or Cl atoms being very particularly preferred.

Preferred C ₁ -C ₆ -monoalkylamino groups are the methylamino group, the ethylamino group and the propylamino group. Preferred C ₁ -C ₆ dialkylamino groups are the dimethylamino group, the methylethylamino group and the diethylamine group.

The 2-aminoethyl and the 3-aminopropyl group are inventively preferred amino-C ₂ -C ₆ -alkyl groups.

The 2-dimethylaminoethyl group and the 3-dimethylaminopropyl group are particularly preferred C ₁ -C ₆ -dialkylamino-C ₂ -C ₆ -alkyl groups according to the invention.

The 2-methylaminoethyl group is a C ₁ -C ₆ -monoalkylamino-C ₂ -C ₆ -alkyl group preferred according to the invention.

preferred Alkoxycarbonyl groups are the methoxycarbonyl group, the ethoxycarbonyl group and the propoxycarbonyl group.

The remaining These groupings are derived from the definitions given here from.

For the case that one or more of the substituents R1, R2, R3, R5, R6 and / or R7 bears a cationic charge lie this compound of formula (I) in the form of one of its physiological acceptable salts. Suitable counterions are, for example selected from halide (chloride, bromide, iodide or fluoride), Hydrogen sulfate, ½ sulfate, ½ tetrachlorozincate, p-benzenesulfonate, p-toluenesulfonate, acetate, tetrafluoroborate, trifluoromethanesulfonate, Hexafluorophosphate, methanesulfate or methanesulfonate.

wobei n steht für eine ganze Zahl von 2 bis 6 und X^– steht für ein physiologisch verträgliches Anion wie oben definiert.Preferred (C ₁ to C ₆ ) -alkyl radicals bearing a substituent having at least one nitrogen atom and one positive charge are the groups:

where n is an integer from 2 to 6 and X ^- is a physiologically acceptable anion as defined above.

It may, in the context of a specific embodiment of the present Be preferred if exactly one of the radicals R1, R2, R3, R5, R6 and / or R7 stands for a cationic group.

It is preferred according to the invention if the radical R _{1 is} a hydrogen atom, a C ₁ -C ₆ -alkyl group which may optionally carry a substituent which has at least one nitrogen atom and optionally a positive charge, or a C ₂ -C ₆ -alkenyl group , It is particularly preferred according to the invention if R _{1 is} a hydrogen atom or a C ₁ -C ₆ -alkyl group. It is very particularly preferred if R 1 is a hydrogen atom or a methyl group. A particularly preferred radical R1 is a hydrogen atom.

Furthermore, it is preferred according to the invention if the radicals R 2 and R 3 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -alkoxy group, a halogen atom, a hydroxy group, an amino group or a di (C ₁ -C ₆ -alkyl) amino group or together form a 6-membered aromatic, carbocyclic or heterocyclic fused ring, which may also carry further substituents. It is particularly preferred if the radicals R 2 and R 3 independently of one another represent a hydrogen atom, a hydroxy group or a methoxy group or together form a fused benzene ring or pyridine ring. In this case, it is preferred if the fused ring system optionally still carries a hydroxy group. In addition, it is preferred if the fused ring system formed from the radicals R 2 and R 3 occupies the ortho and the meta position to the azo grouping.

in the Frame of a first particularly preferred embodiment compounds of the formula (I) are preferred in the present invention, where the group -K is a radical -OR5. As part of This embodiment is particularly advantageous proved when R5 is a hydrogen atom, a methyl group or an ethyl group. Compounds of the formula (I) in which R5 represents a hydrogen atom or a methyl group very particularly preferred. Explicit preference is given to the compounds of the formula (I) wherein R5 is a hydrogen atom.

in the For the purposes of this first embodiment, the general ones apply Remarks on the residues R1, R2 and R3, made above were.

The Group K is preferably in this embodiment ortho position or in para position to the azo grouping.

• – 4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-phenol
  
• – 2-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-phenol
  
• – 4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-1-naphthol
  
• – 1-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-2-naphthol
  
• – 4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-naphthalen-1,3-diol
  
• – 4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-naphthalen-1,5-diol
  
• – 1-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-naphthalen-2,7-diol
  
• – 5-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-chinolin-8-ol
  
• – 4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-2,6-dimethoxyphenol
  
• – 4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-3,5-dimethoxyphenol
  
• – 5-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-benzen-1,2,3-triol
  
• – 2-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-benzen-1,3,5-triol
  
• – 4-[(1-Methyl-1H-1,2,3-benzotriazol-5-yl)diazenyl]phenol
  
• – 2-[(1-Methyl-1H-1,2,3-benzotriazol-5-yl)diazenyl]phenol
  
• – 4-[(1-Methyl-1H-1,2,3-benzotriazol-5-yl)diazenyl]-1-naphthol
  
• – 1-[(1-Methyl-1H-1,2,3-benzotriazol-5-yl)diazenyl]-2-naphthol
  
• – 4-[(1-Methyl-1H-1,2,3-benzotriazol-5-yl)diazenyl]naphthalene-1,3-diol
  
• – 2,6-Dimethoxy-4-[(1-methyl-1H-1,2,3-benzotriazol-5-yl)diazenyl]phenol
  
• – 3,5-Dimethoxy-4-[(1-methyl-1H-1,2,3-benzotriazol-5-yl)diazenyl]phenol
  
• – 5-[(1-Methyl-1H-1,2,3-benzotriazol-5-yl)diazenyl]benzen-1,2,3-triol
  
• – 2-[(1-Methyl-1H-1,2,3-benzotriazol-5-yl)diazenyl]benzene-1,3,5-triol
  

In the context of this embodiment, the following compounds have proved to be particularly advantageous:

• - 4- (1H-1,2,3-benzotriazol-5-yldiazenyl) -phenol
  
• - 2- (1H-1,2,3-benzotriazol-5-yldiazenyl) -phenol
  
• - 4- (1H-1,2,3-benzotriazol-5-yldiazenyl) -1-naphthol
  
• - 1- (1H-1,2,3-benzotriazol-5-yldiazenyl) -2-naphthol
  
• - 4- (1H-1,2,3-benzotriazol-5-yldiazenyl) -naphthalene-1,3-diol
  
• - 4- (1H-1,2,3-benzotriazol-5-yldiazenyl) -naphthalene-1,5-diol
  
• - 1- (1H-1,2,3-benzotriazol-5-yldiazenyl) -naphthalene-2,7-diol
  
• - 5- (1H-1,2,3-benzotriazol-5-yldiazenyl) quinolin-8-ol
  
• - 4- (1H-1,2,3-benzotriazol-5-yldiazenyl) -2,6-dimethoxyphenol
  
• - 4- (1H-1,2,3-benzotriazol-5-yldiazenyl) -3,5-dimethoxyphenol
  
• - 5- (1H-1,2,3-benzotriazol-5-yldiazenyl) -benzene-1,2,3-triol
  
• 2- (1H-1,2,3-benzotriazol-5-yldiazenyl) -benzene-1,3,5-triol
  
• - 4 - [(1-Methyl-1H-1,2,3-benzotriazol-5-yl) diazenyl] phenol
  
• - 2 - [(1-Methyl-1H-1,2,3-benzotriazol-5-yl) diazenyl] phenol
  
• - 4 - [(1-Methyl-1H-1,2,3-benzotriazol-5-yl) diazenyl] -1-naphthol
  
• - 1 - [(1-Methyl-1H-1,2,3-benzotriazol-5-yl) diazenyl] -2-naphthol
  
• - 4 - [(1-Methyl-1H-1,2,3-benzotriazol-5-yl) diazenyl] naphthalene-1,3-diol
  
• - 2,6-dimethoxy-4 - [(1-methyl-1H-1,2,3-benzotriazol-5-yl) diazenyl] phenol
  
• 3,5-dimethoxy-4 - [(1-methyl-1H-1,2,3-benzotriazol-5-yl) diazenyl] phenol
  
• - 5 - [(1-Methyl-1H-1,2,3-benzotriazol-5-yl) diazenyl] benzene-1,2,3-triol
  
• - 2 - [(1-methyl-1H-1,2,3-benzotriazol-5-yl) diazenyl] benzene-1,3,5-triol
  

• – 4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-1-naphthol,
• – 1-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-2-naphthol,
• – 4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-naphthalen-1,5-diol,
• – 1-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-naphthalen-2,7-diol,
• – 5-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-chinolin-8-ol,
• – 5-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-benzen-1,2,3-triol und
• – 2-(1H-1,2,3-Benzotriazol-5-yldiazenyl)-benzen-1,3,5-triol.

Particularly preferred representatives of this embodiment are the following compounds:

• 4- (1H-1,2,3-benzotriazol-5-yldiazenyl) -1-naphthol,
• 1- (1H-1,2,3-benzotriazol-5-yldiazenyl) -2-naphthol,
• 4- (1H-1,2,3-benzotriazol-5-yldiazenyl) -naphthalene-1,5-diol,
• 1- (1H-1,2,3-benzotriazol-5-yldiazenyl) -naphthalene-2,7-diol,
• 5- (1H-1,2,3-benzotriazol-5-yldiazenyl) quinolin-8-ol,
• - 5- (1H-1,2,3-benzotriazol-5-yldiazenyl) -benzene-1,2,3-triol and
• 2- (1H-1,2,3-benzotriazol-5-yldiazenyl) -benzene-1,3,5-triol.

in the Frame of a second particularly preferred embodiment In the present invention, the group K is a Group -NR6R7.

in the In the context of this embodiment, the above apply Statements concerning the preferred substituents R1, R2 and R3. Nevertheless, it is very special according to the invention preferred when the radicals R1, R2 and R3 are each a Hydrogen atom stand.

Furthermore it has proven to be extremely beneficial when compounds of the formula (I) are used in which the Group K is in para-position to the azo grouping.

In the context of this embodiment, it is also advantageous if the radicals R6 and R7 for a What hydrogen atom, a C ₁ -C ₆ alkyl group which may optionally bear a substituent which has at least one nitrogen atom and optionally a positive charge, a C ₂ -C ₆ alkenyl group or a C ₂ -C ₆ monohydroxyalkyl group.

Particularly preferred are the following substitution patterns for the radicals R6 and R7:

• – 4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)anilin
  
• – N-[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl]-N,N-dimethylamin
  
• – N,N-Diallyl-N-[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl]amin
  
• – 2-{[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](2-hydroxyethyl)amino}ethanol
  
• – Salze des 1-(2-{[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](methyl)amino}ethyl)-3-methyl-1H-imidazoliums
  
• – Salze des 1-(2-{[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](ethyl)amino}ethyl)-3-methyl-1H-imidazoliums
  
• – Salze des 1-(2-{[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl]-(methyl)amino}ethyl)pyridiniums
  
• – Salze des 1-(2-{[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl]-(ethyl)amino}ethyl)pyridiniums
  
• – Salze des 1-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](methyl)-amino}ethyl)-1-methylpyrrolidiniums
  
• – Salze des 1-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl]-(ethyl)-amino}ethyl)-1-methylpyrrolidiniums
  
• – Salze des 1-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](methyl)-amino}ethyl)-1-methylpiperidiniums
  
• – Salze des 1-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](ethyl)-amino}-ethyl)-1-methylpiperidiniums
  
• – Salze des 4-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](methyl)-amino}ethyl)-4-methylmorpholiniums
  
• – Salze des 4-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](ethyl)amino}ethyl)-4-methylmorpholiniums
  
• – Salze des 1,1-Dimelhyl-4-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](methyl)amino}ethyl)piperaziniums
  
• – Salze des 1,1-Dimethyl-4-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](ethyl)amino} ethyl)piperaziniums
  
• – Salze des 2-{[4-(1H-1,2,3-Benzotriazol-5-yl-diazenyl)phenyl](methyl)amino}-N,N,N-trimethylethanaminiums
  
• – Salze des 2-{[4-(1H-1,2,3-Benzotriazol-5-yl-diazenyl)phenyl](ethyl)amino}-N,N,N-trimethylethanaminiums
  

The following representatives have proven to be particularly suitable in the context of this particular embodiment:

• - 4- (1H-1,2,3-benzotriazol-5-yldiazenyl) aniline
  
• N- [4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] -N, N-dimethylamine
  
• - N, N-diallyl-N- [4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] amine
  
• - 2 - {[4- (1H-1,2,3-Benzotriazol-5-yldiazenyl) phenyl] (2-hydroxyethyl) amino} ethanol
  
• Salts of 1- (2 - {[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (methyl) amino} ethyl) -3-methyl-1H-imidazolium
  
• Salts of 1- (2 - {[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (ethyl) amino} ethyl) -3-methyl-1H-imidazolium
  
• Salts of 1- (2 - {[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (methyl) amino} ethyl) pyridinium
  
• Salts of 1- (2 - {[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (ethyl) amino} ethyl) pyridinium
  
• Salts of 1- ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (methyl) amino} ethyl) -1-methylpyrrolidinium
  
• Salts of 1- ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (ethyl) amino} ethyl) -1-methylpyrrolidinium
  
• Salts of 1- ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (methyl) amino} ethyl) -1-methylpiperidinium
  
• Salts of 1- ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (ethyl) amino} ethyl) -1-methylpiperidinium
  
• - Salts of 4 - ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (methyl) amino} ethyl) -4-methylmorpholinium
  
• - Salts of 4 - ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (ethyl) amino} ethyl) -4-methylmorpholinium
  
• Salts of 1,1-dimethyl-4 - ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (methyl) amino} ethyl) piperazini killed
  
• Salts of 1,1-dimethyl-4 - ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (ethyl) amino} ethyl) piperaziniums
  
• Salts of 2 - {[4- (1H-1,2,3-benzotriazol-5-yl-diazenyl) phenyl] (methyl) amino} -N, N, N-trimethylethane-amine
  
• Salts of 2 - {[4- (1H-1,2,3-benzotriazol-5-yl-diazenyl) phenyl] (ethyl) amino} -N, N, N-trimethylethanamine
  

• – N-[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl]-N,N-dimethylamin,
• – 2-{[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](2-hydroxyethyl)amino}ethanol,
• – Salze des 1-(2-{[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](methyl)amino}ethyl)-3-methyl-1H-imidazoliums,
• – Salze des 1-(2-{[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](ethyl)amino}ethyl)-3-methyl-1H-imidazoliums,
• – Salze des 1-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](methyl)-amino}ethyl)-1-methylpyrrolidiniums,
• – Salze des 1-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl]-(ethyl)-amino}ethyl)-1-methylpyrrolidiniums,
• – Salze des 1,1-Dimethyl-4-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](methyl)amino}ethyl)piperaziniums,
• – Salze des 1,1-Dimethyl-4-({[4-(1H-1,2,3-Benzotriazol-5-yldiazenyl)phenyl](ethyl)amino}ethyl)piperaziniums,
• – Salze des 2-{[4-(1H-1,2,3-Benzotriazol-5-yl-diazenyl)phenyl](methyl)amino}-N,N,N-trimethylethanaminiums sowie
• – Salze des 2-{[4-(1H-1,2,3-Benzotriazol-5-yl-diazenyl)phenyl](ethyl)amino}-N,N,N-trimethylethanaminiums.

