DE102010038714A1 - Composition, useful for coloring keratin fibers, preferably human hair, comprises a cationic 1-(3-amino-benzyl)-4-aza-1-azonia-bicyclo(2.2.2)octane phenylamine compound as developer component, in a carrier - Google Patents

Abstract

Composition comprises at least one cationic 1-(3-amino-benzyl)-4-aza-1-azonia-bicyclo[2.2.2]octane phenylamine compound (I) as developer component, in a carrier. Composition comprises at least one cationic 1-(3-amino-benzyl)-4-aza-1-azonia-bicyclo[2.2.2]octane phenylamine compound of formula (I) or its salts as developer component, in a carrier. Y1 : amino, OH, NR2H or NR2R3; R1 : H, 1-6C-alkyl, 2-6C-alkenyl, 1-6C-hydroxyalkyl, 2-6C-polyhydroxyalkyl, halo (such as Cl, Br, F or I), 1-6C-alkoxy, hydroxy-2-6C-alkoxy or 1-6C-alkoxy-2-6C-alkyloxy; R2, R3 : 1-6C-alkyl, 2-6C-alkenyl, 1-6C-hydroxyalkyl, 2-6C-polyhydroxyalkyl or 1-6C-alkoxy-2-6C-alkyl; and X ->monovalent anion, preferably halide, hydrogen sulfate, 1/2 sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methane sulfate or methane sulfonate. An independent claim is included for the compound (I). [Image].

Description

The present invention relates to agents for coloring keratinic fibers containing specific p-phenylenediamine derivatives and / or p-aminophenol derivatives having a cationic grouping of 1,4-diazabicyclo [2.2.2] octane, a process for dyeing hair with these agents, the Use of these p-phenylenediamine derivatives and / or p-Aminophenolderviate in oxidative colorants and the derivatives themselves.

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

The developer components are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives ,

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-carboxyamido-4-amino-pyrazolone-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy -4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2-hydroxyethyl) -N , N'-bis (4-aminophenyl) -diamino-propan-2-ol.

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

Good oxidation dye precursors are primarily intended to meet the following requirements: They must form the desired color shades in sufficient intensity and authenticity in the oxidative coupling. You must also have a good Aufziehvermögen on the fiber, especially in human hair no significant differences between strained and freshly regrowed hair may exist (leveling ability). Another important aspect in the development of hair dyes is the quality of the gray coverage of the agents.

They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, eg. B. permanent wave fluids. Finally, if applied as a hair dye, they should not stain the scalp too much and above all they should be safe in terms of toxicology and dermatology. Furthermore, the coloring achieved by bleaching should be easily removed from the hair, if it does not meet the individual wishes of each person and should be reversed.

But with a developer component or a special coupler / developer combination, it is usually not possible to obtain a natural color shade on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used. There is therefore a constant need for new, improved dye components which are unproblematic in terms of toxicology and dermatology.

The object of the present invention was therefore to develop new developer components which meet the requirements imposed on oxidation dye precursors, in particular with regard to the toxicological and dermatological properties, and allow dyeings in the natural sound range with good performance properties.

Surprisingly, it has now been found that specific p-phenylenediamine derivatives and / or p-aminophenol derivatives which carry a cationic grouping of 1,4-diazabicyclo [2.2.2] octane, fulfill the requirements placed on developer components to a high degree. The invention Developer components enable the production of rich and intense nuances, especially in the field of natural tones, which are characterized by very good fastness properties.

in der
Y steht für eine Aminogruppe, eine Hydroxygruppe, eine Gruppe -NR²H oder eine Gruppe -NR²R³,
R¹ steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, ein Halogenatom (Cl, Br, F oder J), eine C₁-C₆-Alkoxygruppe, eine Hydroxy-C₂-C₆-alkoxygruppe oder eine C₁-C₆-Alkoxy-C₂-C₆-alkyloxygruppe,
R², R³ stehen unabhängig voneinander für eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe oder eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe,
X^– steht für ein einwertiges Anion, vorzugsweise für Halogenid, Hydrogensulfat, ½ Sulfat, p-Benzolsulfonat, p-Toluolsulfonat, Acetat, Citrat, Lactat, Tetrafluoroborat, Trifluormethansulfonat, Hexafluorophosphat, Methansulfat oder Methansulfonat.A first subject of the present invention are therefore agents for coloring keratinic fibers, which in a cosmetically acceptable carrier as the developer component at least one p-phenylenediamine derivative and / or p-aminophenol derivative of the formula (I)

in the
Y is an amino group, a hydroxy group, a group -NR ² H or a group -NR ² R ³ ,
R ¹ represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a halogen atom (Cl, Br, F or J), a C ₁ -C ₆ -alkoxy group, a hydroxy-C ₂ -C ₆ -alkoxy group or a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyloxy group,
R ² , R ³ are each independently a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group or a C ₁ -C _6- alkoxy-C ₂ -C ₆ -alkyl group,
X ^- is a monovalent anion, preferably halide, hydrogensulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate.

According to the invention, keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair. Although the oxidation dyes according to the invention are primarily suitable for dyeing keratin fibers, in principle, there is nothing to prevent their use in other fields, in particular in color photography.

Since the p-phenylenediamine derivatives or p-aminophenol derivatives according to the invention are amino compounds, the known acid addition salts can be prepared therefrom in the customary manner. All statements of this document and accordingly the scope claimed therefore relate both to the present in free form compounds as well as their physiologically acceptable salts of organic or inorganic acids.

Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred. Very particular preference according to the invention is given to the monohydrochlorides, the dihydrochloride and the trihydrochlorides.

Examples of the C ₁ - to C ₆ -alkyl groups mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl, n-butyl, 2-methylpropyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl , n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl and 2,2-dimethylbutyl. Ethyl and methyl are preferred preferred C ₁ to C ₆ alkoxy groups alkyl groups. A preferred C ₁ to C ₆ alkenyl groups is the allyl group. the groups are methoxy and ethoxy. Furthermore, as preferred examples of a C ₁ to C ₆ monohydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₆ polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. The 2- (hydroxy) ethoxy group and the 3- (hydroxy) propoxy group are examples of particularly preferred hydroxy-C ₂ -C ₆ alkoxy groups. As an example of particularly advantageous C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyloxy groups, the 2- (methoxy) ethoxy group and the 3- (methoxy) propoxy group can be mentioned. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived from the definitions given here.

The p-phenylenediamine derivatives and p-aminophenol derivatives of the formula (I) can be prepared by conventional organic methods. For example, reference is made at this point to the experimental procedures in the context of the embodiments.

The derivatives of the formula (I) according to the invention which have been claimed as developer components have hitherto not been described in the literature, so that there are also no indications of their advantageous properties in the context of oxidative dyeing of keratinic fibers.

It has proved to be preferred according to the invention when the radical R _{1 represents} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a halogen atom (Cl, Br, F or J) or a C ₁ -C ₆ -alkoxy group.

• – Salzen des 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-(2,5-Diamino-4-methylbenzyl)-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-(2,5-Diamino-4-chlorbenzyl)-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-(2,5-Diamino-4-brombenzyl)-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-(2,5-Diamino-4-methoxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-(2,5-Diamino-4-ethoxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-[5-Amino-2-(methylamino)benzyl]-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-[5-Amino-2-(dimethylamino)benzyl]-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-[2-(Allylamino)-5-aminobenzyl]-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-[2-(Diallylamino)-5-aminobenzyl]-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-{5-Amino-2-[(2-hydroxyethyl)amino)benzyl}-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-{5-Amino-2-[bis(2-hydroxyethyl)amino]benzyl}-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-(5-Amino-4-chlor-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-(5-Amino-4-brom-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-(5-Amino-4-methoxy-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octans
  
• – Salzen des 1-(5-Amino-4-ethoxy-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octans
  

Within the scope of a particularly preferred embodiment, the agents according to the invention for dyeing keratinic fibers comprise at least one novel developer component selected from

• - Salts of 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- (2,5-diamino-4-methylbenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- (2,5-diamino-4-chlorobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- (2,5-diamino-4-bromobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- (2,5-diamino-4-methoxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- (2,5-diamino-4-ethoxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- [5-amino-2- (methylamino) benzyl] -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- [5-amino-2- (dimethylamino) benzyl] -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- [2- (allylamino) -5-aminobenzyl] -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- [2- (diallylamino) -5-aminobenzyl] -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- {5-amino-2 - [(2-hydroxyethyl) amino) benzyl} -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- {5-amino-2- [bis (2-hydroxyethyl) amino] benzyl} -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- (5-amino-4-chloro-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- (5-amino-4-bromo-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- (5-amino-4-methoxy-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane
  
• - Salts of 1- (5-amino-4-ethoxy-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane
  

• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid
• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Bromid
• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Hydrogensulfat
• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Benzolsulfonat
• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, p-Toluolsulfonat
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Bromid
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Hydrogensulfat
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Benzolsulfonat
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, p-Toluolsulfonat

als explizit ganz besonders bevorzugte kationische Entwickler der Formel (I) eine herausragende Stellung ein.Within this group take the connections

• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride
• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, bromide
• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, hydrogen sulfate
• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, benzenesulfonate
• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, p-toluenesulfonate
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, bromide
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, hydrogen sulfate
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, benzenesulfonate
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, p-toluenesulfonate

as explicitly very particularly preferred cationic developer of formula (I) a prominent position.

In addition to the novel developer components of the formula (I), the colorants according to the invention may further comprise at least one coupler component.

Coupler components according to the invention allow 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. Couplers are preferably cyclic compounds which carry on cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups. When the cyclic compound is a six-membered ring (preferably aromatic), said groups are 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,
• – o-Aminophenolderivate, wie beispielsweise o-Aminophenol,
• – 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,

Gemische aus zwei oder mehrer Verbindungen aus einer oder mehrerer dieser Klassen sind im Rahmen dieser Ausführungsform ebenso erfindungsgemäß.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,
• O-aminophenol derivatives, such as o-aminophenol,
• 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, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine Amino-(C₁ bis C₆)-alkylgruppe, eine (C₁ bis C₆)-Dialkylamino-(C₁ bis C₆)-alkylgruppe oder eine (C₁ bis C₆)-Alkoxy-(C₁ bis C₆)-alkylgruppe, wobei G¹ und G² gemeinsam mit dem Stickstoffatom einen fünfgliedrigen, sechsgliedrigen oder siebengliedrigen Ring bilden können,
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, eine (C₁ bis C₆)-Alkyox-(C₂ bis C₆)-alkoxygruppe, eine Arylgruppe oder eine Heteroarylgruppe. 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, a (C ₂ to C ₄₎ -polyhydroxyalkyl group, a (C ₂ to C ₄₎ -Perfluoracylgruppe, an aryl (C ₁ to C ₆₎ alkyl, amino (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) dialkylamino (C ₁ to C ₆ ) alkyl group or a (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl group, wherein G ¹ and G ² together with the nitrogen atom can form a five-membered, six-membered or seven-membered ring,
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, a (C ₁ to C ₆ ) -alkoxy (C ₂ to C ₆ ) alkoxy group, an aryl group or a heteroaryl.

Particularly preferred m-aminophenol coupler components are selected from at least one compound selected from the group consisting of 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 physiologically acceptable salts of all the abovementioned compounds.

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 (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Heteroaryl-(C₁ bis C₄)-alkylgruppe, 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-Diaminophenyloxy)-(C₁ bis C₄)-alkoxygruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Alkoxy-(C₂ bis C₄)-alkoxygruppe, eine Arylgruppe, eine Heteroarylgruppe, 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 ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl group, an aryl (C ₁ to C ₄ ) alkyl group, a heteroaryl (C ₁ to C ₄ ) alkyl 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-diaminophenyloxy) - (C ₁ to C ₄ ) alkoxy group, a (C ₁ to C ₄ ) alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) alkoxy (C ₂ to C ₄ ) alkoxy group, an aryl group, a heteroaryl 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.

Particularly preferred m-diaminobenzene coupler components are selected from at least one compound from the group formed from m-phenylenediamine, 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-hydroxyethylamino] -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-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene and the physiologically acceptable salts of all the abovementioned compounds.

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 (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Heteroaryl-(C₁ bis C₄)-alkylgruppe, 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 ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl group, an aryl (C ₁ to C ₄ ) alkyl group, a heteroaryl (C ₁ to C ₄ ) alkyl 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.

Particularly preferred o-diaminobenzene coupler components are selected from at least one compound selected from the group consisting of 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all of the aforementioned compounds.

Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group 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 Arylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Heteroaryl-(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 hydroxyl group or a group - NG ²¹ G ²² ,
wherein G ²¹ and G ^{22 are} independently 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, an aryl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl group, an aryl (C ₁ to C ₄ ) alkyl group, a heteroaryl (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.

Particularly preferred pyridine derivatives are selected from at least one 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, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiologically 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 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, eine Aryl-(C₁ bis C₄)-alkylgruppe,
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, an aryl (C ₁ to C ₄ ) alkyl 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.

Particularly preferred indole derivatives are selected from at least one compound of the group which is formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable salts of the abovementioned 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, eine Aryl-(C₁ bis C₄)-alkylgruppe,
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, an aryl (C ₁ to C ₄ ) alkyl 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.