Within the scope of this group, the following compounds of the formula (I) have proven to be very particularly preferred:

• N- [4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] -N, N-dimethylamine,
• - 2 - {[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (2-hydroxyethyl) amino} ethanol,
• Salts of 1- (2 - {[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (methyl) amino} ethyl) -3-methyl-1H-imidazolium,
• Salts of 1- (2 - {[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (ethyl) amino} ethyl) -3-methyl-1H-imidazolium,
• Salts of 1- ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (methyl) amino} ethyl) -1-methylpyrrolidinium,
• Salts of 1- ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (ethyl) amino} ethyl) -1-methylpyrrolidinium,
• Salts of 1,1-dimethyl-4 - ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (methyl) amino} ethyl) piperaziniums,
• Salts of 1,1-dimethyl-4 - ({[4- (1H-1,2,3-benzotriazol-5-yldiazenyl) phenyl] (ethyl) amino} ethyl) piperaziniums,
• Salts of 2 - {[4- (1H-1,2,3-benzotriazol-5-yl-diazenyl) -phenyl] (methyl) -amino} -N, N, N-trimethylethanamine and
• Salts of 2 - {[4- (1H-1,2,3-benzotriazol-5-yl-diazenyl) phenyl] (ethyl) amino} -N, N, N-trimethylethanamine.

The inventive dyeing agent and optionally simultaneously lightening keratin fibers the compound (s) of the formula (I) preferably in amounts above of 1 ppm and below 10 wt .-%, each based on the total Medium. Preferred agents according to the invention for Dyeing and possibly simultaneous lightening of keratinischer Fibers are characterized by having the compound (s) of the formula (I) in amounts of 0.001 to 5 wt .-%, preferably from 0.0025 to 2.5 wt .-%, particularly preferably from 0.005 to 1.5 wt .-% and in particular from 0.01 to 1 wt .-%, each based on the entire medium, included.

The agents of the invention serve to change the color keratinic fibers, especially human hair. The color change can be done solely on the basis of the compound (s) of formula (I) which but agents of the invention can also additional color-changing substances contain, for example, direct dyes and / or oxidation colorants. Inventive means for dyeing and optionally simultaneous lightening of keratinic fibers, the additionally - based on their weight - 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes, are preferred.

For permanent, intensive colorations with corresponding fastness properties so-called oxidation dyes are used. Such Colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or atmospheric oxygen with each other or under coupling with one or more coupler components the actual dyes. The oxidation colorants Although distinguished by excellent, long-lasting staining results out. For natural-looking dyeings but usually it has to be a mixture of a larger one Number of oxidation dye precursors are used; in many Cases continue to be substantive dyes for shading used.

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

wobei

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

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which

• G ¹ represents a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) - Alkoxy (C ₁ to C ₄ ) alkyl, 4'-aminophenyl or (C ₁ to C ₄ ) alkyl substituted with a nitrogen-containing group, a phenyl or a 4'-aminophenyl;
• G ² represents a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) - Alkoxy (C ₁ to C ₄ ) alkyl or (C ₁ to C ₄ ) alkyl substituted with a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a (C ₁ to C ₄ ) -alkyl, a (C ₁ to C ₄ ) -monohydroxyalkyl, a (C ₂ to C ₄ ) -polyhydroxyalkyl, a (C ₁ to C ₄ ) -hydroxyalkoxy, a (C ₁ to C ₄ ) -alkoxy - (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -acetylaminoalkoxy radical, a mesylamino (C ₁ to C ₄ ) -alkoxy radical or a (C ₁ to C ₄ ) -carbamoylaminoalkoxy radical;
• G ⁴ represents a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl radical or a (C ₁ to C ₄ ) -alkoxy (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.

Especially Preferred p-phenylenediamines of formula (E1) are selected one or more compounds of the group that is formed 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-methoxymethyl-p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine, 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

Completely according to the invention Particularly preferred p-phenylenediamine derivatives of the formula (E1) are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine, 2-methoxymethyl-p-phenylenediamine and the physiologically acceptable salts of these compounds.

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

wobei:

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

mit der Maßgabe, dass die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten.Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

• - Z ¹ and Z ² independently of one another are a hydroxyl or NH ₂ radical which is optionally substituted by a (C ₁ to C ₄ ) -alkyl radical, by a (C ₁ to C ₄ ) -hydroxyalkyl radical and / or by a bridge Y is substituted 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 interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be substituted by one or more hydroxyl or (C ₁ to C ₈ ) alkoxy, or a direct bond,
• G ⁵ and G ⁶ independently of one another 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 ) -polyhydroxyalkyl radical, - (C ₁ to C ₄ ) -aminoalkyl radical or a direct compound for bridging Y,
• G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a (C ₁ to C ₄ ) -alkyl radical,

with the proviso that the compounds of the formula (E2) contain only one bridge Y per molecule.

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

preferred binuclear developer components of the formula (E2) are especially selected from at least one of the following: N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) tetramethylenediamine, N, N'-bis (4- (methylamino) phenyl) tetramethylenediamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, Bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane as well as their physiologically acceptable salts.

All particularly preferred binuclear developer components of the formula (E2) are selected from 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, 1,10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane or one of the physiologically acceptable salts of these compounds.

wobei:

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

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

in which:

• G ¹³ represents a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl, (C ₁ to C ₄ ) aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, (C ₁ to C ₄ ) hydroxyalkoxy, a (C ₁ to C ₄ ) hydroxyalkyl (C ₁ to C ₄ ) aminoalkyl radical or a (di - [(C ₁ to C ₄ ) alkyl] amino) - (C ₁ to C ₄ ) alkyl radical, and
• G ¹⁴ is a hydrogen or halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ 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 (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

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

preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methyl-phenol, 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 its physiological compatible salts.

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

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

Furthermore, the developer component may be selected from heterocyclic developer component nenten, such as pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives or their physiologically acceptable salts.

worin

• – G¹⁷, G¹⁸ und G¹⁹ unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁ bis C₄)-Alkoxygruppe oder eine Aminogruppe steht und
• – G²⁰ für eine Hydroxygruppe oder eine Gruppe -NG²¹G²² steht, worin G²¹ und G²² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe,

mit der Maßgabe, dass maximal zwei der Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ Hydroxygruppe bedeuten und höchstens zwei der Reste G¹⁷, G¹⁸ und G¹⁹ für ein Wasserstoffatom stehen. Dabei ist es wiederum bevorzugt, wenn gemäß Formel (E4) mindestens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Gruppe -NG²¹G²² stehen und höchstens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Hydroxygruppe stehen.Preferred pyrimidine derivatives are selected according to the invention from compounds of the formula (E4) or their physiologically tolerated salts,

wherein

• G ¹⁷ , G ¹⁸ and G ¹⁹ independently of one another represent a hydrogen atom, a hydroxy group, a (C ₁ to C ₄ ) alkoxy group or an amino group and
• G ^{20 is} a hydroxy group or a group -NG ²¹ G ²² in which G ²¹ and G ²² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group .

with the proviso that a maximum of two of the groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 are} hydroxy and at most two of the radicals G ¹⁷ , G ¹⁸ and G ^{19 are} a hydrogen atom. In this case, it is again preferred if, according to formula (E4), at least two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a group -NG ²¹ G ²² and at most two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a hydroxy group.

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

worin

• – G²³, G²⁴, G²⁵ stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte Aryl-(C₁ bis C₄)-alkylgruppe, mit der Maßgabe dass, wenn G²⁵ für ein Wasserstoffatom steht, G²⁶ neben den vorgenannten Gruppen zusätzlich für eine Gruppe -NH₂ stehen kann,
• – G²⁶ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe oder eine (C₂ bis C₄)-Polyhydroxyalkylgruppe und
• – G²⁷ steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe, eine (C₁ bis C₄)-Alkylgruppe oder eine (C₁ bis C₄)-Monohydroxyalkylgruppe, insbesondere für ein Wasserstoffatom oder eine Methylgruppe.

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

wherein

• G ²³ , G ²⁴ , G ²⁵ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -monohydroxyalkyl group, a (C ₂ to C ₄ ) -polyhydroxyalkyl group, a optionally substituted aryl group or an optionally substituted aryl- (C ₁ to C ₄ ) -alkyl group, with the proviso that when G ^{25 is} a hydrogen atom, G ^{26 may} additionally be a group -NH _{2 in} addition to the abovementioned groups,
• G ²⁶ represents a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group or a (C ₂ to C ₄ ) polyhydroxyalkyl group and
• G ²⁷ represents a hydrogen atom, an optionally substituted aryl group, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -monohydroxyalkyl group, in particular a hydrogen atom or a methyl group.

Preferably in formula (E5) the radical -NG ²⁵ G ²⁶ binds to the 5 position and the radical G ²⁷ to the 3 position of the pyrazole cycle.

Particularly preferred pyrazole derivatives are in particular the compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5- Diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3 phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4 5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4.5 Diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4.5- Diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropyl pylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, and their physiologically acceptable salts.

wobei:

• – G²⁸, G²⁹ und G³⁰, G³¹ unabhängig voneinander stehen für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen Aryl-Rest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁ bis C₄)-Alkylamino-(C₁ bis C₄)-alkylrest, einen Di-[(C₁ bis C₄)-alkyl]-(C₁ bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C₁ bis C₄)-Monohydroxyalkyl- oder einen Di[(C₁ bis C₄)-Hydroxyalkyl]-(C₁ bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen Aryl-Rest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)- Polyhydroxyalkylrest, einen (C₁ bis C₄)-Aminoalkylrest, einen (C₁ bis C₄)-Alkylamino-(C₁ bis C₄)-alkylrest, einen Di-[(C₁ bis C₄)alkyl]-(C₁ bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C₁ bis C₄)-Hydroxyalkyl- oder einen Di-[(C₁ bis C₄)-hydroxyalkyl]amino-(C₁ bis C₄)-alkylrest, einen Aminorest, einen (C₁ bis C₄)-Alkyl- oder Di-[(C₁ bis C₄)-hydroxyalkyl]aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1,

mit der Maßgabe, dass

• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG²⁸G²⁹ und NG³⁰G³¹ belegen die Positionen (2, 3); (5, 6); (6, 7); (3, 5) oder (3, 7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG²⁸G²⁹ (oder NG³⁰G³¹) und die Gruppe OH belegen die Positionen (2, 3); (5, 6); (6, 7); (3, 5) oder (3, 7);

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

in which:

• G ²⁸ , G ²⁹ and G ³⁰ , G ³¹ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, an aryl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical is a (C ₁ to C ₄ ) -alkoxy- (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -aminoalkyl radical which is optionally substituted by an acetyl-ureide or a sulfonyl radical Rest may be protected, a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) aminoalkyl where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a (C ₁ to C ₄ ) monohydroxyalkyl or a di [(C ₁ to C ₄ ) hydroxyalkyl] - (C ₁ to C ₄ ) aminoalkyl radical,
• The X radicals independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, an aryl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -hydroxyalkyl radical, a (C ₁ to C ₄ ) aminoalkyl radical, a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl radical, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) -aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a (C ₁ to C ₄ ) -hydroxyalkyl or a di - [(C ₁ to C ₄ ) -hydroxyalkyl] amino (C ₁ to C ₄ ) alkyl, an amino, 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 ²⁸ G ²⁹ and NG ³⁰ G ³¹ occupy the positions (2, 3); (5, 6); (6, 7); (3, 5) or (3, 7);
• If p + q is 1, n is 1, and the groups NG ²⁸ G ²⁹ (or NG ³⁰ G ³¹ ) and the group OH occupy the positions (2, 3); (5, 6); (6, 7); (3, 5) or (3, 7);

The used in formula (E7) substituents are analogous to the invention defined to the above statements.

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

• – Pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – Pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-7-ol;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-5-ol;
• – 2-(3-Aminopyrazolo[1,5-a]pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazolo[1,5-a]pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazolo[1,5-a]pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.In particular, among the pyrazolo [1,5-a] pyrimidines of the above formula (E7):

• - pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
• 3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
• 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-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 (E6) as described in the literature by cyclization starting from an aminopyrazole or hydrazine.

All particularly preferred developer components are selected from at least one compound from the group that is formed p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-Dihydroxyethyl) -p-phenylenediamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H- imidazol-1-yl) propyl] amine, 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, 1,10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, and the physiologically acceptable salts of these compounds.

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (E1) to (E6): Examples of (C ₁ to C ₄ ) -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ .

Examples of (C ₁ to C ₄ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group.

Furthermore, as preferred examples of a (C ₁ to C ₄ ) monohydroxyalkyl group, -CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CHCH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, with the group -CH ₂ CH ₂ OH being preferred.

A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group.

Examples for halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.

Examples of nitrogen-containing groups are in particular -NH ₂ , (C ₁ to C ₄ ) -monoalkylamino groups, (C ₁ to C ₄ ) -dialkylamino groups, (C ₁ to C ₄ ) -trialkylammonium groups, (C ₁ to C ₄ ) -monohydroxyalkylamino groups, Imidazolinium and -NH ₃ ⁺ .