Particularly preferred indoline derivatives are selected from at least one 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.

In the following, examples of the radicals mentioned as substituents of the compounds of the formulas (K1) to (K6) are listed: 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 ₃ to C ₆ ) cycloalkyl groups according to the invention are cyclopropyl, cyclopentyl and cyclohexyl.

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

An example of aryl groups is the phenyl group, which may also be substituted.

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

Particularly preferred coupler components according to the invention are selected from m-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol , 5- (2'-Hydroxyethyl) -amino-2-methylphenol, 2,4-dichloro-3- aminophenol, o-aminophenol, m-phenylenediamine, 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-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis - (2'-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2, 6-Dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydro xyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds.

In a most preferred embodiment of the present invention, the colorants contain at least one coupler component selected from 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4 -chloro-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-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-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4 Trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxy pyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene or mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds.

In a further preferred embodiment, the colorants according to the invention contain at least one further developer component.

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 (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 a further 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 radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) -hydroxyalkoxy radical, 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 or (C ₁ to C ₄ ) carbamoylaminoalkoxy;
• - 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, 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.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from one or more compounds of the group which is formed from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine. 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- (p-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.

Very particularly preferred p-phenylenediamine derivatives of the formula (E1) according to the invention 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, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole) 1-yl) propyl] amine, as well as the physiologically acceptable salts of these compounds.

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

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 an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, of one or more nitrogen-containing groups and / or one or more Heteroatoms such as oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may 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 substituents used in formula (E2) are defined according to the invention analogously to the above statements.

Preferred dinuclear developing agents of the formula (E2) are in particular selected from at least one of the following compounds: 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 and their physiologically acceptable salts.

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

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

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

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

Furthermore, the developer component may be selected from heterocyclic developer components, 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 eine 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 is} a hydroxy group 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.

Particularly 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-isopropylpyrazole, 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 ) -polyhydroxyalkyl 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 substituents used in formula (E7) are defined according to the invention analogously 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) can be prepared as described in the literature by cyclization from an aminopyrazole or hydrazine.

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 of 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₎ -Acetylaminoalkoxyreste 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₎ -Cyanoalkylreste 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 .

An 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.

Very particularly preferred developer components are selected from at least one compound from the group formed from 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, as well as the physiologically acceptable salts of these compounds.

• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/5-Amino-2-methylphenol
• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/3-Amino-2-chlor-6-methylphenol
• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/2,4-Dichlor-3-aminophenol
• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/2-(2,4-Diaminophenoxy)ethanol
• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/1,3-Bis(2,4-diaminophenoxy)propan
• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/2-Methylresorcin
• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/2-Amino-3-hydroxypyridin
• – 1-(2,5-Diaminobenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/3-Amino-2-methylamino-6-methoxypyridin
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/5-Amino-2-methylphenol
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/3-Amino-2-chlor-6-methylphenol
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/2,4-Dichlor-3-aminophenol
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/2-(2,4-Diaminophenoxy)ethanol
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/1,3-Bis(2,4-diaminophenoxy)propan
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/2-Methylresorcin
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/2-Amino-3-hydroxypyridin
• – 1-(5-Amino-2-hydroxybenzyl)-4-aza-1-azoniabicyclo[2.2.2]octan, Chlorid/3-Amino-2-methylamino-6-methoxypyridin

The following coupler / developer combinations have proved particularly suitable according to the invention:

• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 5-amino-2-methylphenol
• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 3-amino-2-chloro-6-methylphenol
• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 2,4-dichloro-3-aminophenol
• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 2- (2,4-diaminophenoxy) ethanol
• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 1,3-bis (2,4-diaminophenoxy) propane
• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 2-methylresorcinol
• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 2-amino-3-hydroxypyridine
• - 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 3-amino-2-methylamino-6-methoxypyridine
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 5-amino-2-methylphenol
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 3-amino-2-chloro-6-methylphenol
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 2,4-dichloro-3-aminophenol
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 2- (2,4-diaminophenoxy) ethanol
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 1,3-bis (2,4-diaminophenoxy) propane
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 2-methylresorcinol
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 2-amino-3-hydroxypyridine
• - 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride / 3-amino-2-methylamino-6-methoxypyridine

The hair colorants of the invention contain both the developer components and the coupler components preferably in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total oxidation colorant. In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has been found to be useful, so a certain excess of individual oxidation dye precursors is not detrimental, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , may be included.

In a further embodiment of the present invention, the colorants may contain at least one precursor of a naturally-analogous dye.

The dyestuff precursors of naturally-analogous dyes are preferably indoles and indolines which have at least two groups selected from hydroxyl and / or amino groups, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. B. in the form of a Etherification or esterification of the hydroxy group or alkylation of the amino group. In a further embodiment, the colorants contain at least one indole and / or indoline derivative. Compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – R² steht für Wasserstoff oder eine -COOOH-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 -COOOH 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.

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

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

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 ,

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

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

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

The indoline or the indole derivatives can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the hydrochlorides, sulfates and hydrobromides are used.

The indoline and indole derivatives can be used in the colorants of the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for. As the hydrochlorides, sulfates and hydrobromides are used.

The indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

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

In addition to the cationic developer components of the formula (I) according to the invention, in a further preferred embodiment of the present invention, the colorants according to the invention may contain one or more substantive dyes for shading. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes.

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 disodium 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) azo] 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-sulfonaphthalene) 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 -naphthalene-disulfonic acid trisodium salt (CI 16.185, Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalenedisulfonic acid disodium salt (CI 17, 400; Acid Red 33, Red 33), 5- (acetylamino) -4-hydroxy-3 - [(2-methylphenyl) azo] -2,7-naphthalenedisulfonic acid disodium salt (CI 18.065, Acid Red 35), 2- (3-hydroxy-2,4, 5,7-tetraiodo-dibenzopyran-6-one-9-yl) -benzoic acid disodium salt (CI 45,430; Acid Red 51), N- [6- (Diethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethyl-urethane-ammonium hydroxide, inner salt, sodium salt (CI 45, 100; Acid red 52), 8 - [(4- (phenylazo) phenyl) aro] -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-tetrachloro-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) -xanthen] -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 (CI 14,700, 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 internal 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-cyclohexadiene-1 -ylidene] -N-ethylbenzene methanaminium hydroxide, inner 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) -9.1 0-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, D & C Violet No. 2, Acid Violet 43), bis [3-nitro-4 - [(4-phenylamino) -3-sulfophenylamino] -phenyl] -sulfone (CI 10.410; Acid 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 those under the international 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) -ph enyl] carbenium chloride (C. I. 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-trimethylbenzolaminium 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 oride (C. I. 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 bisulfate ( 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-anthraquinone 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 known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).