Examples of (C ₁ to C ₄ ) monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ , -NHCH ₂ CH ₂ CH ₃ , -NHCH (CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) trialkylammonium groups are -N ⁺ (CH ₃ ) ₃ , -N ⁺ (CH ₃ ) ₂ (CH ₂ CH ₃ ), -N ⁺ (CH ₃ ) (CH ₂ CH ₃ ) ₂ ,

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino radicals are -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ), -CH ₂ CH ₂ CH ₂ -O-CH (CH ₃ ).

Examples of hydroxy (C ₁ to C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH, -O-CHCH (OH) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) -acetylaminoalkoxy radicals are -O-CH ₂ NHC (O) CH ₃ , -O-CH ₂ CH ₂ NHC (O) CH ₃ , -O-CH ₂ CH ₂ CH ₂ NHC (O ) CH ₃ , -O-CH ₂ CH (NHC (O) CH ₃ ) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ NHC (O) CH ₃ .

Examples of (C ₁ to C ₄ ) -carbamoylaminoalkoxy radicals are -O-CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ .

Examples of (C ₁ to C ₄ ) -aminoalkyl radicals are -CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH (NH ₂ ) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ .

Examples of (C ₁ to C ₄ ) -cyanoalkyl radicals are -CH ₂ CN, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ CH ₂ CN.

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH.

Examples of di [(C ₁ to C ₄ ) -hydroxyalkyl] amino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N ( CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ .

One Example of aryl groups is the phenyl group.

Examples of aryl (C ₁ to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

Kupplerkomponenten do not form a significant part of the oxidative staining alone Coloring, but always need the present of developer components. Therefore, it is preferred according to the invention that when using at least one developer component in addition at least one coupler component is used.

Kupplerkomponenten For the purposes of the invention, at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component out. Couplers are preferred cyclic compounds that participate in the cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups. These Groups are conjugated through a double bond system. If the cyclic compound is a six-membered ring, so are the said groups preferably in ortho position or meta position to each other.

• – m-Aminophenol und/oder dessen Derivate,
• – m-Diaminobenzol und/oder dessen Derivate,
• – o-Diaminobenzol und/oder dessen Derivate,
• – Naphthalinderivate mit mindestens einer Hydroxygruppe,
• – Di- beziehungsweise Trihydroxybenzol und/oder deren Derivate,
• – Pyridinderivate,
• – Pyrimidinderivate,
• – Monohydroxyindol-Derivate und/oder Monoaminoindol-Derivate,
• – Monohydroxyindolin-Derivate und/oder Monoaminoindolin-Derivate,
• – Pyrazolonderivate, wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin oder 6-Amino-benzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,

Coupler components according to the invention are preferably selected as at least one compound from one of the following classes:

• M-aminophenol and / or its derivatives,
• M-diaminobenzene and / or its derivatives,
• O-diaminobenzene and / or its derivatives,
• Naphthalene derivatives having at least one hydroxy group,
• Di- or trihydroxybenzene and / or derivatives thereof,
• - pyridine derivatives,
• - pyrimidine derivatives,
• Monohydroxyindole derivatives and / or monoamine indole derivatives,
• Monohydroxyindoline derivatives and / or monoaminoindoline derivatives,
• Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Morpholine derivatives such as, for example, 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

mixtures of two or more compounds from one or more of these Classes are also within the scope of this embodiment according to the invention.

worin
G¹ und G² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₂ bis C₄)-Perfluoracylgruppe,
G³ und G⁴ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe.The m-aminophenols or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K1) and / or from at least one physiologically tolerated salt of a compound of the formula (K1),

wherein
G ¹ and G ² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) -alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₂ to C ₄ ) perfluoroacyl group,
G ³ and G ⁴ independently represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) monohydroxyalkyl group , a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group.

Especially preferred m-aminophenol coupler components are selected from at least one compound from the group that is formed from m-aminophenol, 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, 2,4-dichloro-3-aminophenol and the physiological compatible salts of all the compounds mentioned above.

worin
G⁵, G⁶, G⁷ und G⁸ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₂ bis C₄)-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterozyklus bilden
G⁹ und G¹⁰ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₄)-Alkylgruppe, eine ω-(2,4-Diaminophenyl)-(C₁ bis C₄)-alkylgruppe, eine ω-(2,4-Diaminophenyl)-(C₁ bis C₄)-alkoxygruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe.The m-diaminobenzenes or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K2) and / or from at least one physiologically tolerated salt of a compound of the formula (K2),

wherein
G ⁵ , G ⁶ , G ⁷ and G ⁸ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) -alkenyl group , a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G ⁹ and G ¹⁰ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl group, an ω- (2,4-diaminophenyl) - (C ₁ to C ₄ ) -alkyl group, an ω- (2,4-diaminophenyl) - (C ₁ to C ₄ ) alkoxy group, a (C ₁ to C ₄ ) alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) Polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group.

Especially preferred m-diaminobenzene coupler components are selected from at least one compound from the group that is formed from 2- (2,4-diaminophenoxy) ethanol, 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, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxy-ethoxy) -5-methyl-phenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene and the physiological compatible salts of all the compounds mentioned above.

worin
G¹¹, G¹², G¹³ und G¹⁴ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₂ bis C₄)-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterozyklus bilden
G¹⁵ und G¹⁶ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine Carboxylgruppe, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe.The o-diaminobenzenes or their derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K3) and / or from at least one physiologically tolerated salt of a compound of the formula (K3),

wherein
G ¹¹ , G ¹² , G ¹³ and G ¹⁴ independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group , a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G ¹⁵ and G ¹⁶ independently of one another represent a hydrogen atom, a halogen atom, a carboxyl group, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) Monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group.

Especially preferred o-diaminobenzene coupler components are selected from at least one compound from the group that is formed from 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all above mentioned compounds.

preferred Di- or trihydroxybenzenes and their derivatives selected from at least one compound of the group, which is formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, Pyrogallol and 1,2,4-trihydroxybenzene.

worin
G¹⁷ und G¹⁸ stehen unabhängig voneinander für eine Hydroxygruppe oder eine Gruppe -NG²¹G²² worin G²¹ und G²² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylgruppe,
G¹⁹ und G²⁰ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₄)-Alkylgruppe oder eine (C₁ bis C₄)-Alkoxygruppe.The pyridine derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K4) and / or from at least one physiologically tolerable salt of a compound of the formula (K4),

wherein
G ¹⁷ and G ¹⁸ independently of one another represent a hydroxy group or a group -NG ²¹ G ²² in which G ²¹ and G ²² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) Cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, an optionally substituted aryl group, a (C ₁ to C ₄ ) Alkoxy (C ₁ to C ₄ ) alkyl group,
G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -alkoxy group.

It is preferred if, according to formula (K4), the radicals G ¹⁷ and G ^{18 are} in the ortho position or in the meta position relative to one another.

Especially preferred pyridine derivatives are selected from at least a compound of the group formed from 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, 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiological acceptable salts of the aforementioned compounds.

preferred Naphthalene derivatives having at least one hydroxy group are selected from at least one compound of the group that is formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.

worin
G²³ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe,
G²⁴ steht für eine Hydroxygruppe oder eine Gruppe -NG²⁶G²⁷, worin G²⁶ und G²⁷ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe,
G²⁵ Wasserstoffatom, ein Halogenatom oder eine (C₁ bis C₄)-Alkylgruppe,
mit der Maßgabe, dass G²⁴ in meta-Position oder ortho-Position zum Strukturfragment NG²³ der Formel bindet.The indole derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K5) and / or from at least one physiologically tolerated salt of a compound of the formula (K5),

wherein
G ²³ represents a hydrogen atom, a C ₁ to C ₄ alkyl group, a C ₃ to C ₆ cycloalkyl group, a C ₂ to C ₄ alkenyl group, a C ₁ to C ₄ monohydroxyalkyl group , a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ²⁴ represents a hydroxy group or a group -NG ²⁶ G ²⁷ , in which G ²⁶ and G ²⁷ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ^{25 is a} hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) -alkyl group,
with the proviso that G ²⁴ binds in the meta position or ortho position to the structural fragment NG ^{23 of} the formula.

Especially Preferred indole derivatives are selected from at least a compound of the group formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable Salts of the aforementioned compounds.

worin
G²⁸ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe,
G²⁹ steht für eine Hydroxygruppe oder eine Gruppe -NG³¹G³², worin G³¹ und G³² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe,
G³⁰ Wasserstoffatom, ein Halogenatom oder eine (C₁ bis C₄)-Alkylgruppe,
mit der Maßgabe, dass G²⁹ in meta-Position oder ortho-Position zum Strukturfragment NG²⁸ der Formel bindet.The indoline derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K6) and / or from at least one physiologically tolerable salt of a compound of the formula (K6),

wherein
G ²⁸ represents a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group , a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ²⁹ represents a hydroxy group or a group -NG ³¹ G ³² , in which G ³¹ and G ³² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ^{30 is a} hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) -alkyl group,
with the proviso that G ²⁹ binds in the meta position or ortho position to the structural fragment NG ^{28 of} the formula.

Especially preferred indoline derivatives are selected from at least a compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable Salts of the aforementioned compounds.

preferred Pyrimidine derivatives are selected from at least one Compound of the group formed from 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 and the physiologically acceptable Salts of the aforementioned compounds.

Particularly preferred coupler components according to the invention are selected from m-aminophenol, 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, 2,4- Dichloro-3-aminophenol, 2- (2,4-diaminophenoxy) ethanol, 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, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5- methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4, 5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-Ami no-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2 Chlororesorcinol, 4-chlororesorcinol, pyrogallol, 1,2,4-trihydroxybenzene, 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, 3,5-diamino-2 , 6-dimethoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino 3-aminopyridine, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6 -Hydroxyindoline, 7-hydroxyindoline, 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 mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds.

The Coupler components are preferably present in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use oxidation colorants.

there become developer components and coupler components in general used in about molar amounts to each other. If also the molar use has proved to be useful, so is a certain excess of individual oxidation dye precursors not detrimental, leaving developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2, can stand.

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (K1) to (K6): Examples of (C ₁ to C ₄ ) -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ .

Examples of (C ₁ to C ₄ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group.

Furthermore, as preferred examples of a (C ₁ to C ₄ ) monohydroxyalkyl group, -CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, with the group -CH ₂ CH ₂ OH being preferred.

A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group.

Examples for halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.

Examples of nitrogen-containing groups are in particular -NH ₂ , (C ₁ to C ₄ ) -monoalkylamino groups, (C ₁ to C ₄ ) -dialkylamino groups, (C ₁ to C ₄ ) -trialkylammonium groups, (C ₁ to C ₄ ) -monohydroxyalkylamino groups, Imidazolinium and -NH ₃ ⁺ .

Examples of (C ₁ to C ₄ ) monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ , -NHCH ₂ CH ₂ CH ₃ , -NHCH (CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) trialkylammonium groups are -N ⁺ (CH ₃ ) ₃ , -N ⁺ (CH ₃ ) ₂ (CH ₂ CH ₃ ), -N ⁺ (CH ₃ ) (CH ₂ CH ₃ ) ₂ ,

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino radicals are -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ -O -CH (CH ₃ ) ₂ .

Examples of hydroxy (C ₁ to C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH, -O-CH ₂ CH (OH) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) -acetylaminoalkoxy radicals are -O-CH ₂ NHC (O) CH ₃ , -O-CH ₂ CH ₂ NHC (O) CH ₃ , -O-CH ₂ CH ₂ CH ₂ NHC (O ) CH ₃ , -O-CH ₂ CH (NHC (O) CH ₃ ) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ NHC (O) CH ₃ .

Examples of (C ₁ to C ₄ ) -carbamoylaminoalkoxy radicals are -O-CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ .

Examples of (C ₁ to C ₄ ) -aminoalkyl radicals are -CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH (NH ₂ ) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ .

Examples of (C ₁ to C ₄ ) -cyanoalkyl radicals are -CH ₂ CN, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ CH ₂ CN.

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH.

Examples of di [(C ₁ to C ₄ ) -hydroxyalkyl] amino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N ( CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ .

One Example of aryl groups is the phenyl group.

Examples of aryl (C ₁ to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

For temporary stains become common Dyeing or toning agents used as coloring Component so-called Direktzieher included. This is it around dye molecules that are directly on the substrate raise and no oxidative process to form the color need. These dyes include, for example that already from the antiquity to the coloring of body and hairs known henna. These dyes are against shampooing usually much more sensitive than oxidative stains, so much faster then a much undesirable Shade shift or even a visible homogeneous color loss entry.

Farther the agents according to the invention can be at least contain a direct dye. This is about Dyes that grow directly on the hair and no oxidative Need process for color training. Substantive Dyes are usually nitrophenylenediamines, nitroaminophenols, Azo dyes, anthraquinones or indophenols.

The substantive dyes are each preferably in an amount from 0.001 to 20% by weight, based on the total application preparation, used. The total amount of substantive dyes is preferably at most 20% by weight.

Substantive Dyes can be anionic, cationic and nonionic substantive dyes are subdivided.

Anionic substantive dyes:

Particularly suitable anionic direct dyes are 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (CI 15.985, Food Yellow No. 3, FD & C Yellow No. 6), 2,4-dinitro-1 naphthol-7-sulfonic acid disodium salt (CI 10,316, Acid Yellow 1, Food Yellow No. 1), 2- (indan-1,3-dion-2-yl) quinoline-x, x-sulfonic acid (mixture of mono- and di-sodium Disulfonic acid) (CI 47,005, D & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10), 4 - ((4-amino-3-sulfophenyl) azo) benzenesulfonic acid disodium salt (CI 13,015, Acid Yellow 9 ), 5-hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt (CI 19.140, Food Yellow No. 4, Acid Yellow 23), 3 - [( 4-phenylamino) phenyl] azobenzenesulfonic acid, sodium salt (CI 13.065, Ki406, Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthen-3-one (CI 45, 350; Acid Yellow 73, D & C Yellow No 8), 5 - [(2,4-dinitrophenyl) amino] -2-phenylaminobenzenesulfonic acid, sodium salt (CI 10,385; Acid Orange 3), 4 - [(2,4-dihydroxyphenyl) az o] -benzenesulfonic acid sodium salt (CI 14,270; Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid, sodium salt (CI 15.510, Acid Orange 7), 4 - [(2,4-dihydroxy-3 - [(2,4-) dimethylphenyl) azo] -phenyl) azo] -benzenesulfonic acid, sodium salt (CI 20,170; Acid Orange 24), 4-hydroxy-3 - [(2-methoxyphenyl) azo] -1-naphthalenesulfonic acid, sodium salt (CI 14,710, Acid Red 4) , 4-Hydroxy-3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalenesulfonic acid disodium salt (CI 14,720; Acid Red No. 14), 6-hydroxy-5 - [(4-sulfonaphth-1-yl) azo] -2,4-naphthalenedisulfonic acid trisodium salt (CI 16,255; Ponceau 4R; Acid Red 18). , 3-Hydroxy-4 - [(4-sulfonaphth-1-yl) azo] -2,7-naphthalenedisulfonic acid trisodium salt (CI 16.185, Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo ) -3,6-naphthalenedisulfonic acid disodium salt (CI 17,200, Acid Red 33, Red 33), 5- (acetylamino) -4-hydroxy-3 - [(2-methylphenyl) azo] -2,7-naphthalene disulfonic acid disodium salt (CI 18.065, Acid Red 35), 2- (3-hydroxy-2,4,5,7-tetraiodedibenzopyran-6-on-9-yl) benzoic acid disodium salt (CI 45,430; Acid Red 51 ), N- [6- (Diethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethylethanammonium hydroxide, inner salt, sodium salt (CI 45, 100; Acid Red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1,3-disulfonic acid disodium salt (CI 27.290; Acid Red 73), 2 ', 4', 5 ', 7'-tetrabromo-3', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one disodium salt (CI 45,380; Acid Red 87), 2', 4 ', 5', 7'-tetrabromo-4 , 5,6,7-tet achloro-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9'] [9H] xanthene] -3-one disodium salt (CI 45.410; Acid Red 92), 3 ', 6'-dihydroxy-4', 5'-diiodospiro [isobenzofuran-1 (3H), 9 '(9H) -xanthene] -3-one-disodium salt (CI 45425; Acid Red 95). , 2-Hydroxy-3 - ((2-hydroxynaphth-1-yl) azo) -5-nitrobenzenesulfonic acid, sodium salt (CI 15,685, Acid Red 184), 3-hydroxy-4- (3-methyl-5-oxo-1 -phenyl-4,5-dihydro-1H-pyrazol-4-ylazo) -naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red 195), 3-hydroxy-4 - [(4-methyl-2-sulfonphenyl ) azo] -2-naphthalenecarboxylic acid calcium salt (CI 15.850: 1, Pigment Red 57: 1), 3 - [(2,4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid disodium salt Food Red No. 1, Ponceau SX, FD & C Red No. 4), 1,4-bis [(2-sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (CI 61.570; Acid Green 25), bis [4- (dimethylamino) phenyl] - (3,7-disulfo-2-hydroxynaphth-1-yl) carbenium inner salt, sodium salt (CI 44,090, Food Green No. 4, Acid Green 50). , Bis [4- (diethylamino) -phenyl] (2,4-disulfophenyl) carbenium inner salt, sodium salt (2: 1) (CI 42.045, Food Blue No. 3; Acid Blue 1), bis [4- (diethylamino) phenyl] (5-hydroxy-2,4-disulfophenyl) carbenium inner salt, calcium salt (2: 1) (CI 42,051; Acid Blue 3), N- [4 - [(2,4-disulfophenyl) [4- [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5-cyclohexadien-1-ylidene] -N-ethylbenzene methanaminium hydroxide, internal salt, sodium salt (CI 42.080; Acid Blue 7), (2-sulfophenyl) di [4- (ethyl ((4-sulfophenyl) methyl) amino) phenyl] -carbenium disodium salt betaine (CI 42.090; Acid Blue 9; FD & C Blue No. 1), 1-amino-4- (phenylamino) -9,10-anthraquinone-2-sulfonic acid (CI 62.055, Acid Blue 25), 1-amino-4- (cyclohexylamino) -9,10-anthraquinone 2-sulfonic acid sodium salt (CI 62045; Acid Blue 62), 2- (1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene) -2,3-dihydro-3-oxo 1H-indole-5-sulfonic acid disodium salt (CI 73.015, Acid Blue 74), 9- (2-carboxyphenyl) -3 - [(2-methylphenyl) amino] -6 - [(2-methyl-4-sulfophenyl) amino ] xanthylium inner salt, sodium salt (CI 45.190, Acid Violet 9), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone sodium salt (CI 60,730; 2, Acid Violet 43), bis [3-nitro-4 - [(4-phenylamino) -3-sulfophenylamino] -phenyl] -sulfone (CI 10.410, Aci d Brown 13), 5-amino-4-hydroxy-6 - [(4-nitrophenyl) azo] -3- (phenylazo) -2,7-naphthalenedisulfonic acid disodium salt (CI 20,470; Acid Black 1), 3-hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7-nitro-1-naphthalenesulfonic acid-chromium complex (3: 2) (CI 15,711, Acid Black 52), 4 - (acetylamino) -5-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo] naphth-1-yl) azo] -1,7-naphthalenedisulfonic acid tetrasodium salt (CI 28,440; Food Black No 1), 3 ', 3 ", 5', 5" -tetrabromophenolsulfonephthalein (bromophenol blue).

preferred anionic substantive dyes are among the international ones Designations or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds.

Cationic direct dyes:

Particularly suitable cationic direct dyes are 9- (dimethylamino) benzo [a] phenoxazine-7-ium chloride (CI 51.175; Basic Blue 6), di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium chloride (CI 42.595; Basic Blue 7), di- (4- (dimethylamino) phenyl) (4- (methylphenylamino) -naphthalen-1-yl) carbenium chloride (CI 42.563, Basic Blue 8), 3, 7-Di (dimethylamino) phenothiazine-5-ium chloride (CI 52.015 Basic Blue 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (CI 44.045, Basic Blue 26), 2 - [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methylbenzothiazolium methylsulfate (CI 11.154, Basic Blue 41), 8-amino-2-bromo-5- hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (CI 56.059; Basic Blue No. 99), bis [4- (dimethylamino) phenyl] - [ 4- (methylamino) phenyl] carbenium chloride (CI 42,535, Basic Violet 1), tri (4-amino-3-methylphenyl) carbenium chloride (CI 42,520, Basic Violet 2), tri [4- (dimethylamino) -phenyl ] carbenium chloride (CI 42.555; Basic Violet 3), 2- [3,6- (diethylamino) dibenzopyranium-9-yl] benzoic acid chloride (CI 45,170, Basic Violet 10), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (CI 42.510 Basic Violet 14), 1,3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (CI 21.010, Basic Brown 4), 1 - [(4-aminophenyl) azo] -7 - (trimethylammonio) -2-naphthol chloride (CI 12.250; Basic Brown 16), 1 - [(4-amino-2-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride, 1 - [(4- Amino-3-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (CI 12,251; Basic Brown 17), 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzylaminium chloride (CI 12,605, Basic Orange 69), 3,7-diamino-2,8-dimethyl 5-phenylphenazinium chloride (CI 50.240, Basic Red 2), 1,4-dimethyl-5 - [(4- (dimethylamino) phenyl) azo] -1,2,4-triazolium chloride (CI 11.055, Basic Red 22 ), 2-hydroxy-1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) naphthalene chloride (CI 12.245, Basic Red 76), di [4- (dimethylamino) phenyl] iminomethane hydrochloride (CI 41,000 Basic Yellow 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indol-1-ium chloride (CI 48,055, Basic Yellow 11), 3-Methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo) pyrazol-5-one chloride (CI 12,719; Basic Yellow 57), bis [4- (diethylamino) phenyl] phenylcarbenium hydrogensulfate (1: 1) (CI 42.040; Basic Green 1), di (4- (dimethylamino) phenyl) -phenylmethanol (CI 42,000, Basic Green 4), 1- (2-morpholiniumpropylamino) -4-hydroxy-9,10- anthraquinone methylsulfate, 1 - [(3- (dimethylpropylaminium) -propyl) amino] -4- (methylamino) -9,10-anth rachinone chloride and substantive dyes containing a heterocycle having at least one quaternary nitrogen atom.

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

Preferred cationic substantive dyes are included

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

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

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

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

Nonionic substantive dyes:

When Nonionic substantive dyes are particularly suitable nonionic nitro and quinone dyes and neutral azo dyes.

Suitable blue nitro dyes are in particular:
1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene (HC Blue 2), 1-Methylamino-4- [methyl- (2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Blue 6), 1 - [(2,3-dihydroxypropyl) amino] -4- [ethyl- (2- hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 9), 1 - [(2,3-dihydroxypropyl) amino] -4- [methyl (2-hydroxyethyl) amino] -2-nitrobenzene (HC Blue 10) , 4- [di (2-hydroxyethylamino] -1 - [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue 11), 4- [ethyl- (2-hydroxyethyl) amino] -1 - [(2 -hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 12), 2 - ((4-amino-2-nitrophenyl) amino) -5-dimethylaminobenzoic acid (HC Blue 13), 1-amino-3-methyl 4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet 1), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet 2), 1- (2-aminoethylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene, 4- (di (2-hydroxyethyl) amino) -2-nitro-1-phenylaminobenzene.

Suitable red nitro dyes are in particular:
1-Amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 7), 2-amino-4,6-dinitrophenol (picramic acid) and its salts, 1,4-diamino-2-nitrobenzene ( CI 76,070), 4-amino-2-nitrodiphenylamine (HC Red 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red 13), 1-amino-4- [(2-hydroxyethyl) amino] -5-chloro-2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 3), 4 - [(2-hydroxyethyl) methylamino] -1- (methylamino) -2-nitrobenzene, 1-amino-4 - [(2,3-dihydroxypropyl) amino] -5-methyl-2-nitrobenzene, 1-amino-4- (methylamino) -2- nitrobenzene, 4-amino-2-nitro-1 - [(prop-2-en-1-yl) amino] benzene, 4-amino-3-nitrophenol, 4 - [(2-hydroxyethyl) amino] - 3-nitrophenol, 4 - [(2-nitrophenyl) amino] phenol (HC Orange 1), 1 - [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2-nitrobenzene (HC Orange 2), 4 - (2,3-dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Orange 3), 1-amino-5-chloro-4 - [(2,3-dihydroxypropyl) amino] - 2-nitrobenzene (HC Red 10), 5-chloro-1,4- [di (2,3-dihydroxypropyl) amino] -2-nitrobenzene zol (HC Red 11), 2 - [(2-hydroxyethyl) amino] -4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 2 Chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol (HC Red BN), 2,5-diamino-6 -nitropyridine, 6-amino-3 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino-6 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino-6- (ethylamino) 2-nitropyridine, 3 - [(2-hydroxyethyl) amino] -6- (methylamino) -2-nitropyridine, 3-amino-6- (methylamino) -2-nitropyridine, 6- (ethylamino) -3 - [( 2-hydroxyethyl) amino] -2-nitropyridine, 1,2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red 14 ).

Suitable yellow nitro dyes are in particular:
1,2-diamino-4-nitrobenzene (CI 76,020), 1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow 2), 1- (2-hydroxyethoxy) -2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 4), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 5), 4 - [(2,3-dihydroxypropyl) amino] - 3-nitro-1-trifluoromethylbenzene (HC Yellow 6), 2- [di (2-hydroxyethyl) amino] -5-nitrophenol, 2 - [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene, 2-Amino-3-nitrophenol, 2-amino-4-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1- (2-hydroxyethoxy) -3-methylamino-4-nitrobenzene, 2,3- (dihydroxypropoxy ) -3-methylamino-4-nitrobenzene, 3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride (HC Yellow 9), 1-chloro-2,4-bis [(2-hydroxyethyl) amino ] -5-nitrobenzene (HC Yellow 10), 2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow 11), 1 - [(2'-ureidoethyl) amino] -4-nitrobenzene, 1-amino -4 - [(2-aminoethyl) amino] -5-methyl-2-nitrobenzene, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-chloro-4 - [(2-hydroxyethyl ) amino] -3-nitrobenzene (HC Yellow 12), 4 - [( 2-hydroxyethyl) amino] -3-nitro-1-trifluoromethylbenzene (HC Yellow 13), 4 - [(2-hydroxyethyl) amino] -3-nitrobenzonitrile (HC Yellow 14), 4 - [(2 -Hydroxyethyl) amino] -3-nitrobenzamide (HC Yellow 15) 3 - [(2-hydroxyethyl) amino] -4-methyl-1-nitrobenzene, 4-chloro-3 - [(2-hydroxyethyl) amino] - 1-nitrobenzene.

Suitable quinone dyes are in particular:
1,4-di [(2,3-dihydroxypropyl) amino] -9,10-anthraquinone, 1,4-di [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 61.545, Disperse Blue 23), 1 - [(2-hydroxyethyl) amino] -4-methylamino-9,10-anthraquinone (CI 61,505, Disperse Blue 3), 2 - [(2-aminoethyl) amino] -9,10-anthraquinone (HC Orange 5) , 1-amino-4-hydroxy-9,10-anthraquinone (CI 60.710, Disperse Red 15), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone, 7- Beta-D-glucopyranosyl-9,10-dihydro-1-methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracenecarboxylic acid (CI 75,470, Natural Red 4), 1 - [(3 Aminopropyl) amino] -4-methylamino-9,10-anthraquinone (HC Blue 8), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red 8), 1,4-diamino-2 -methoxy-9,10-anthraquinone (CI 62.015, Disperse Red 11, Solvent Violet No. 26), 1,4-dihydroxy-5,8-bis [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 62,500, Disperse Blue 7, Solvent Blue No. 69), 1,4-diamino-9,10-anthraquinone (CI 61.100, Disperse Violet 1), 1-amino-4- (methylamino) -9,10-anthraquinone (CI 61,105, Disperse Viole t 4, Solvent Violet No. 12), 2-hydroxy-3-methoxy-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-hydroxy-3-methyl-1,4-naphthoquinone, N- {6 - [( 3-chloro-4- (methylamino) phenyl) imino] -4-methyl-3-oxo-1,4-cyclohexadien-1-yl} urea (HC Red 9), 2 - {{4- [di (2- hydroxyethyl) amino] phenyl} amino} -5 - [(2-hydroxyethyl) amino] -2,5-cyclohexadiene-1,4-dione (HC Green 1), 5-hydroxy-1,4-naphthoquinone (CI 75,500, Natural Brown 7), 2-hydroxy-1,4-naphthoquinone (CI 75,480, Natural Orange 6), 1,2-dihydro-2- (1,3-dihydro-3-oxo-2H-indol-2-ylidene) 3H-indol-3-one (CI 73,000), 4 - {{5 - [(2-hydroxyethyl) amino] -1-methyl-1H-pyrazol-4-yl} imino} -4,5-dihydro-5 - [(2-hydroxyethyl) -imino] -1-methyl-1H-pyrazole sulfate (1: 1), hydrate (1: 1).