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

Nonionic substantive dyes:

Suitable nonionic substantive dyes are in particular nonionic nitro and quinone dyes and neutral azo dyes.

In another classification, the substantive dyes are classified according to their colorations.

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-hydroxyethyl) amino] -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-nitrophenylamino) -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-hydroxyethynamino] -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-nitrophenynamino) 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-nitrobenzo 1 (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-hydroxyethynamino] -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-hydroxyethynamino] - 5-nitrobenzene (HC Yellow 10), 2 - [(2-hydroxyethynamino] -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-hydroxyethynamino] -3- nitrobenzene (HC Yellow 12), 4 - [(2-Hy droxyethyl) 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-hydroxyethynamino] -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-aminoethynamino] -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 Violet 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-hydroxyethynamino] -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 substantive dyes are those under the international 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 HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 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-nitro phenol.

It is not necessary that the substantive dyes each represent uniform compounds. Rather, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing or for other reasons, eg. As toxicological, must be excluded.

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

Furthermore, natural dyes can also be used as substantive dyes. As natural dyes in the context of the invention are dyes to be understood, which are obtained from parts of plants. For this purpose, preferably different parts of plants, depending on the desired dye. It is understood, however, that a dye can be obtained from more than one plant part.

The preferred plant parts for obtaining natural dyes are included in the group formed by root, stems, bark, heartwood, resin, flower, leaf, fruit and sap. For the purposes of the invention it is furthermore not necessary for natural dyes that the agents obtained from the plant parts represent dyes as such, but that they optionally also represent dye precursors which form the actual dye by subsequent chemical reactions. Mentioned here in particular the oxidation with atmospheric oxygen to form the chromophore.

It is not necessary, in particular for the purposes of the invention, that the dyes or dye precursors in each case represent uniform compounds. Due to different, non-uniform extraction methods such as different extraction or fermentation conditions or by using different, regional subspecies and different parts of plants or partly from culture-historical tradition, some natural dyes mentioned deliberately contain no uniform compounds, but mixtures of dyes, dye precursors and other components , in particular tannins.

For the purposes of the invention, a natural dye is, of course, also understood to mean a discrete colorant compound isolated from such a mixture or optionally also a plurality of discrete colorant compounds isolated from such a mixture. Detailed descriptions of the natural dyes can be found inter alia in the handbook of natural dyes known to those skilled in the art: occurrence, use, detection, H. Schweppe, ecomed Verlagsgesellschaft, 1993, Landsberg / Lech.

• a) Diaryloylmethanfarbstoffe, wie beispielsweise in Kurkuma (Gelbwurzel) enthalten (C. I. Natural Yellow 3) – Curcuma domestica mit den färbenden Inhaltsstoffen Curcumin (C. I. 75300), Demethoxycurcumin und Bisdemethoxycurcumin.
  
• b) Naphthochinonfarbstoffe, wie beispielsweise in Henna, rot (C. I. Natural Orange 6) aus den Blättern des Hennastrauchs – Lawsonia inermis L. mit dem färbenden Inhaltsstoff Lawson (C. I. 75480):
  
  in Fruchtschalen und Blättern (C. I. Natural Brown 7) des Walnussbaums – Juglus regia L. mit dem färbenden Inhaltsstoff Juglon (C. I. 75500):
  
  in Alkannawurzel oder Shikoninwurzel (C. I. Natural Red 20) – Alkanna tinctoria beziehungsweise Lithospermum erythrorhizon mit dem färbenden Inhaltsstoffen Alkannan (C. I. 75520) und Alkannin (C. I. 75530) beziehungsweise Shikonin (C. I. 75535):
  
  in Lapachoholz von Tecoma ipé, Tecoma lapacho, Tecoma leucoxylon oder Tecoma achracea (C. I. Natural Yellow 16) mit dem färbenden Inhaltsstoffen Lapachol (C. I. 75490), sowie untergeordnet Desoxylapachol, -Lapachon, -Lapachon, Melchinon I, Lapachononund Dehydro-lapachon:
  
• c) Anthrachinonfarbstoffe, wie beispielsweise in Krapp-Wurzeln (C. I. Natural Red 8) – Rubia peregrina und Rubia tinctorum mit den färbenden Inhaltsstoffen Purpurin (C. I. 75410), Pseudopurpurin (C. I. 75420; C. I. 58220-snythetisch), Alizarin (C. I. 75330), Rubiadin (C. I. 75350) und Munjistin (C. I. 75370):
  
  in den Wurzeln und Stengeln des Indischen Krapp (C. I. Natural Red 16) – Rubia cordifolia und Rubia sikkimensis mit den färbenden Inhaltsstoffen Purpurin (C. I. 75410), Pseudopurpurin (C. I. 75420; C. I. 58220-snythetisch), Alizarin (C. I. 75330), und Munjistin (C. I. 75370) sowie Nordamnacanthal, Physcion und Purpuroxanthin (C. I. 75340):
  
  in Rharbarber-Wurzeln – Rheum undulatum L. Rheum palmatum L. und weitere Rheum-Spezies mit den färbenden Inhaltsstoffen Emodin, Chrystophanol (C. I. 75400; C. I. Natural Yellow 23), Aloeemodin, Physcion, Rhein, den Heterodianthronen Rhéidin A, B, C, Palmidin A, B, C, D und Sennidin C sowie davon abgeleitete Anthra- und Diglykoside:
  
  in den Wurzeln des Echten Labkraut – Galium verum L., Gemeinen Labkraut – Galium mollugo L., Klebkraut – Galium aparine L., Waldmeister – Galium odoratum (C. I. Natural Red 14) mit den färbenden Inhaltsstoffen Purpurin (C. I. 75410), Pseudopurpurin (C. I. 75420; C. I. 58220-snythetisch), Alizarin (C. I. 75330), Rubiadin (C. I. 75350), Purpuroxanthin (C. I. 75340), Lucidin, Alizarin-1-methylether, Alizarin-2-methylether, 2-Hydroxyanthrachinon und 1-Hydroxy-2-methylanthrachinon:
  
  in Färbermeisterwurzel (C. I. Natural Red 13) – Asperula tinctoria mit den färbenden Inhaltsstoffen Purpurin (C. I. 75410), Pseudopurpurin (C. I. 75420; C. I. 58220-snythetisch) und Alizarin (C. I. 75330), in Rinde des Faulbaum – Rhamnus fragula L. tinctoria mit den färbenden Inhaltsstoffen Emodin, 4 Emodin-Glukoside: Glucofragulin A, Glucofrangulin B, Frangulin A, Frangulin B, Physcion und Chrysophanol (C. I. 75400):
  