Suitable neutral azo dyes are in particular:
1- [di (2-hydroxyethyl) amino] -3-methyl-4 - [(4-nitrophenyl) azo] benzene (CI 11.210, Disperse Red 17), 1- [di (2-hydroxyethyl) amino] -4 - [(4-nitrophenyl) azo] benzene (Disperse Black 9), 4 - [(4-aminophenyl) azo] -1- [di (2-hydroxyethyl) amino] -3-methylbenzene (HC Yellow 7), 2 , 6-diamino-3 - [(pyridin-3-yl) azo] pyridine, 2 - {[4- (acetylamino) phenyl] azo} -4-methylphenol (CI 11855, Disperse Yellow 3), 4 - [( 4-nitrophenyl) azo] -aniline (CI 11.005, Disperse Orange 3).

preferred Nonionic direct dyes are among the international ones Designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds, and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic 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-4-nitrophenol.

It It is not necessary that the substantive dyes each represent uniform connections. Rather, conditioned by the manufacturing processes for the individual Dyes, in minor amounts still contain other components be, as far as they do not adversely affect the dyeing result or for other reasons, e.g. B. toxicological, excluded Need to become.

Farther can also be used as direct dyes in nature occurring dyes are used, as for example in henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and Alkana root are included.

After all another dyeing process has received a lot of attention found. In this process, precursors of the natural Hair Dye Melanin on the substrate, eg. As hair applied; These then form natural analogues in the course of oxidative processes in the hair Dyes off. At, in particular multiple, application of means With 5,6-dihydroxyindoline it is possible to give people with graying Hair to reproduce the natural hair color. The coloration can be done with atmospheric oxygen as the sole oxidant, so that resorted to no further oxidizing agents must become. In persons with originally mittelblondem to brown hair, indoline can be the sole dye precursor be used. For use with persons with original red and especially dark to black hair color can against it Satisfactory results often only through co-use further dye components, in particular special oxidation dye precursors, be achieved.

When Dye precursors of naturally-analogous dyes are preferably those Indoles and indolines were used, which selected at least two groups from hydroxy and / or or amino groups, preferably as a substituent at the six-ring, exhibit. These groups may have additional substituents wear, z. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group. In a further embodiment the colorants contain at least one indole and / or Indoline. Compositions according to the invention, contain the precursors of natural dyes, are preferred used as air-oxidative coloring agents. In this embodiment Therefore, the said compositions will not be associated with an additional Oxidizing agent added.

in der unabhängig voneinander

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

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (RN1),

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,

and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially preferred derivatives of indoline are the 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid.

Especially noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and in particular the 5,6-dihydroxyindoline.

in der unabhängig voneinander

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

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (RN2),

in the independently of each other

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

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

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

A offers further possibility for color change the use of colorants, which are so-called oxo dye precursors contain. A first class of oxo dye precursors are compounds with at least one reactive carbonyl group. This first class will referred to as component (Oxo1). A second class of oxo dye precursors form CH-acidic compounds and compounds with primary or secondary amino group or hydroxy group, which in turn are selected from compounds of the group that formed is made from primary or secondary aromatic Amines, nitrogen-containing heterocyclic compounds and aromatic Hydroxy compounds. This second class is called Component (Oxo2) designated. The aforementioned components (Oxo1) and (Oxo2) are generally themselves no dyes, and are therefore suitable for each taken alone, not for coloring keratin-containing Fibers. In combination, they form in a non-oxidative process of the so-called oxo dyeing dyes. The resulting Dyeings have partial color fastness on the keratin-containing Fiber comparable to those of oxidation staining are.

The Nuance spectrum achievable with gentle oxo staining is very wide and the obtained color often shows an acceptable brilliance and color depth. Under compounds of However, component (Oxo2) can also be corresponding Developing and / or coupling agent oxidation dye precursors with or use without the use of an oxidizing agent. Consequently the method of oxo staining can be easily determined combine with the oxidative dyeing system.

• – mindestens einer Verbindung, die mindestens eine reaktive Carbonylgruppe enthält (Komponente (Oxo1)) mit mindestens einer Verbindung (Komponente Oxo2)
• – Verbindungen, ausgewählt aus (Oxo2a) CH-aciden Verbindungen und/oder aus (Oxo2b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus mindestens einer Verbindung der Gruppe, die gebildet wird aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen zum Einsatz.

As Oxofarbstoffvorprodukte preferably a combination of

• At least one compound containing at least one reactive carbonyl group (component (Oxo1)) with at least one compound (component Oxo2)
• Compounds selected from (oxo2a) CH-acidic compounds and / or from (oxo2b) compounds having primary or secondary amino group or hydroxy group selected from at least one compound of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.

• a) von Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Additionsverbindung
• b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Additionsverbindung
• c) von Wasser unter Bildung von Hydraten als Additionsverbindung (Komponente (Oxo1) leitet sich in diesem Fall c) von einem Aldehyd ab)

an das Kohlenstoffatom der Carbonylgruppe der reaktiven Carbonylverbindung.Reactive carbonyl compounds as component (oxo1) have in the context of the invention at least one carbonyl group as a reactive group which reacts with the component (oxo2) to form a covalent bond. Preferred reactive carbonyl compounds are selected from compounds which carry at least one formyl group and / or at least one keto group, in particular at least one formyl group. Furthermore, those compounds according to the invention are also suitable as component (Oxo1) in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the component (Oxo2) is always present. These derivatives are preferably addition compounds

• a) amines and derivatives thereof to form imines or oximes as addition compound
• b) of alcohols to form acetals or ketals as addition compound
• c) of water with formation of hydrates as addition compound (component (oxo1) is derived in this case c) from an aldehyde)

to the carbon atom of the carbonyl group of the reactive carbonyl compound.

Preferred reactive carbonyl compounds of the component (oxo1) are selected from the group consisting of benzaldehyde and its derivatives, naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine -9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3 trimethylindoline (Fischer's aldehyde or tribasic aldehyde), 2-indolealdehyde, 3-indolealdehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 2- (1 ', 3', 3'-trimethyl-2- indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, pyridoxal, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl trifluoro-acetone, chromone-3 aldehyde, 3- (5'-nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein, and imidazole-2-aldehyde, 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, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 9-methyl-3-carbazolaldehyde, 9- Ethyl 3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1,4,9-trimethyl-3-carbazolaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid,
4-Formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1 benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 5-formyl-1 methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl 1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5 -Formyl-1-allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7-formyl-1-allyl-quinolinium and 8-formyl-1-allyl-quinolinium-benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methylisatin, 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 Methylquinisatin, as well as any mixtures of the above compounds.

worin

• • R¹, R² und R³ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine Formylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine (C₁ bis C₆)-Dialkylaminogruppe, eine Di(C₂-C₆-hydroxyalkyl)aminogruppe, eine Di(C₁ bis C₆)-alkoxy-(C₁ bis C₆)-alkyl)aminoguppe, eine (C₁ bis C₆)-Hydroxyalkyloxygruppe, eine Sulfonylgruppe, eine Carboxylgruppe, eine Sulfonsäuregruppe, eine Sulfonamidgruppe, eine Carbamoylgruppe, eine (C₂ bis C₆)-Acylgruppe, eine Acetylgruppe oder eine Nitrogruppe,
• • Z' steht für eine direkte Bindung oder eine Vinylengruppe,
• • R⁴ und R⁵ stehen für ein Wasserstoffatom oder bilden gemeinsam, zusammen mit dem Restmolekül einen 5- oder 6-gliederigen aromatischen oder aliphatischen Ring.

Benzaldehyde and / or cinnamaldehyde and / or naphthaldehyde and / or at least one derivative of these abovementioned aldehydes, which in particular carry one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl component in the oxo dyeing. In this case, preference is again given to the reactive carbonyl compound of the component (oxo1) selected from at least one compound of the formula (AC-1),

wherein

• R ¹ , R ² and R ³ are each independently hydrogen, halogen, (C ₁ to C ₆ ) alkyl, (C ₂ to C ₆ ) alkenyl, formyl, hydroxy, C ₁ C ₆ alkoxy group, a (C ₁ to C ₆ ) dialkylamino group, a di (C ₂ -C ₆ hydroxyalkyl) amino group, a di (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl) amino group, (C ₁ to C ₆ ) hydroxyalkyloxy group, sulfonyl group, carboxyl group, sulfonic acid group, sulfonamide group, carbamoyl group, (C ₂ to C ₆ ) acyl group, acetyl group or 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 benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component (Oxo1) are preferably selected from at least one compound of 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, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxy benzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dim ethylbenzaldehyde, 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-methylbenzaldehyde, 2,4-dihydroxy- 3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2,5-dihydro xybenzaldehyde, 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-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3, 5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3 Chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4- Dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-Hy 4-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 3-carboxy-4-hydroxy-benzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy 5-ethoxy-4-hydroxybenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3-allyl-4 hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methoxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-diallyl-4-hydroxybenzaldehyde, 3 allyl-5-carboxy-4-hydroxybenzalde hyd (3-allyl-5-formyl-2-hydroxybenzoic acid), 3-allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde) and piperonal.

When CH-acidic compounds generally become such compounds which is bound to an aliphatic carbon atom Carrying hydrogen atom, due to electron-withdrawing Substituents an activation of the corresponding carbon-hydrogen bond is effected. In principle, the choice of CH-acidic compounds no limits, as long as after condensation with the reactive Carbonyl compounds of the component (Oxo1) one for the human eye visible colored compound is obtained. It deals according to the invention preferably to such CH-acid Compounds which have an aromatic and / or a heterocyclic Rest included. The heterocyclic radical may in turn be aliphatic or be aromatic. Most preferably, the CH-acidic compounds are selected from heterocyclic compounds, in particular cationic, heterocyclic Links.

worin

• • R⁶ steht für eine lineare oder cyclische (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine (C₁ bis C₆)-Alkoxy-(C₁ bis C₆)-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,
• • R⁷ steht für eine (C₁ bis C₆)-Alkylgruppe, insbesondere für eine Methylgruppe,
• • X^– steht für ein physiologisch verträgliches Anion,
• • der Zyklus der Formel (CH-1) repräsentiert alle Ringstrukturen, die zusätzlich weitere Heteroatome wie Stickstoff, Sauerstoff oder Schwefel enthalten können und ferner ankondensierte Ringstrukturen tragen können, wobei alle diese Ringsstrukturen zusätzliche Substituenten tragen können,
• • Het steht für einen gegebenenfalls substituierten Heteroaromaten,
• • X¹ steht für eine direkte Bindung oder eine Carbonylgruppe.

Very particular preference is given to using as component (oxo2a) at least one CH-acidic compound having an aromatic or aliphatic, heterocyclic basic body which is selected from cyclic onium compounds having the structural unit of the formula (CH-1) and / or compounds of the formula (CH-) 2)

wherein

• R ⁶ is a linear or cyclic (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) polyhydroxyalkyl group, a (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl group, a group R ^I R ^{II is} N- (CH ₂ ) _m -, in which R ^I and R ^II independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -hydroxyalkyl group or an aryl- ( C ₁ to C ₆ ) -alkyl group, wherein R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
• R ⁷ is a (C ₁ to C ₆ ) -alkyl group, in particular a methyl group,
• • X ^- is a physiologically acceptable anion,
• The cycle of the formula (CH-1) represents all ring structures which may additionally contain other heteroatoms such as nitrogen, oxygen or sulfur and may further carry fused ring structures, all of these ring structures being able to carry additional substituents,
• Het is an optionally substituted heteroaromatic,
• • X ¹ represents a direct bond or a carbonyl group.

preferred Ring structures bearing the structural unit of the formula (CH-1), are preferably selected according to the invention from 3H indolium, benzothiazolium, benzoxazolium, 1,2-dihydro-2-oxopyrimidinium, Quinolinium, quinoxaline or pyridinium.

According to the invention, compounds of the formula (CH-2) are particularly suitable for those in which the radical Het according to formula (CH-2) is derived from one of the heteroaromatic compounds 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, phenazine, benzocinnoline, benzoquinazoline, benzoquinoxaline, phenoxazine, phenothiazine, nephthyridine, phenanthroline, indolizine, quinolizine, carboline, purine, pteridine or coumarin, the aforementioned heteroaromatics having at least one group selected from a halogen atom, a nitro group, a thio group, a thio (C ₁ to C ₆ ) alkyl group, a heteroaryl group, an aryl group, a (C ₁ to C ₆ ) alkyl group, a (C ₁ b is C ₆ ) -alkoxy, hydroxy, (C ₂ to C ₆ ) -hydroxyalkyl, (C ₂ to C ₆ ) -polyhydroxyalkyl, (C ₁ to C ₆ ) -alkoxy (C ₁ to C ₆ ) alkyl group, an aryl (C ₁ to C ₆ ) alkyl group, an amino group, a (C ₁ to C ₆ ) monoalkylamino group, a (C ₁ to 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 (CH-2) are selected from at least one compound of the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 2- (5-methyl-2-trifluoromethyl-3-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5-fluoro-2-thenoyl) -acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) -acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl) -acetonitrile, 2- (1,2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1H-benzimidazol-2-ylacetonitrile, 1H-benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indol-3-oyl) -acetonitrile, 2- (2-methyl-indol-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-carboxylic acid tert-butyl ester, 2- (6-Hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile and 2- (1-phenyl-1,4-dihydrothiochromeno [4,3-c] pyrazol-3-oyl) - acetonitrile.

worin

• • R⁸ und R⁹ stehen unabhängig voneinander für eine lineare oder cyclische (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine (C₁ bis C₆)-Alkoxy-(C₁ bis C₆)-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₄)-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,
• • R¹⁰ und R¹² stehen unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe, wobei mindestens einer der Reste R¹⁰ und R¹² eine (C₁ bis C₆)-Alkylgruppe bedeutet,
• • R¹¹ steht für ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine (C₁ bis C₆)-Alkoxygruppe, eine (C₁ bis C₆)-Hydroxyalkoxygruppe, eine Gruppe R^IIIR^IVN-(CH₂)_q-, worin R^III und R^IV stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe und q steht für eine Zahl 1, 2, 3, 4, 5 oder 6, wobei der Rest R¹¹ zusammen mit einem der Reste R¹⁰ oder R¹² einen 5- oder 6-gliedrigen aromatischen Ring bilden kann, der gegebenenfalls mit einem Halogenatom, einer (C₁ bis C₆)-Alkylgruppe, einer (C₁ bis C₆)-Hydroxyalkylgruppe, einer (C₂ bis C₆)-Polyhydroxyalkylgruppe, einer (C₁ bis C₆)-Alkoxygruppe, einer (C₁ bis C₆)-Hydroxyalkoxygruppe, einer Nitrogruppe, einer Hydroxygruppe, einer Gruppe R^VR^VIN-(CH₂)_s-, worin R^V und R^VI stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe und s steht für eine Zahl 0, 1, 2, 3, 4, 5 oder 6 substituiert sein kann,
• • Y steht für ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe NR^VII, worin R^VII steht für ein Wasserstoffatom, eine Arylgruppe, eine Heteroarylgruppe, eine (C₁ bis C₆)-Alkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe,
• • X^– steht für ein physiologisch verträgliches Anion.

The CH-acidic compounds of the oxo dye precursors of the component (oxo2a) are preferably selected from at least one compound of the formula (CH-3),

wherein

• R ⁸ and R ⁹ are each independently a linear or cyclic (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) polyhydroxyalkyl group, a (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl group , a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) hydroxyalkyl group or an aryl (C ₁ to C ₄ ) alkyl group, wherein R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
• R ¹⁰ and R ¹² independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group, where at least one of the radicals R ¹⁰ and R ¹² denotes a (C ₁ to C ₆ ) -alkyl group,
• R ¹¹ represents a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group, a (C ₂ to C ₆ ) -polyhydroxyalkyl group, a (C ₁ to C ₆ ) - Alkoxy group, a (C ₁ to C ₆ ) -hydroxyalkoxy group, a group R ^III R ^IV N- (CH ₂ ) _q -, in which R ^III and R ^IV independently of one another represent a hydrogen atom, a (C ₁ to C ₆ ) - Alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group or an aryl (C ₁ to C ₆ ) alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ¹¹ together with one of the radicals R ¹⁰ or R ^{12 may form} a 5- or 6-membered aromatic ring optionally substituted by a halogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group, a ( C ₂ to C ₆ ) polyhydroxyalkyl group, a (C ₁ to C ₆ ) alkoxy group, a (C ₁ to C ₆ ) 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 independently is a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group or an aryl (C ₁ to C ₆ ) -alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,
• Y is an oxygen atom, a sulfur atom or a group NR ^VII , where R ^VII is a hydrogen atom, an aryl group, a heteroaryl group, a (C ₁ to C ₆ ) alkyl group or an aryl (C ₁ to C ₆ ) alkyl group,
• • X ^- stands for a physiologically compatible anion.

At least one group R ¹⁰ or R ¹² according to formula (CH-3) necessarily stands for a (C ₁ to C ₆ ) -alkyl group. This alkyl group preferably carries at least two hydrogen atoms on its α-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 In a preferred embodiment, Y is of the formula (CH-3) for an oxygen or a sulfur atom, more preferred for an oxygen atom.

The radical R ^{8 of} the formula (CH-3) is preferably selected from a (C ₁ to C ₆ ) -alkyl group (particularly preferably a methyl group), a (C ₂ to C ₆ ) -alkenyl group (in particular an allyl group), a (C ₂ to C ₆ ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.

R ^{11 of} the formula (CH-3) is preferably a hydrogen atom.

Particularly preferred in formula (CH-3) are the radicals R ⁹ , R ¹⁰ and R ^{12 is} a methyl group, the radical R ^{11 is} a hydrogen atom, Y is an oxygen or sulfur atom and the radical R ⁸ is selected from a ( C ₁ to C ₆ ) alkyl group (particularly preferably a methyl group), a (C ₂ to C ₆ ) alkenyl group (especially an allyl group), a (C ₂ to C ₆ ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or a optionally substituted benzyl group.

• – 1,2-Dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4,6-dimethyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1,3,4-trimethyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4-methyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidiniums,
• – Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1-(2-hydroxyethyl)-3,4,6-trimethyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4,6-dimethyl-2-thioxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
• – 1,2-Dihydro-1,3,4-trimethyl-2-thioxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4-methyl-2-thioxo-pyrimidiniums,
• – 1,2-Dihydro-1,3-diphenyl-4-methyl-2-thioxo-pyrimidiniums,
• – 1,2-Dihydro-3,4-dimethyl-2-oxo-chinazoliniums und
• – 1,2-Dihydro-3,4-dimethyl-2-thioxo-chinazoliniums.

Preferably, the compounds according to formula (CH-3) are selected from one or more compounds of the group of salts with physiologically acceptable counterion X ^- , which is formed from salts of

• 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,
• 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-pyrimidinium,
• 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium,
• 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,
• 1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidinium,
• 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.

• – 1,2-Dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1,3,4-trimethyl-2-oxo-pyrimidiniums,
• – Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,
• – 1,2-Dihydro-1-(2-hydroxyethyl)-3,4,6-trimethyl-2-oxo-pyrimidiniums und
• – 1,2-Dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidiniums.

Very particularly preferred compounds according to formula (CH-3) are selected from one or more compounds of the group of salts with physiologically acceptable counterion X, which is formed from salts of

• 1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium,
• 1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidinium,
• Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium,
• 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium and
• 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium.

X ^- is in the formulas (CH-1) and (CH-3) and in the above lists preferably for halide, benzenesulfonate, p-toluenesulfonate, (C ₁ to C ₄ ) alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogen sulfate, Tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. The anions chloride, bromide, iodide, hydrogensulfate or p-toluenesulfonate are particularly preferably used as X ^- .

links of the formula (CH-3) according to the invention are particularly preferably used.

The CH-acidic compounds of the oxo dye precursors of the component (oxo2a) are most preferably selected from at least one compound of 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-di methylpyrrol-3-oyl) -acetonitrile, 2- (1,2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1H-benzimidazol-2-ylacetonitrile, 1H-benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indol-3-oyl) -acetonitrile, 2- (2-methyl-indol-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- (quinoxaline -2-yl) -acetonitrile, 2- (cumarone-2-yl) -acetonitrile, 6,7-dichloro-5- (cyanoacetyl) -2,3-dihydro-1-benzofuran-2-carboxylic acid tert -butyl ester , 2- (6-Hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile, 2- (1-phenyl-1,4-dihydrothiochromeno [4,3-c] pyrazol-3-oyl) acetonitrile, 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 , 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, 3-ethyl-2-methylbenzoxazolium miodide, 3-ethyl-2-methyl-benzothiazolium iodide, 1-ethyl-4-methyl-quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,2,3-trimethylquinoxaluminum iodide, 3-ethyl-2-methyl-benzoxazolium-p- toluenesulfonate, 3-ethyl-2-methyl-benzothiazolium-p-toluenesulfonate, 1-ethyl-4-methyl-quinolinium-p-toluenesulfonate, 1-ethyl-2-methyl-quinolinium-p-toluenesulfonate, 1,2,3-trimethyl-quinoxalinium p-toluenesulfonate, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl- 2-oxopyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2- oxo-pyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium chloride, 1-allyl-1,2-dihydro-3,4,6-trimethyl- 2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3,4,6-tetramethyl- 2-oxo-pyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium hydroge sulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium chloride, 1,2-Dihydro-1,3,4-trimethyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium chloride, 1,2- Dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxopyrimidinium chloride, 1,2-dihydrochloride 1,3-dipropyl-4-methyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium chloride, 1,2-dihydro-1, 3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydrochloride 1,3,4,6-tetramethyl-2-thioxo-pyrimidinium bisulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium bisulfate, 1,2-dihydroxy 1,3,4-trimethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-thioxo-pyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-diethyl 4-methyl-2-thioxo-pyrimidinium chloride, 1,2- Dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium hydrogensulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium chloride and 1,2-dihydroxy 1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium hydrogensulphate.

Of Furthermore, as component (Oxo2b) at least one oxidation dye precursor with at least one primary or secondary Amino group and / or at least one hydroxy group can be used. Preferred suitable representatives can be found under the execution the oxidation dye precursors. However, it is preferred according to the invention if the compounds of the component (Oxo2) only under CH-acidic Connections are selected.

The above-mentioned compounds of the component (Oxo1) and of the component (Oxo2), if they are used, respectively preferably in an amount of 0.03 to 65 mmol, in particular of 1 to 40 mmol, based on 100 g of the total agent used.

The agents according to the invention additionally preferably comprise hydrogen peroxide. Here, agents according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers are particularly preferred, which contain 0.5 to 15% by weight, preferably 1 to 12.5% by weight, particularly preferably 2.5 to 10% by weight and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H ₂ O ₂ ) included.

The hydrogen peroxide may also be used in the form of its attachment compounds to solid supports, preferably hydrogen peroxide itself is 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.

Completely according to the invention Particular preference is given to aqueous hydrogen peroxide solutions. The concentration of a hydrogen peroxide solution is on the one hand by the legal requirements and on the other hand by the determines the desired effect; preferably 6- to 12 percent solutions used in water.

For a color change by means of brightening or equation of the substrate, for example the hair, is preferably used in the cosmetic compositions according to the invention in addition to the oxidizing agents additionally at least one bleach booster.

Bleach boosters are preferably used to increase the bleaching action of the oxidizing agent, in particular the hydrogen peroxide. Suitable bleach boosters are
(BV-i) compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids and / or optionally substituted perbenzoic acid,
and or
(BV-ii) carbonate salts and / or bicarbonate salts,
and or
(BV-iii) organic carbonates,
and or
(BV-iv) carboxylic acids,
and or
(BV-v) Peroxo compounds.

When Bleach enhancers can be compounds that are listed under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, be used. Suitable substances are the oxygen and / or nitrogen-bonded acyl groups with the stated number of carbon atoms and / or optionally substituted benzoyl groups. Prefers are polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

The Carbonate or bicarbonate salts are preferably selected at least one compound of the group consisting of ammonium, Alkali (especially sodium and potassium), and alkaline earth (in particular Calcium), carbonate salts and bicarbonate salts. Especially preferred carbonate or bicarbonate salts are ammonium bicarbonate, Ammonium carbonate, sodium bicarbonate, disodium carbonate, potassium bicarbonate, Dipotassium carbonate and calcium carbonate. These most preferred Salts may be used alone or in mixtures thereof of at least two representatives are used as bleaching amplifiers.

Prefers usable organic carbonates are selected from at least a compound of the group of carbonic acid monoesters and / or from at least one compound of the group of carbonic acid monoamides.

in der R für einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest, oder eine substituierte oder unsubstituierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus steht.Preferably usable carbonic acid monoesters are the carbonic acid monoesters of the formula (BV-1),

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

Particularly according to the invention preferred compositions are characterized the radical R is selected in formula (BV-1) from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl and hydroxymethyl and hydroxyethyl radicals.

in der R für einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest, oder eine substituierte oder unsubstituierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus steht.Preferred carbonic acid monoamides are the compounds of the formula (BV-2),

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 (BV-2), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably, R is a C _1-6 alkyl group. Examples of C ₁ -C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Particularly according to the invention preferred bleaching enhancers of formula (BV-2) are thereby characterized in that the radical R is selected in formula (BV-2) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl and hydroxymethyl and hydroxyethyl radicals.

The Acid H atom of the carbonic acid monoester or monoamide may also be in neutralized form, d. H. it can According to the invention, salts of carbonic acid monoesters or carbonic monoamides are used. Here are Carbonic acid monoester according to the invention or the carbonic acid monoamide, in whole or partially neutralized form, preferably in the form of the alkali metal, ammonium, Alkaline earth metal or aluminum salt and in particular in the form of its Sodium salt.

When Bleach-enhancing carboxylic acid can be used in the inventive Compositions preferably at least one compound from the group, consisting of acetic acid, lactic acid, tartaric acid, Citric acid, salicylic acid and ortho-phthalic acid, be included.

bleach booster are preferably peroxo compounds, in particular inorganic peroxo compounds. Among the bleaching according to the invention Peroxo compounds are not subject to the addition of hydrogen peroxide to other components and not even hydrogen peroxide itself. The choice of peroxo compounds is also subject no restrictions. Preferred peroxo compounds are Peroxydisulfate salts, persulfate salts, peroxyphosphate salts (especially Ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, Ammonium persulfate, potassium persulfate, sodium persulfate, potassium peroxide phosphate) and peroxides (such as barium peroxide and magnesium peroxide). Under these Peroxo compounds, which can also be used in combination According to the invention, the peroxydisulfates, in particular ammonium peroxydisulfate, prefers. Here are means according to the invention Dyeing and possibly simultaneous lightening of keratinischer Fibers which additionally contain 0.01 to 2 wt .-% at least a solid peroxo compound selected from ammonium, Alkali metal and alkaline earth metal persulfates, peroxomonosulfates and peroxidisulfates, preferred agents being peroxydisulfates which are preferably selected from sodium peroxydisulfate and / or potassium peroxydisulfate and / or ammonium peroxydisulfate and particularly preferred agents being at least two different peroxydisulfates contain.

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

The Bleach amplifiers are in the inventive, cosmetic agents preferably in amounts of 5 to 30 wt .-%, in particular in amounts of 8 to 20 wt .-%, each based on the weight of ready to use agent, included.

Farther it has proved to be advantageous if the inventive Dyeing and / or brightening agent nonionic surfactant Contain substances.