• d) Indigoide Farbstoffe, wie beispielsweise in den Blättern und teilweise Stengeln des Indischem Indigo – Indigofera tinctoria (Indigofera argentea), Färberwaid – Isatis tinctoria, Färberoleander – Wrightia tinctoria und Wildem Indigo – Baptisia tinctoria (C. I. Natural Blue 1) mit den Farbstoffvorprodukten Isatan B und Indican, welche durch einen Gärungsprozess oxidativ in den eigentlichen Farbstoff Indigo (C. I. 75780; C. I. 73000) sowie untergeordnet Indirubin (C. I. 75790; C. I. 73200) und Isatin überführt werden:
  
  unter anderem unter den Namen Indigofera folium oder Henna, schwarz als Handelsprodukt, zumeist in Kombination mit Extrakten von Lawsonia Inermis, erhältlich,
• e) Flavonoidfarbstoffe, wie beispielsweise in den Blütenköpfen von Römischer Kamille – Chamaemelum nobile (C. I. Natural Yellow 1) und Deutscher Kamille – Chamomilla recutica mit den färbenden Inhaltsstoffen Apigenin (C. I. 75580; C. I. Natural Yellow 1,2), Rutin (C. I. 75730; Natural Yellow 10), sowie untergeordnet Luteolin (C. I. 75590), Kämpferol (C. I. 75460, C. I. Natural Yellow 13, 10) und Quercetin (C. I. 75670; C. I. Natural Yellow 10,13; C. I. Natural Red 1) und davon abgeleitete Glukoside:
  
  in den Blättern und Stengeln von Salbei – Salvia tribola L. mit den färbenden Inhaltsstoffen Luteolin (C. I. 75590) und Salvigenin:
  
  in den Blättern und Stengeln von Rosmarin – Rosmarinus Officinalis mit den färbenden Inhaltsstoffen Luteolin (C. I. 75590) und Apigenin (C. I. 75580; C. I. Natural Yellow 1,2) sowie weiteren Flavonoiden,
• f) Neoflavanoidfarbstoffe, wie beispielsweise in Blauholz (C. I. Natural Black 1), Kernholz von Haematoxylum campechianum L. mit dem färbenden Flavinoid Quercetin und dem Farbstoffvorprodukt Hämatoxylin, welches oxidativ in den Farbstoff Hämatein (C. I. 75290, C. I. Natural Black 1 und 2) umgewandelt wird:
  
  in Sappanholz – Caesalpinia sappan L., Brazilienholz – Caesalpinia brasiliensis L., Nicaraguaholz – Caesalpinia echinata, Pernambunkholz – Caesalpinia crista L., Brasilietteholz – Haematoxylum braziletto, jeweils als Kernholz (C. I. Natural Red 24), mit dem Farbstoffvorprodukt Brasilin, welches oxidativ in den Farbstoff Brasilein (C. I. 75280, C. I. Natural Red 24) umgewandelt wird:
  
• g) unlösliche Rotholz-Farbstoffe, wie beispielsweise in Rotem Sandelholz, Kernholz von Pterocarpus santalinus L. Narraholz – Pterocarpus indicus L., Barholz – Pterocarpus soyauxii L., Camholz – Bahia nitida (C. I. Natural Red 22) mit den färbenden Inhaltsstoffen Santalin A, Santalin B, Tetra-O-methyl-santarubin, Hompterocarpin, Pterocarpin, Maackiain, den Isoflavioniden Formononetin und Santal, sowie dem Chalkon Isoliquiritigenin und dem Flavon Liquiritigenin:
  
• h) Betalainfarbstoffe wie beispielsweise in Rote Beete Wurzeln – Beta vulgaris mit den färbenden Hauptinhaltsstoffen Betanidin und Praebetanin sowie untergeordnet weiteren Betacyaninen, Betaxanthinen, Vulgaxanthinen, Anthocyanen und Eisen- und Kupfer-Komplexen:
  
• i) Gallotanninfarbstoffe wie beispielsweise in der Rinde von Stiel- oder Sommereiche – Quercus robur L. mit den färbenden Hauptinhaltsstoffen aus der Gruppe der Gallotannine und Ellagentannine (Glykoside der Gallussäure beziehungsweise der Ellagsäure; C. I. 75270):
  
• j) Farbstoffe aus kondensierten Gerbstoffen, wie beispielsweise in Catechu (C. I. Natural Brown 3), eine Mischung aus Extrakten von Färbepflanzen, vorzugsweise Acacia catechu, Areca catechu und Uncaria gambier, mit einem hohen Anteil von kondensierten Gerbstoffen (,Proanthocyanidine') vom Catechin-Typ:
  
  wie in den Blättern von grünem und schwarzem (= fermentiertem grünen) Tee – Camellia sinensis, mit den Inhaltsstoffen Gallussäure, m-Digallussäure, Catechin, Glykosiden von Flavonoiden wie, unter anderen, Luteolin, Apigenin, Kämpferol, Quercetin, Myriecetin, sowie Thearubingenine (,Proanthocyanidine'), Theaflavin und Isotheaflavin:
  

The following classes of natural dyes are preferred in the compositions according to the invention as colorants for keratinic fibers:

• a) Diaryloylmethanfarbstoffe, such as in turmeric (Goldenseal) (CI Natural Yellow 3) - Curcuma domestica with the coloring ingredients curcumin (CI 75300), demethoxycurcumin and bisdemethoxycurcumin.
  
• b) Naphthoquinone dyes, such as in henna, red (CI Natural Orange 6) from the leaves of henna - Lawsonia inermis L. with the coloring ingredient Lawson (CI 75480):
  
  in fruit peel and leaves (CI Natural Brown 7) of the walnut tree - Juglus regia L. with the coloring ingredient Juglon (CI 75500):
  
  in alkana root or shikonin root (CI Natural Red 20) - Alkanna tinctoria or Lithospermum erythrorhizon with the coloring ingredients alkannane (CI 75520) and alkanine (CI 75530) or shikonin (CI 75535):
  
  in lapacho wood of Tecoma ipé, Tecoma lapacho, Tecoma leucoxylon or Tecoma achracea (CI Natural Yellow 16) with the coloring constituents lapachol (CI 75490), as well as subordinate desoxylapachol, lapachone, lapachone, melchinone I, lapachonone and dehydro-lapachone:
  
• c) anthraquinone dyes, such as in madder roots (CI Natural Red 8) - Rubia peregrina and Rubia tinctorum with the coloring ingredients purpurin (CI 75410), pseudopurpurine (CI 75420, CI 58220-synthetic), alizarin (CI 75330), rubiadin (CI 75350) and Munjistine (CI 75370):
  
  in the roots and stems of Indian madder (CI Natural Red 16) - Rubia cordifolia and Rubia sikkimensis with the coloring ingredients purpurin (CI 75410), pseudopurpurine (CI 75420, CI 58220-synthetic), alizarin (CI 75330), and munjistine ( CI 75370) as well as Nordamnacanthal, Physcion and Purpuroxanthin (CI 75340):
  
  in Rharbarber roots - Rheum undulatum L. Rheum palmatum L. and other Rheum species with the coloring constituents Emodin, Chrystophanol (CI 75400, CI Natural Yellow 23), Aloeemodin, Physcion, Rhine, the heterodianthrones Rhéidin A, B, C, Palmidin A, B, C, D and sennidine C as well as derived anthra- and diglycosides:
  
  in the roots of the genus Labium - Galium verum L., common labweed - Galium mollugo L., Catchstraw - Galium aparine L., Woodruff - Galium odoratum (CI Natural Red 14) with the coloring ingredients purpurin (CI 75410), pseudopurpurine (CI CI 58220-snythetic), alizarin (CI 75330), rubiadin (CI 75350), purpuroxanthin (CI 75340), lucidin, alizarin 1-methyl ether, alizarin 2-methyl ether, 2-hydroxyanthraquinone and 1-hydroxy-2- methylanthraquinone:
  
  in Dyer's master's root (CI Natural Red 13) - Asperula tinctoria with the coloring ingredients purpurin (CI 75410), pseudopurpurine (CI 75420, CI 58220-synthetic) and alizarin (CI 75330), in bark of the decoy - Rhamnus fragula L. tinctoria with the coloring ingredients Emodin, 4 Emodin-Glucosides: Glucofragulin A, Glucofrangulin B, Frangulin A, Frangulin B, Physcion and Chrysophanol (CI 75400):
  
• d) Indigoid dyes, such as, for example, in the leaves and partial stems of Indian Indigo - Indigo Farmera (Indigofera argentea), Fawnwort - Isatis tinctoria, Dyeing Colanders - Wrightia tinctoria and Wild Indigo - Baptisia tinctoria (CI Natural Blue 1) with the dye precursors Isatan B and Indican, which are oxidatively converted into the actual dye indigo (CI 75780; CI 73000) as well as subordinated indirubin (CI 75790; CI 73200) and isatin by a fermentation process:
  
  under the names Indigofera folium or Henna, black as a commercial product, mostly in combination with extracts from Lawsonia Inermis, available,
• e) flavonoid dyes, such as, for example, in the flower heads of Roman chamomile - Chamaemelum nobile (CI Natural Yellow 1) and German chamomile - Chamomilla recutica with the coloring ingredients apigenin (CI 75580, CI Natural Yellow 1.2), rutin (CI 75730, Natural Yellow 10), as well as subordinated luteolin (CI 75590), kaempferol (CI 75460, CI Natural Yellow 13, 10) and quercetin (CI 75670, CI Natural Yellow 10, 13; CI Natural Red 1) and glucosides derived therefrom:
  
  in the leaves and stems of sage - Salvia tribola L. with the coloring ingredients luteolin (CI 75590) and salvigenin:
  
  in the leaves and stems of rosemary - Rosmarinus officinalis with the coloring ingredients luteolin (CI 75590) and apigenin (CI 75580; CI Natural Yellow 1,2) and other flavonoids,
• f) Neoflavanoidfarbstoffe, such as in wood (CI Natural Black 1), heartwood of Haematoxylum campechianum L. with the coloring flavinoid quercetin and the dye precursor hematoxylin, which is converted oxidatively into hematin dye (CI 75290, CI Natural Black 1 and 2) :
  
  in sappan wood - Caesalpinia sappan L., brazil wood - Caesalpinia brasiliensis L., Nicaraguan wood - Caesalpinia echinata, pernambunk wood - Caesalpinia crista L., braziliette wood - Haematoxylum braziletto, each as heartwood (CI Natural Red 24), with the dye precursor Brasilin, which oxidatively in the colorant is Brasilein (CI 75280, CI Natural Red 24) is converted:
  
• g) insoluble redwood dyes, such as in red sandalwood, heartwood of Pterocarpus santalinus L. Narrawood - Pterocarpus indicus L., Barwood - Pterocarpus soyauxii L., Camwood - Bahia nitida (CI Natural Red 22) with the coloring ingredients Santalin A, Santalin B, Tetra-O-methyl-santarubin, Hompterocarpin, Pterocarpine, Maackiain, the Isoflavioniden Formononetin and Santal, as well as the Chalkon Isoliquiritigenin and the Flavon Liquiritigenin:
  
• h) Betaine dyes such as beetroot roots - Beta vulgaris containing the main coloring constituents betanidine and prebetanine and subordinate further betacyanines, betaxanthines, vulgaxanthines, anthocyanins and iron and copper complexes:
  
• i) Gallotannin dyes as in the bark of stem or Sommereiche - Quercus robur L. with the coloring main ingredients from the group of gallotannins and ellagnetins (glycosides of gallic acid or ellagic acid, CI 75270):
  
• j) condensed tannin dyes, such as in Catechu (CI Natural Brown 3), a mixture of extracts of staining plants, preferably Acacia catechu, Areca catechu and Uncaria gambier, with a high proportion of condensed tannins ('proanthocyanidins') from catechin Type:
  
  as in the leaves of green and black (= fermented green) tea - Camellia sinensis, with the ingredients gallic acid, m-digallic acid, catechin, glycosides of flavonoids such as, among others, luteolin, apigenin, kaempferol, quercetin, myriecetine, and thearubingenins ( Proanthocyanidins), theaflavin and isotheaflavin:
  

In particular, the cosmetic compositions of the invention contain at least one natural dye selected from the group comprising diaryloylmethane dyes, naphthoquinone dyes, flavonoid dyes, anthraquinone dyes, betalain dyes, gallotannin dyes and indigoid dyes.

Particularly preferred natural dyes according to the present invention are those obtained from a plant selected from the group consisting of Indigofera tinctoria, Curcuma longa, Lawsonia inermis, Chamomilla recutita, Quercus robur, Rosmarinus officinalis, Rheum undulatum and Beta vulgaris.

Very particular preference is given to the group which is formed from diaryloylmethane dyes, naphthoquinone dyes and indigoid dyes.

Very particular preference is given in the cosmetic compositions according to the invention to natural dyes of plants which are selected from the group consisting of Curcuma longa (turmeric, CI Natural Yellow 3), Lawsonia inermis (Henna, red, CI Natural Orange 6) and Indigofera tinctoria ( Henna, black, CI Natural Blue 1).

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

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

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

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

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

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

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C₁₂-C₂₂-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – C₆-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga sowie
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl.

Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

• Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• - C ₆ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs and
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil.