Such surfactants having an HLB of 5.0 and greater are preferred. For the definition of the HLB value, express reference is made to the remarks in Hugo Janistyn, Handbook of Cosmetics and Fragrances, III. Volume: The personal care products, 2nd edition, Dr. med. Alfred Hüthig Verlag Hei delberg, 1973, pages 68-78 and Hugo Janistyn, Paperback of modern perfumery and cosmetics, 4th edition, Scientific Publishing Company mb H. Stuttgart, 1974, pages 466-474 , as well as the original works cited therein.

Especially preferred nonionic surfactants are because of the ease of processing substances that are commercially available as solids or liquids in pure form are. The definition of purity refers to this Not related to chemically pure compounds. Rather, especially when it comes to natural products is used, mixtures of different homologues, for example with different alkyl chain lengths, as with products Base of natural fats and oils are obtained. Even with alkoxylated products are usually mixtures different degrees of alkoxylation. The term purity refers in this context rather to the fact that the selected substances are preferably free of solvents, Adjusting agents and other accompanying substances should be.

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

Preferred nonionic surfactants are

• - Alkoxylated fatty alcohols having 8 to 22, in particular 10 to 16, carbon atoms in the fatty alkyl group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty alkyl groups are, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl groups. Particularly preferred compounds of this class are, for example, lauryl alcohol with 2 to 4 ethylene oxide units, oleyl and cetyl alcohol with 5 to 10 ethylene oxide, cetyl alcohol and stearyl alcohol and mixtures thereof with 10 to 30 ethylene oxide units and the commercial product Aethoxal ^® B (Henkel), Lauryl alcohol with 5 ethylene oxide and 3 propylene oxide units. In addition to the usual alkoxylated fatty alcohols, so-called "end-capped" compounds can also be used according to the invention. In these compounds, the alkoxy group at the end of no OH group, but is in the form of an ether, in particular a C1-C4-alkyl ether, "closed". An example of such a compound is the commercially available product ^® Dehypon LT 054, a C _12-18 -Fettalkoholol + 4.5 ethylene oxide-butyl ether.
• - alkoxylated fatty acids having 8 to 22, in particular 10 to 16, carbon atoms in the fatty acid group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty acids are, for example, lauric, myristic, palmitic, stearic, isostearic and oleic acids.
• - alkoxylated, preferably propoxylated and especially ethoxylated, mono-, di- and triglycerides. Examples of preferred compounds are glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide.
• Polyglycerol esters and alkoxylated polyglycerol esters. Preferred compounds of this class are for example poly (3) glycerol diisostearate (commercial product: Lameform ^® TGI (Henkel)) and poly (2) glycerinpolyhydroxystearat (commercial product: Dehymuls ^® PGPH (Henkel)).
• Sorbitan fatty acid esters and alkoxylated sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monolaurate + 20 ethylene oxide (EO).
• - Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15, carbon atoms in the alkyl chain and 0 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 4 EO, nonylphenol + 9 EO, octylphenol + 3 EO and octylphenol + 8 EO.

Especially preferred classes of nonionic surfactants Substances are the alkoxylated fatty alcohols that alkoxylated Fatty acids and the alkylphenols and alkylphenol alkoxylates represents.

When have particularly advantageous according to the invention Proved to be the non-ionic surfactants contained in amounts of 1-5 wt .-%.

Farther the dyeing and / or lightening agent all known in such preparations active, Additives and auxiliaries included. In many cases included the agents at least one surfactant, where in principle both anionic as well as zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proven to be advantageous The surfactants from anionic, cationic or nonionic Select surfactants. Anionic surfactants can be particularly preferred.

Preferred anionic surfactants are alkyl sulfates, ether carboxylic acid salts having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule such as C 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 in solid, in particular powder form available. Very particularly preferred are at room temperature solid soaps, in particular sodium stearate. These are preferred in amounts of 5 to 20 wt .-%, in particular 10 to 15 wt .-%, before.

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

Examples for in the hair treatment compositions according to the invention Usable cationic surfactants are especially quaternary Ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, Dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, z. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic used according to the invention Surfactants are the quaternized protein hydrolysates.

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

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

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

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

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl-ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazolinium-methochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Malein-säureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• – Strukturanten wie Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• – quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genusssäuren und Basen,
• – Wirkstoffe wie Panthenol, Pantothensäure, Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• – Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennnessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Rosskastanie, Sandelholz, Wacholder, Kokosnuss, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine, Fettalkohole und Fettsäureester,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien,

enthaltenFurthermore, the dyeing and / or brightening agents according to the invention may contain further active ingredients, auxiliaries and additives, such as

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers, quaternary group polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• Zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• Anionic polymers, for example polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Fiber-structure-improving active substances, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• Quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• Defoamers like silicones,
• Dyes for staining the agent,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, for example customary acids, in particular edible acids and bases,
• - active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as extracts of green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, melissa, 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 alcohols and fatty acid esters,
• Fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizer for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants,

contain

With regard to further optional components 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 the cosmetics, 2nd edition, Hüthig book publishing house, Heidelberg, 1989 , referenced.

The Selection of these other substances will be apparent to those skilled in the art according to desired properties of the agents meet.

The agents according to the invention may contain the ingredients in a suitable aqueous, alcoholic or aqueous-alcoholic Carrier included. For the purpose of hair coloring are such carriers, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as Shampoos, foam aerosols or other preparations intended for the application on the hair are suitable. But it is also possible a powdery or tablet-shaped To provide formulation, what dyeing and / or Lightening agent is preferred.

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

preferred Means according to the invention are characterized that they additionally contain a nonaqueous solvent contain, with particularly preferred inventive Means the solvent in a concentration of 0.1-30 Percent by weight, preferably in a concentration of 1-20 Percent by weight, most preferably in one concentration from 2 to 10% by weight, based in each case on the composition.

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

Of the pH of the compositions of the invention can by suitable ingredients such as acidifiers or alkalizers be adjusted in a wide range.

A oxidative staining of the fibers may be in the presence of oxidation dye precursors always done with atmospheric oxygen. It is preferred However, a chemical oxidizing agent used, especially then, if in addition to the coloring a whitening effect on human Hair is desired. This whitening effect can be independent be desired from the staining method. The presence of oxidation dye precursors is therefore not mandatory Prerequisite for the use of oxidants in the agents according to the invention. As oxidizing agent come persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate in question.

According to the invention but also the oxidation dye along with one Catalyst can be applied to the hair, the oxidation of the Dye precursors, eg. B. by atmospheric oxygen activated. Such Catalysts are z. As 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.

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

Suitable enzymes are z. As peroxidases, which 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, for. B.

• - pyranose oxidase and z. D-glucose or galactose,
• Glucose oxidase and D-glucose,
• - glycerol oxidase and glycerin,
• Pyruvate oxidase and pyruvic acid or its salts,
• Alcohol oxidase and alcohol (MeOH, EtOH),
• Lactate oxidase and lactic acid and their salts,
• Tyrosinase oxidase and tyrosine,
• Uricase and uric acid or their salts,
• - choline oxidase and choline,
• - amino acid oxidase and amino acids.

at An application of oxidants becomes the actual colorant expediently immediately before use by mixing the preparation of the oxidizing agent with the preparation, containing the compounds of the formula (Ia) and, if appropriate, dye precursors, produced. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Particularly preferred is the application of the hair dye in a slightly alkaline environment. The application temperatures can range between 15 and 40 ° C. After a contact time of 5 to 45 minutes, the hair dye by rinsing away from the hair to be dyed. The washing with a shampoo is eliminated if a strong surfactant-containing carrier, for. B. a dyeing shampoo, has been used.

Especially with hair that is difficult to color, 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 is then rinsed and nachshampooniert if desired. 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, first an air oxidation is desired, wherein the applied agent be 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 agents according to the invention the hair becomes the coloring and / or brightening agent immediately mixed with a hydrogen peroxide solution before application. The concentration of this hydrogen peroxide solution is on the one hand by the legal requirements and on the other hand by the determines the desired effect; usually 6- to 12 percent solutions used in water. The proportions of coloring and / or brightening agent and hydrogen peroxide solution are usually in the range 1: 1 to 1: 2, wherein an excess of hydrogen peroxide solution in particular is then chosen, if not too pronounced Blondierwirkung is desired.

additionally the agents according to the invention can be further Contain ingredients. A use of certain metal ions or For example, complexes may be preferred to provide intense colorations to obtain. Here are means according to the invention preferably, additionally Cu, Fe, Mn, Ru ions or Complexes of these ions contain.

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

According to the invention preferred is also the use of so-called complexing agents. Complex images are Substances that can complex metal ions. preferred Complexing agents are so-called chelate complexing agents, ie substances, which form cyclic compounds with metal ions, wherein a single Ligand occupies more than one coordination site on a central atom, d. H. at least "bidentate". In this Traps are thus usually stretched compounds through complex formation over closed an ion to rings. The number of bound ligands depends on the coordination number of the central ion.

common and in the context of the present invention, preferred chelate complex images For example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and hydroxyethanediphosphonic acids or their alkali metal salts. Also complexing polymers, ie polymers, either in the main chain itself or side by side to carry functional groups that can act as ligands and with suitable metal atoms usually under formation of Chelate complexes react, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can come from only one macromolecule or belong to different polymer chains. The latter leads to the networking of the material, provided that the complexing Polymers have not previously been crosslinked via covalent bonds were.

complexing Groups (ligands) of conventional complex-forming polymers are Iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, Dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and crown ether radicals with z. T. very specific. Activities towards ions different metals. Many base polymers are also commercially available important complexing polymers are polystyrene, polyacrylates, Polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethylenimines. Also natural polymers like cellulose, starch or chitin are complexing polymers. Furthermore these can be prepared by polymer-analogous transformations with others Ligand functionalities are provided.

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

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

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

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

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

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

When Polycarboxylic acids a) are used in this patent application Carboxylic acids - including monocarboxylic acids - understood, where the sum of carboxyl and contained in the molecule Hydroxyl groups is at least 5. Complexing agent the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. In the invention required alkaline pH values of the treatment solutions are these Chelating agents at least partially as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts become. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, especially sodium salts.

As well are further preferred complexing agents polymeric aminodicarboxylic acids, to mention their salts or their precursors. Especially Preference is given to polyaspartic acids or their salts and Derivatives, in addition to Cobuilder properties also a bleach-stabilizing Have effect.

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

A provide another substance class with complexing properties the phosphonates. These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt alkaline (pH 9). When Aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologs in question. They are preferably in shape the neutral reacting sodium salts, eg. B. as hexasodium salt the EDTMP or as Hepta- and Octa sodium salt of DTPMP used. As a complexing agent is preferred from the class of phosphonates HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it may, in particular if the agents also contain bleach, it is preferable to use aminoalkanephosphonates, DTPMP in particular, or mixtures of the above To use phosphonates. These substances will be described below.

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

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

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

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

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

wobei bevorzugte Mittel Phosphonate, vorzugsweise Hydroxyalkan- bzw. Aminoalkanphosphonate und insbesondere 1-Hydroxyethan-1,1-diphosphonat (HEDP) bzw. dessen Di- oder Tetranatriumsalz und/oder Ethylendiamintetramethylenphosphonat (EDTMP) bzw. dessen Hexanatriumsalz und/oder Diethylentriaminpentamethylenphosphonat (DTPMP) bzw. dessen Hepta- oder Octanatriumsalz, enthalten.From the above-mentioned groups of substances, some representatives are particularly preferred in the context of the present invention. Particularly preferred according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers 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 diethylene triamine pentamethylene phosphonate (DTPMP) or its hepta- or octa-sodium salt.

preferred agents according to the invention become water-poor or formulated anhydrous.

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

wobei

• – der Rest R1 steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, die gegebenenfalls einen Substituenten tragen kann, der mindestens ein Stickstoffatom und gegebenenfalls eine positive Ladung aufweist, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Monohydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe oder eine Di-(C₁ -C₆-alkyl)amino-C₂-C₆-alkylgruppe,
• – die Reste R2 und R3 stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, die gegebenenfalls einen Substituenten tragen kann, der mindestens ein Stickstoffatom und gegebenenfalls eine positive Ladung aufweist, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Monohydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, ein Halogenatom, eine Carboxylgruppe, eine Nitrilgruppe, eine Carbamoylgruppe, eine Sulfonamidogruppe, eine Carboxamidogruppe, eine C₁-C₆-Alkyloxycarbonylguppe, eine Sulfonsäuregruppe, eine Hydroxygruppe, eine Aminogruppe, eine Mono-(C₁-C₆-alkyl)aminogruppe, eine Di-(C₁-C₆-alkyl)aminogruppe oder die beiden Reste R2 und R3 bilden gemeinsam einen 6-gliedrigen aromatischen, carbozyklischen oder heterozyklischen anellierten Ring, welcher gegebenenfalls weitere Substituenten tragen kann und
• – der Rest K steht für eine Gruppierung -NR6R7, wobei die Reste R6 und R7 stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, die gegebenenfalls einen Substituenten tragen kann, der mindestens ein Stickstoffatom und gegebenenfalls eine positive Ladung aufweist, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Hydroyxalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe oder eine Di-(C₁-C₆-alkyl)amino-C₂-C₆-alkylgruppe.

mit der Maßgabe, dass mindestens einer der Reste R1, R2, R3, R5, R6 und/oder R7 eine kationische Ladung aufweist.Since some of the compounds of the formula (I) according to the invention have not hitherto been described in the literature, a second subject of the present invention comprises the cationic compounds of the formula (Ia)

in which

• The radical R ₁ is a hydrogen atom, a C ₁ -C ₆ -alkyl group which may be a substituent which has at least one nitrogen atom and optionally a positive charge, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy C ₂ -C ₆ alkyl group or a di (C ₁ -C ₆ alkyl) amino C ₂ -C ₆ alkyl group,
• - The radicals R2 and R3 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group which may optionally bear a substituent which has at least one nitrogen atom and optionally a positive charge, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ monohydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C ₁ -C ₆ alkoxy, halogen, carboxyl, nitrile, carbamoyl, sulfonamido, carboxamido, C ₁ -C ₆ Alkyloxycarbonyl group, a sulfonic acid group, a hydroxy group, an amino group, a mono (C ₁ -C ₆ alkyl) amino group, a di (C ₁ -C ₆ alkyl) amino group or the two radicals R 2 and R 3 together form a 6 -membered aromatic, carbocyclic or heterocyclic fused ring, which may optionally bear further substituents, and
• - the radical K is a grouping -NR6R7, wherein the radicals R6 and R7 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group which may optionally bear a substituent which has at least one nitrogen atom and optionally a positive charge , a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group or a di- (C ₁ -C ₆ -alkyl) -amino group C ₂ -C ₆ alkyl group.

with the proviso that at least one of R1, R2, R3, R5, R6 and / or R7 has a cationic charge.

In terms of the inventively preferred representative of this Subject of the present invention is explicit at this point to the statements in the context of the second embodiment of the first article. The said there applies to this Place mutatis mutandis.

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

A third object of the present invention is a process for dyeing and optionally simultaneously lightening keratin fibers, in particular human hair, in which

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

The Accordingly, agents according to the invention can be used as one-component agent (coloring and brightening agent M2), as a two-component agent (M2 + M3) or as a three-component agent (M2 + M3 + M4) and applied accordingly. A Separation in multicomponent systems is particularly useful there where to expect incompatibilities of the ingredients or to be feared; the means to be used becomes in such systems by the consumer right before the application through Mixing the components produced.

One Dyeing and whitening process in which the whitening cream and the oxidizing agent is initially separate preferred. Another object of the present invention is therefore a method of dyeing and lightening human Hair, in which an aqueous-based composition, containing hydrogen peroxide, with an inventive Means mixed into a homogeneous composition, and this on the hair is applied.

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

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

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

In terms of further preferred embodiments of the invention Method applies mutatis mutandis to the invention Means said.

Especially it is preferred to color by physical means to support. Inventive method, in which the application by the action of heat and / or Supports UV radiation during the exposure time is, are hereby particularly preferred.

One Fourth object of the present invention is the use of compounds of the formula (I) for coloring and, if appropriate simultaneous whitening of keratinic fibers.

• – Steigerung der Echtheitseigenschaften der Färbungen und/oder
• – Steigerung der Farbbrillanz und/oder
• – Steigerung der Hautverträglichkeit von Färbe bzw. Aufhellmitteln.

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

• Increasing the fastness properties of the dyeings and / or
• - Increase color brilliance and / or
• - Increase the skin compatibility of dye or brightening agents.

In terms of further preferred uses according to the invention mutatis mutandis, the one that applies to the preferred means applies.

Examples

1 Synthesis Examples:

1.1 Synthesis Example 1: Synthesis of 1- (1H-1,2,3-benzotriazol-5-yldiazenyl) -2-naphthol

1.1.1 Diazotization

13.4 g (0.10 mol) of 5-aminobenzotriazole were semi-concentrated in 60 ml Dissolved hydrochloric acid and cooled to 0 to 5 ° C. To this was added 6.9 g (0.10 mol) of sodium nitrite while cooling dissolved in 50 ml of water added dropwise. After completion of the Dropping was stirred for an additional 15 minutes.

1.1.2 Azocoupling

After completion of the diazotization, the diazonium salt solution was transferred to a coolable dropping funnel and added dropwise with cooling to 14.4 g (0.10 mol) of 2-naphthol, which had been dissolved in 120 ml of 10% aqueous sodium hydroxide solution. After completion of the dropwise addition, stirring was continued for a further 30 minutes. Over time, a fine crystal slurry formed, which was diluted with water so that a stirrable suspension was formed. With dilute hydrochloric acid, a pH of 6 was set, the solid was filtered off and dried in vacuo.
Yield: 10.3 g (37%)
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 6.45 (d, 1H); 7.43 (m, 1H); 7.60 (m, 1H); 7.77 (d, 1H); 7.94 (d, 1H); 7.99 (m, 1H); 8.04 (d, 1H); 8.32 (s, 1H); 8,59 (m, 1H)
¹³ C-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 106.1; 116.6; 117.0; 121.3; 123.0; 125.6; 127.8; 128.7; 128.8; 129.2; 132.5; 139.0; 139.1; 144.0; 165.7

2 coloration examples:

2.1 Preparation of the coloring creams

The following coloring creams were prepared: 2.1.1 Nonionic coloring cream Hydrenol ^® D 6.0 g Lorol ^® (technical) 6.0 g Eumulgin ^® RH 40 1.0 g Eumulgin ^® B1 3.0 g Eumulgin ^® B2 3.0 g PHB Methylester 0.3 g PHB propyl 0.2 g phenoxyethanol 1.0 g Polydiol ^® 400 5.0 g direct Dyes 1.0 g ammonium sulfate 1.0 g (in 30.0 g of water) Natrosol ^® 250 HR 1.0 g (in 15.0 g of water) NaOH 0.1% pH value adjustment water ad 100 g

The first nine components were melted together at 80 ° C, after which the dye was added. This mixture was emulsified with a solution of the ammonium sulfate in 30 g of water. Then, a swelling of 1.0 g Natrosol 250 HR ^® was added in 15.0 grams of water. The pH stated in Table 2 was adjusted with 0.1% sodium hydroxide solution, then made up to 100 g with water. 2.1.2 Cationic Dyeing Cream Stenol ^® 16/18 4.0 g Eumulgin ^® B1 1.0 g Dehyquart® ^® A-CA 2.0 g ammonium sulfate 1.0 g (in 30.0 g of water) direct Dyes 1.0 g water ad 100 g

The Stenol ^® 16/18 was melted together with Eumulgin ^® B1 and Dehyquart ^® A-CA, the melt was then emulsified with hot water. Then, the dye and the aqueous ammonium sulfate solution were added. The pH was with ammonia bwz. Citric acid was adjusted to the value given in the table, then it was made up to 100 g with water. 2.1.3 Anionic dye cream Hydrenol ^® D 1.0 g Lorol® ^® techn. 1.0 g Akypo Soft ^® RLM 45N 1.1 g PHB propyl 0.1 g PHB Methylester 0.1 g ammonium sulfate 1.0 g (in 30.0 g of water) Direct drawers DZ 1.0 g water ad 100 g

The first five components were melted together. This melt was emulsified with hot water, then the water-dissolved or predispersed dye was added and the ammonium sulfate solution was added. The pH stated in the table was adjusted with ammonia or citric acid, then made up to 100 g with water. 2.2 List of raw materials used Akypo RLM 45 NV ^® Lauryl alcohol 4.5 EO acetic acid sodium salt (at least 22% active ingredient content, INCI name: sodium laureth-5 carboxylates) (Chem-Y) Dehyquart® ^® A-CA Trimethylhexadecylammonium chloride (about 24-26% active ingredient, INCI name: Aqua (Water), Cetrimonium Chloride) (Cognis) Eumulgin ^® B1 Cetylstearyl alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis) Eumulgin ^® B2 Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis) Eumulgin ^® RH 40 hardened castor oil with approx. 40 EO units (INCI name: PEG-40 Hydrogenated Castor Oil) (Cognis) Hydrenol ^® D C _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis) Lorol (techn.) ^® C _12-18 fatty alcohol (INCI name: Coconut Alcohol) (Cognis) Natrosol ^® 250 HR Hydroxyethylcellulose (INCI name: Hydroxyethylcellulose) (Hercules) Polydiol ^® 400 Polyethylene glycol (INCI name: PEG-8) (Cognis) Stenol ^® 1618 C _16-18 fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis)

2.3 colorations

Each 1.8 g of the dyeing cream were applied to an approximately 6 cm long strand of human hair (Kerling Euronaturhaar, blond) and left there for 30 minutes at 30 ° C. After completion of the exposure time, the hair was rinsed, washed with a conventional shampoo and then dried. The hair tresses were dyed in the shades indicated in Table 2. Table 2: dye coloring cream PH value shade 1- (1H-1,2,3-benzotriazole-5-yldiazenyl) -2-naphthol 1 7.0 orange 1- (1H-1,2,3-benzotriazole-5-yldiazenyl) -2-naphthol 1 9.0 orange 11- (1H-1,2,3-benzotriazole-5-yldiazenyl) -2-naphthol 2 7.0 orange 1- (1H-1,2,3-benzotriazole-5-yldiazenyl) -2-naphthol 2 9.0 orange 1- (1H-1,2,3-benzotriazole-5-yldiazenyl) -2-naphthol 3 7.0 bright orange 1- (1H-1,2,3-benzotriazole-5-yldiazenyl) -2-naphthol 3 9.0 bright orange

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 998908 A2 [0141]

Cited non-patent literature

• - Hugo Janistyn, Handbook of Cosmetics and Fragrances, III. Volume: The personal care products, 2nd edition, Dr. med. Alfred Hüthig Verlag Heidelberg, 1973, pages 68-78 [0207]
• - Hugo Janistyn, Paperback of modern perfumery and cosmetics, 4th edition, Scientific Publishing Company mb H. Stuttgart, 1974, pages 466-474 [0207]
• - Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989 [0222]

Claims (10)

Agent for dyeing and, if appropriate, simultaneous lightening of keratin fibers, in particular human hair, containing at least one compound of the formula (I):

where R ₁ is a hydrogen atom, a C ₁ -C ₆ -alkyl group which may optionally bear a substituent which has at least one nitrogen atom and optionally a positive charge, a C ₂ -C ₆ -alkenyl group, a C ₂ - C ₆ monohydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C ₁ -C ₆ alkoxy C ₂ -C ₆ alkyl or di (C ₁ -C ₆ alkyl) amino C ₂ -C ₆ R 2 and R 3 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group which may optionally bear a substituent which has at least one nitrogen atom and optionally a positive charge, a C ₂ -C ₆ -alkyl group. Alkenyl, C ₂ -C ₆ monohydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C ₁ -C ₆ alkoxy, halogen, carboxyl, nitrile, carbamoyl, sulfonamido, carboxamido, C ₁ -C ₆ alkyloxycarbonyl group, a sulfonic acid group, a hydroxy group, an amino group, a mono- (C ₁ -C ₆ alkyl) amino group, a di (C ₁ -C ₆ alkyl) amino group or the two radicals R 2 and R 3 together form a 6-membered aromatic, carbocyclic or heterocyclic fused ring, which may optionally carry further substituents and - the radical K is a group -OR5 or a grouping -NR6R7, wherein the radicals R5 or R6 and R7 are each independently a hydrogen atom, a C ₁ -C ₆ alkyl group which may optionally bear a substituent having at least one nitrogen atom and optionally a positive charge, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl, a C ₁ -C ₆ alkoxy-C ₂ -C _6- alkyl group or a di- (C ₁ -C ₆ alkyl) amino-C ₂ -C ₆ alkyl group. Dyeing agent and optionally simultaneous Lightening keratinic fibers according to claim 1, characterized in that that it contains at least one compound of the formula (I), wherein the radical R1 is a hydrogen atom or a methyl group stands. Dyeing agent and optionally simultaneous Lightening keratinic fibers according to any one of claims 1 or 2, characterized in that it is a compound of formula (I), in which exactly one of the radicals R1, R2, R3, R5, R6 and / or R7 stands for a cationic group. An agent for dyeing and optionally simultaneously brightening keratinic fibers according to any one of claims 1 to 3, characterized in that it contains a compound of formula (I), wherein at least one of the radicals R1, R2, R3, R5, R6 and / or R7 is selected for a group

Dyeing agent and optionally simultaneous Lightening keratinic fibers according to any one of claims 1 to 4, characterized in that it is a compound of formula (I), wherein the radical K is a Group -OR5, which is in p position to the azo group. Dyeing agent and optionally simultaneous Lightening keratinic fibers according to any one of claims 1 to 4, characterized in that it is a compound of formula (I), wherein the radical K is a Group -OR5, which is in o-position to the azo group. Dyeing agent and optionally simultaneous Lightening keratinic fibers according to any one of claims 1 to 4, characterized in that it is a compound of formula (I), wherein the radical K is a group -NR6R7, which is in p position to the azo group. Cationic compounds of the formula (Ia)

where R ₁ is a hydrogen atom, a C ₁ -C ₆ -alkyl group which may optionally bear a substituent which has at least one nitrogen atom and optionally a positive charge, a C ₂ -C ₆ -alkenyl group, a C ₂ - C ₆ monohydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C ₁ -C ₆ alkoxy C ₂ -C ₆ alkyl or di (C ₁ -C ₆ alkyl) amino C ₂ -C ₆ R 2 and R 3 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group which may optionally bear a substituent which has at least one nitrogen atom and optionally a positive charge, a C ₂ -C ₆ -alkyl group. Alkenyl, C ₂ -C ₆ monohydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C ₁ -C ₆ alkoxy, halogen, carboxyl, nitrile, carbamoyl, sulfonamido, carboxamido, C ₁ -C ₆ alkyloxycarbonyl group, a sulfonic acid group, a hydroxy group, an amino group, a mono- (C ₁ -C ₆ alkyl) amino group, a di (C ₁ -C ₆ alkyl) amino group or the two radicals R 2 and R 3 together form a 6-membered aromatic, carbocyclic or heterocyclic fused ring, which may optionally bear further substituents and - the radical K is a grouping -NR6R7, wherein the radicals R6 and R7 are each independently a hydrogen atom, a C ₁ -C ₆ alkyl group which may optionally bear a substituent which has at least one nitrogen atom and optionally a positive charge, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group or a di- (C ₁ -C ₆ -alkyl) amino-C ₂ -C ₆ -alkyl group, with the proviso that at least one of the radicals R 1, R _2, R 3, R 5, R ₆ and / or R 7 has a cationic charge. Method of dyeing and optionally simultaneous lightening of keratin fibers, especially human Hair, characterized in that - if desired a pretreatment agent M1 is applied to the fiber, then - one Means M2 is applied to the fiber, if desired the agent M2 before use another agent M3 added becomes, - this means M2 after a time of 5-30 Rinsed for a few minutes from the fiber - and after treatment optionally an aftertreatment agent M4 applied to the fiber and after a contact time of some Rinsed off again for a few minutes, where at least one the means M1, M2 or M3 means according to one of the claims 1 to 8 is. Use of compounds of the formula (I) for coloring and optionally simultaneous brightening of keratinic fibers.