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

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

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

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

Particular preference is given to those alkylpolyglycosides in which R ¹

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

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

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1.1 to 1.4.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The person skilled in the art will therefore prefer to use this substance class as a further constituent of the preparations according to the invention in the event that an effect of the perfume oil on the hair which exceeds the duration of the hair treatment is desired.

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

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

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

Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances under the name Tegoamid ^® S 18 commercial stearamidopropyl dimethylamine is.

Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

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

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

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl-ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazolinium-methochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/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 Ölamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• – Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• – Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien,

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

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers, quaternary group polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• Zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• Anionic polymers such as, 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,
• Antidandruff active ingredients such as Piroctone Ölamine, Zink Omadine and Climbazole,
• - light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• - active substances such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root,
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• Fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizer for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants,

contain

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

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

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

The actual oxidative coloring of the fibers can be done basically with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the dyeing Whitening effect on human hair is desired. Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate. According to the invention, however, the oxidation dye can also be applied together with a catalyst on the hair, the oxidation of the dye precursors, for. 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.

The actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures can range between 15 and 40 ° C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is eliminated if a strong surfactant-containing carrier, eg. As a dyeing shampoo was used.

Especially with hair that is difficult to dye, the preparation with the dye precursors can also be applied to the hair 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, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent.

A second subject matter of the present invention is a process for coloring keratinic fibers, in which a hair colorant according to the invention is applied to the fibers and rinsed off again after a contact time.

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

in der
Y steht für eine Aminogruppe, eine Hydroxygruppe, eine Gruppe -NR²H oder eine Gruppe -NR²R³,
R¹ steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, ein Halogenatom (Cl, Br, F oder J), eine C₁-C₆-Alkoxygruppe, eine Hydroxy-C₂-C₆-alkoxygruppe oder eine C₁-C₆-Alkoxy-C₂-C₆-alkyloxygruppe,
R², R³ stehen unabhängig voneinander für eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe oder eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe,
X^– steht für ein einwertiges Anion, vorzugsweise für Halogenid, Hydrogensulfat, ½ Sulfat, p-Benzolsulfonat, p-Toluolsulfonat, Acetat, Citrat, Lactat, Tetrafluoroborat, Trifluormethansulfonat, Hexafluorophosphat, Methansulfat oder Methansulfonat,
als Entwicklerkomponente zur oxidativen Färbung keratinischer Fasern.A third object of the present invention is the use of at least one p-phenylenediamine derivative and / or p-aminophenol derivative of the formula (I)

in the
Y is an amino group, a hydroxy group, a group -NR ² H or a group -NR ² R ³ ,
R ¹ represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a halogen atom (Cl, Br, F or J), a C ₁ -C ₆ -alkoxy group, a hydroxy-C ₂ -C ₆ -alkoxy group or a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyloxy group,
R ² , R ³ are each independently a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group or a C ₁ -C _6- alkoxy-C ₂ -C ₆ -alkyl group,
X ^- is a monovalent anion, preferably halide, hydrogensulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate,
as a developer component for the oxidative coloring of keratinic fibers.

With regard to further preferred embodiments of the use according to the invention, what has been said about the agents according to the invention applies mutatis mutandis.

in der
Y steht für eine Aminogruppe, eine Hydroxygruppe, eine Gruppe -NR²H oder eine Gruppe -NR²R³,
R¹ steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, ein Halogenatom (Cl, Br, F oder J), eine C₁-C₆-Alkoxygruppe, eine Hydroxy-C₂-C₆-alkoxygruppe oder eine C₁-C₆-Alkoxy-C₂-C₆-alkyloxygruppe,
R², R³ stehen unabhängig voneinander für eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe oder eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe,
X^– steht für ein einwertiges Anion, vorzugsweise für Halogenid, Hydrogensulfat, ½ Sulfat, p-Benzolsulfonat, p-Toluolsulfonat, Acetat, Citrat, Lactat, Tetrafluoroborat, Trifluormethansulfonat, Hexafluorophosphat, Methansulfat oder Methansulfonat.The cationic compounds contained in the agents according to the invention are hitherto unknown. A further subject of the present invention are therefore cationic p-phenylenediamine derivatives or p-aminophenol derivatives of the formula (I):

in the
Y is an amino group, a hydroxy group, a group -NR ² H or a group -NR ² R ³ ,
R ¹ represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a halogen atom (Cl, Br, F or J), a C ₁ -C ₆ -alkoxy group, a hydroxy-C ₂ -C ₆ -alkoxy group or a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyloxy group,
R ² , R ³ are each independently a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group or a C ₁ -C _6- alkoxy-C ₂ -C ₆ -alkyl group,
X ^- is a monovalent anion, preferably halide, hydrogensulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate.

The following examples are intended to illustrate the subject matter of the present invention without limiting it in any way.

Examples

1 syntheses

1.1. Synthesis of 1- (2-hydroxy-5-nitrobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride

10.0 g (0.16 mol) of 2-chloromethyl-4-nitrophenol and 7.2 g (0.19 mol) of 1,4-diazabicyclo [2.2.2] octane were together in 100 ml of dimethyl sulfoxide at 110 ° C for Stirred for 5 hours. The mixture was allowed to cool to room temperature overnight and then the reaction mixture was admixed with 500 ml of tert-butyl methyl ether. The resulting mixture was then stored in the refrigerator at about 5 ° C for four days to form a brown, crystalline precipitate. This was filtered off, washed with a small amount of acetone and dried.
Ascent: 8.6 g (18%) light brown, crystalline substance 1.2. Synthesis of 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride (E1)

30.0 g (0.25 mol) of tin powder was placed in 250 ml of concentrated hydrochloric acid, then 15.0 g (0.05 mol) of 1- (2-hydroxy-5-nitrobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride from stage 1.1. added in portions (exothermic reaction). After the addition was stirred at 25 to 30 ° C for two hours. The reaction solution was separated from the solid components by filtration, and the filtrate was concentrated to dryness in vacuo on a rotary evaporator. The product was in the form of light beige crystals.
Yield: 13.2 g (> 98%)

2 colorations

2.1 Experimental procedure

The cream base used had the following composition: Hydrenol D ^{® 1} 8.5% by weight Lorol® ^® tech. ² 2.0% by weight Texapon.RTM ^® NSO ³ 20.0% by weight Dehyton ^® K ⁴ 12.5% by weight Eumulgin ^® B2 ⁵ 0.75% by weight propylene glycol 5.0% by weight sodium 1.0% by weight ammonium sulfate 1.0% by weight developer component 3 mmol Kupplerkomponente 3 mmol water ad 100 ¹ C _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)
² C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis)
³ lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)
⁴ N, N-dimethyl-N- (C _8-18 -cocoamidopropyl) -ammonium acetobetaine (about 30% active ingredient, INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)
⁵ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)

Hydrenol D and Lorol techn. were melted together with Texapon NSO, Dehyton K and Eumulgin B2 at 80 ° C. Then, the melt was emulsified with the sodium sulfite dissolved in a part of the water and ammonium sulfate. The developer according to the invention was dissolved in propylene glycol and a further portion of the stated amount of water with heating and added with stirring. The coupler was also dissolved in a portion of the indicated amount of water and added with stirring. Then the formulation was made up to 100% with water and stirred cold.

The coloring cream thus obtained was mixed in a ratio of 2: 1 with the following developer dispersion having a hydrogen peroxide content of 3%. dipicolinic 0.1% by weight sodium pyrophosphate 0.03% by weight Turpinal SL ^{® 6} 1.50% by weight Texapon ^® N28 ⁷ 2.00% by weight Acrysol ^® 22 ⁸ 0.60% by weight Hydrogen peroxide, 50% 6.00% by weight Sodium hydroxide, 45% 0.80% by weight water ad 100% by weight ⁶ 1-Hydroxyethane-1,1-diphosphonic acid (about 58-61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia)
⁷ lauryl ether sulfate sodium salt (at least 26.5% active ingredient content, INCI name: Sodium Laureth Sulfate) (Cognis)
⁸ acrylic polymer (about 29.5-30.5% solids in water, INCI name: Acrylates / Steareth-20 Methacrylate Copolyme)

For the dyeing process, four times the amount of ready-to-use mixture was applied to one strand of 80% gray hair (Kerling). After a contact time of 30 minutes at 32 ° C, the locks were rinsed and washed out with a conventional shampoo. The streaking of the streaks was visually assessed under the daylight lamp after drying. The staining results are summarized in the table below. 2.2. Dyeing with 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride (E1) as a developer component example Kupplerkomponente obtained shade / color intensity 1 resorcinol light brown ++ 2 3-amino-2-methylamino-6-methoxypyridine olive brown ++ 3 5-amino-2-methylphenol red blonde ++ 4 3-amino-2-hydroxypyridine reddish brown ++ 5 1,3-bis (2,4-diaminophenoxy) propane medium brown ++ 6 2,7-dihydroxynaphthalene gray brown ++

The color intensity was rated as follows: +++ high intensity ++ medium intensity + low intensity

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 998908 A2 [0122]
• DE 3725030 A [0147]
• DE 3723354 A [0147]
• DE 3926344 A [0147]

Claims (9)

Agent for coloring keratinic fibers, in particular human hair, characterized in that it contains in a cosmetically acceptable carrier as the developer component at least one cationic compound of the formula (I)

in which Y represents an amino group, a hydroxy group, a group -NR ² H or a group -NR ² R ³ , R ¹ represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ Alkenyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a halogen atom (Cl, Br, F or J), a C ₁ -C ₆ alkoxy group, a hydroxyC ₂ -C ₆ Alkoxy group or a C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkyloxy, R ² , R ³ are independently a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₁ -C ₆ -hydroxyalkyl, C ₂ -C ₆ -polyhydroxyalkyl or C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl, X ^- is a monovalent anion, preferably halide, hydrogensulfate, ½ sulfate, p Benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate. Composition according to Claim 1, characterized in that it contains a developer component of the formula (I) in which the radical R _{1 represents} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a halogen atom (Cl, Br, F or I) or a C ₁ -C ₆ alkoxy group. Composition according to one of claims 1 or 2, characterized in that it comprises as an unwinding component at least one of the compounds selected from the group formed - Salts of 1- (2,5-diaminobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- (2,5-diamino-4-methylbenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- (2,5-diamino-4-chlorobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- (2,5-diamino-4-bromobenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- (2,5-diamino-4-methoxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- (2,5-diamino-4-ethoxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- [5-amino-2- (methylamino) benzyl] -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- [5-amino-2- (dimethylamino) benzyl] -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- [2- (allylamino) -5-aminobenzyl] -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- [2- (diallylamino) -5-aminobenzyl] -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- {5-amino-2 - [(2-hydroxyethyl) amino] benzyl} -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- {5-amino-2- [bis (2-hydroxyethyl) amino] benzyl} -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- (5-amino-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- (5-amino-4-chloro-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- (5-amino-4-bromo-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane - Salts of 1- (5-amino-4-methoxy-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane Salts of 1- (5-amino-4-ethoxy-2-hydroxybenzyl) -4-aza-1-azoniabicyclo [2.2.2] octane, contains. Agent according to one of claims 1 to 3, characterized in that it contains at least one coupler component. Composition according to claim 4, characterized in that the coupler component is selected from 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro 2-methylphenol, 5- (2'-hydroxyethyl) amino-2-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-yl-phenyl) -amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene , 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3 -methylpyrazol-5-one, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene or mixtures of these compounds or the physiologically acceptable salts of the abovementioned compounds. Keratin fiber coloring agent according to any one of Claims 1 to 5, characterized in that it contains the compound (s) of the formula (I) in amounts of from 0.001 to 5% by weight, preferably from 0.0025 to 2.5% by weight. -%, particularly preferably from 0.005 to 1.5 wt .-% and in particular from 0.01 to 1 wt .-%, each based on the total agent contains. A process for coloring keratinic fibers, wherein an agent according to any one of claims 1 to 6 is applied to the fibers and rinsed again after a contact time. Use of a cationic developer component of the formula (I),

in which Y stands for an amino group, a hydroxy group, a group -NR ² H or a group -NR ² R ³ , R ¹ represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group , a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a halogen atom (Cl, Br, F or J), a C ₁ -C ₆ alkoxy group, a hydroxy C ₂ -C ₆ alkoxy group or a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyloxy group, R ² , R ³ are independently of one another a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group or a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, X ^- represents a monovalent anion, preferably halide, hydrogensulfate, ½ sulfate, p-benzenesulfonate , p-toluenesulfonate, acetate, citrate, lactate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate. in agents for dyeing keratinic fibers. Cationic developer component of the formula (I),

in which Y is an amino group, a hydroxy group is a group -NR ² H or a group -NR ² R ³ R ¹ is a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, one C ₁ -C ₆ hydroxyalkyl group, C ₂ -C ₆ polyhydroxyalkyl group, halogen atom (Cl, Br, F or J), C ₁ -C ₆ alkoxy group, hydroxy C ₂ -C ₆ alkoxy group or a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyloxy group, R ² , R ³ are each independently a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ - Hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group or a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group X ^- is a monovalent anion, preferably halide, hydrogensulfate, ½ sulfate, p-benzenesulfonate, p- Toluenesulfonate, acetate, citrate, lactate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate.