DE102008033875A1 - Agent, useful for oxidative coloring of keratin fibers, preferably e.g. human hairs, comprises 6-amino-2-hydroxy-pyridine derivative, as coupler component, in a carrier, further developer component and direct dye - Google Patents

Abstract

Agent for coloring keratin fibers, preferably human hairs, comprises at least a 6-amino-2-hydroxy-pyridine derivative (I), as a coupler component, in a carrier. Agent for coloring keratin fibers, preferably human hairs, comprises at least a 6-amino-2-hydroxy-pyridine derivative of formula (I), as a coupler component, in a carrier. R1 : saturated, 5-15-membered heterocycle exhibiting at least one N atom and optionally containing up to 3 further heteroatoms of O or -NR3-, where the heterocycle is bonded to the aromatic ring system over N; R3 : H, 1-6C-alkyl, 2-6C-alkenyl or 1-6C-hydroxyalkyl; and R2 : H, 1-6C-alkyl, 2-6C-alkenyl, 1-6C-hydroxyalkyl, 2-6C-polyhydroxyalkyl, 1-6C-alkoxy, NH 2, di-(1-6C-alkyl)amino, halo or OH. An independent claim is included for a process for coloring the keratin fibers comprising applying the agent and washing the hair after an influential time. [Image].

Description

The The present invention relates to agents for coloring keratinous Fibers containing specific 6-amino-2-hydroxypyridine derivatives the amino group of which is part of a ring system, a process for Coloring of hair with these means as well as use of these 6-amino-2-hydroxypyridine derivatives in oxidative colorants.

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

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

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

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols used. Particularly suitable coupling agents are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-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.

Quality Oxidation dye precursors are primarily intended to meet the following requirements meet: you need in the oxidative coupling the desired color shades in sufficient intensity and train authenticity. You must also have a good wind up to possess the fiber, in particular in human hair no noticeable differences between strained and fresh may exist after regrown hair (leveling). They should be resistant to light, heat, Sweat, friction and the influence of chemical reducing agents, z. B. permanent wave fluids. Finally, should if used as hair dye coming - do not stain the scalp too much, and above all, they should be toxicological and dermatological Regard safe. Furthermore, the color obtained should can easily be removed from the hair by bleaching, if the person treated expresses a short-term change in color (good color removal behavior).

Alone with a developer component or a special coupler / developer combination Usually it does not succeed, one on the hair of course to get an effective color nuance. In practice, therefore, are usually Combinations of different developer and / or coupler components used. There is therefore a constant need for new, improved Dye components, which are also toxicological and dermatological Regard unproblematic. There is a special need specifically on dye precursors that cause intense dark natural nuances lead, which are long-lasting, have very good fastness properties and completely in the sense of an on / off system again have it removed.

task Therefore, it was the object of the present invention to provide novel coupler components to develop those who put the oxidation dye precursors Requirements, in particular with regard to the toxicological and dermatological properties, fulfill and dyes in a wide color spectrum with good fastness properties as well enable a good deduction behavior.

Surprisingly, it has now been found that special 6-amino-2-hydroxypyridine derivatives which carry a specific heterocycle satisfy the requirements imposed on coupler components to a high degree. The coupler components of the invention enable the production of rich and intense nuances, especially in the field of natural shades, which are characterized by very good wash stabilities, are very lightfast and equalize the hair in an excellent way, the dyeings can be completely reversed by an oxidative treatment.

enthalten, wobei

• – der Rest R1 steht für einen gesättigten, 5- bis 15-gliedrigen Heterocyclus, der mindestens ein Stickstoffatom und gegebenenfalls bis zu 3 weitere Heteroatome, ausgewählt aus einem Sauerstoffatom oder der Gruppe -NR3-, aufweist, wobei der Heterocyclus über ein Stickstoffatom an das aromatische Ringsystem gebunden ist, und R3 steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine C₁-C₆-Hydroxyalkylgruppe, und
• – der Rest R2 steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, eine Aminogruppe, eine Di-(C₁-C₆-Alkyl)aminogruppe, ein Halogenatom oder eine Hydroxygruppe.

A first subject of the present invention are therefore agents for coloring keratinic fibers, in particular human hair, which contain in a cosmetically acceptable carrier as coupler component at least one 6-amino-2-hydroxypyridine derivative of the formula (I)

contain, where

• - the radical R 1 is a saturated, 5- to 15-membered heterocycle having at least one nitrogen atom and optionally up to 3 further heteroatoms selected from an oxygen atom or the group -NR 3 -, wherein the heterocycle via a nitrogen atom to the R3 is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl or C ₁ -C ₆ hydroxyalkyl, and
• The radical R ₂ is 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 C ₁ -C ₆ alkoxy, amino, di- (C ₁ -C ₆ alkyl) amino, halogen or hydroxy.

Under keratinic fibers are according to the invention furs, Wool, feathers and especially human hair to understand. Even though the oxidation colorants of the invention primarily suitable for dyeing keratin fibers, is in principle a use in other fields, in particular in color photography, nothing contrary.

There it is in the inventive 6-amino-2-hydroxypyridinderivaten Amino compounds are, from these in common Way to produce the known acid addition salts. All Statements of this document and accordingly the claimed Protection range therefore refer both to the free form present compounds as well as their physiologically acceptable Salts of organic or inorganic acids. Examples for such salts are the hydrochlorides, the hydrobromides, sulfates, phosphates, acetates, propionates, citrates and the lactates. The hydrochlorides and sulfates are special prefers. Very particularly preferred according to the invention are the monohydrochlorides, the dihydrochlorides 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 alkyl groups. A preferred C ₁ to C ₆ alkenyl groups is the allyl group. Preferred C ₁ to C ₆ alkoxy groups are the methoxy and ethoxy groups. 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. 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 6-amino-2-hydroxypyridine derivatives of the formula (I) can be obtained with Using conventional organic methods. exemplary be at this point on the experimental procedures in Referred to the frame of the embodiments.

Some the now claimed as coupler components 6-amino-2-hydroxypyridine derivatives of formula (I) are in the literature, in particular for medical or pharmaceutical applications, already described; Indications of their advantageous properties in the context of oxidative staining of keratinic fibers However, these references are not apparent.

Within the scope of the work on which this application is based, the compounds of the formula (I) have proved to be particularly advantageous in which the radical R 2 is a hydrogen atom, a halogen atom or a C ₁ -C ₆ -alkyl group. Compounds in which the radical R 2 is a hydrogen atom, a chlorine atom or a methyl group and in particular a hydrogen atom, are very particularly advantageous way.

wobei

• – X steht für eine der Gruppen • -(CH₂)_n-, • -(CH₂)_n-Y1-(CH₂)_m-, • -(CH₂)-Y1-(CH₂)_m-Y2-(CH₂)_o- oder • -(CH₂)-Y1-(CH₂)_m-Y2-(CH₂)_o-Y3-(CH₂)_p-,
• – Y1, Y2 und Y3 stehen unabhängig voneinander für ein Sauerstoffatom oder eine Gruppe -NR3-,
• – R3 steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkylengruppe oder eine C₂-C₆-Hydroxyalkylgruppe, und
• – n, m, o und p stehen unabhängig voneinander jeweils für eine ganze Zahl zwischen 1 und 7, mit der Maßgabe, dass die Summe aus n + m + p + o mindestens 4 und höchstens 13 beträgt.

Furthermore, compounds have proved to be particularly advantageous in which the radical R 1 is a group of the formula (II)

in which

• - X represents one of the groups • - (CH ₂ ) _n -, • - (CH ₂ ) _n -Y 1 - (CH ₂ ) _m -, • - (CH ₂ ) -Y 1 - (CH ₂ ) _m -Y ₂ - (CH ₂ ) _o - or • - (CH ₂ ) -Y 1 - (CH ₂ ) _m -Y ₂ - (CH ₂ ) _o -Y 3 - (CH ₂ ) _p -,
• Y1, Y2 and Y3 independently of one another represent an oxygen atom or a group -NR3-,
• R 3 represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkylene group or a C ₂ -C ₆ -hydroxyalkyl group, and
• - n, m, o and p are each independently an integer between 1 and 7, with the proviso that the sum of n + m + p + o is at least 4 and at most 13.

at the calculation of the sum of n + m + p + o according to the invention are the Indexes m, p and / or o to the value "0", provided these do not occur in the formula for X.

It is inventively preferred when the radicals Y1 and Y2 and, if appropriate, Y3 all represent one oxygen atom or all stand for one group -NR3-.

Further it is inventively preferred if n and m and optionally o and optionally p in a compound stand for an identical number. Compounds of the formula (I), where the relationship n = m = 2 or n = m = o = 2 or n = m = o = p = 2 applies, are particularly according to the invention prefers.

Farther compounds of the formula (I) are particularly preferred in which R3 represents a hydrogen atom, a methyl group or a Hydroxyalkyl group stands.

In a first particularly preferred embodiment of the present invention, compounds of the formula (I) have proved to be particularly preferred in which R 1 is a radical of the formula (II) where X is a group - (CH ₂ ) _n - and n is an integer from 4 to 6.

in the Within this embodiment, compounds are particular in which the radical R 1 is a pyrrolidin-1-yl ring, a piperidin-1-yl ring or an azepan-1-yl ring.

• – 6-(Pyrrolidin-1-yl)pyridin-2-ol
  
• – 6-(Piperidin-1-yl)pyridin-2-ol
  
• – 6-(Azepan-1-yl)pyridin-2-ol
  
• – 4-Methyl-6-(pyrrolidin-1-yl)pyridin-2-ol
  
• – 4-Methyl-6-(piperidin-1-yl)pyridin-2-ol
  
• – 6-(Azepan-1-yl)-4-methylpyridin-2-ol
  
• – 4-Chlor-6-(pyrrolidin-1-yl)pyridin-2-ol
  
• – 4-Chlor-6-(piperidin-1-yl)pyridin-2-ol
  
  und
• – 6-(Azepan-1-yl)-4-chlorpyridin-2-ol
  

Very particularly preferred compounds of this embodiment are

• - 6- (pyrrolidin-1-yl) pyridin-2-ol
  
• - 6- (piperidin-1-yl) pyridin-2-ol
  
• - 6- (azepan-1-yl) pyridin-2-ol
  
• 4-methyl-6- (pyrrolidin-1-yl) pyridin-2-ol
  
• 4-methyl-6- (piperidin-1-yl) pyridin-2-ol
  
• - 6- (azepan-1-yl) -4-methyl-pyridin-2-ol
  
• 4-Chloro-6- (pyrrolidin-1-yl) pyridin-2-ol
  
• 4-Chloro-6- (piperidin-1-yl) pyridin-2-ol
  
  and
• - 6- (azepan-1-yl) -4-chloropyridine-2-ol
  

• – Y1 steht für ein Sauerstoffatom oder eine Gruppe -NR3,
• – n und m stehen unabhängig voneinander für eine ganze Zahl von 1 bis 3, mit der Maßgabe, dass die Summe aus n + m mindestens 4 beträgt und
• – R3 steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkylengruppe oder eine C₂-C₆-Hydroxyalkylgruppe.

In a second particularly preferred embodiment of the present invention, compounds of the formula (I) have proved to be particularly preferred in which R 1 is a radical of the formula (II) where X is a group - (CH ₂ ) _n -Y 1 - (CH ₂ ) _m -, where

• Y1 represents an oxygen atom or a group -NR3,
• - n and m are independently an integer from 1 to 3, with the proviso that the sum of n + m is at least 4 and
• R 3 represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkylene group or a C ₂ -C ₆ -hydroxyalkyl group.

Further it is inventively preferred if n and m stand for an identical number. Compounds of this embodiment, where the relationship n = m = 2 or n = m = 3, are particularly preferred according to the invention. Links, where n = m = 2, are most preferred.

Farther compounds of this embodiment are particularly preferred where R3 is a hydrogen atom, a methyl group or a hydroxyalkyl group.

As well could be shown that compounds in which the rest R1 is derived from a morpholin-4-yl ring or a piperazin-1-yl ring are particularly preferred. Very particular preference is given to compounds of the formula (I) in which R1 represents a morpholin-4-yl ring, a piperazin-1-yl ring, a 4-methylpiperazin-1-yl ring or a 4- (2-hydroxyethyl) piperazin-1-yl ring.

• – 6-(Morpholin-4-yl)pyridin-2-ol
  
• – 6-(Piperazin-1-yl)pyridin-2-ol
  
• – 6-(4-Methylpiperazin-1-yl)pyridin-2-ol
  
• – 6-[4-(2-Hydroxyethyl)piperazin-1-yl]-pyridin-2-ol
  
• – 4-Methyl-6-(morpholin-4-yl)pyridin-2-ol
  
• – 4-Methyl-6-(piperazin-1-yl)pyridin-2-ol
  
• – 4-Methyl-6-(4-methylpiperazin-1-yl)-pyridin-2-ol
  
• – 6-[4-(2-Hydroxyethyl)piperazin-1-yl]-4-methylpyridin-2-ol
  
• – 4-Chlor-6-(morpholin-4-yl)pyridin-2-ol
  
• – 4-Chlor-6-(piperazin-1-yl)pyridin-2-ol
  
• – 4-Chlor-6-(4-methylpiperazin-1-yl)-pyridin-2-ol
  
• – 4-Chlor-6-[4-(2-Hydroxyethyl)piperazin-1-yl]pyridin-2-ol
  

Particularly preferred representatives of this embodiment are

• - 6- (morpholin-4-yl) pyridin-2-ol
  
• - 6- (piperazin-1-yl) pyridin-2-ol
  
• - 6- (4-methylpiperazin-1-yl) pyridin-2-ol
  
• - 6- [4- (2-hydroxyethyl) piperazin-1-yl] -pyridin-2-ol
  
• 4-methyl-6- (morpholin-4-yl) pyridin-2-ol
  
• 4-methyl-6- (piperazin-1-yl) pyridin-2-ol
  
• 4-methyl-6- (4-methylpiperazin-1-yl) -pyridin-2-ol
  
• - 6- [4- (2-hydroxyethyl) piperazin-1-yl] -4-methylpyridin-2-ol
  
• 4-chloro-6- (morpholin-4-yl) pyridin-2-ol
  
• 4-chloro-6- (piperazin-1-yl) pyridin-2-ol
  
• 4-chloro-6- (4-methylpiperazin-1-yl) -pyridin-2-ol
  
• 4-Chloro-6- [4- (2-hydroxyethyl) piperazin-1-yl] pyridin-2-ol
  

• – Y1 und Y2 stehen unabhängig voneinander für ein Sauerstoffatom oder eine Gruppe –NR3-,
• – n, m und o stehen unabhängig voneinander für eine ganze Zahl von 1 bis 3, mit der Maßgabe, dass die Summe aus n + m + o mindestens 4 beträgt und
• – R3 steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkylengruppe oder eine C₂-C₆-Hydroxyalkylgruppe.

In a third particularly preferred embodiment of the present invention, compounds of the formula (I) have proved to be particularly preferred in which R1 is a radical of the formula (II) wherein X is a group - (CH ₂ ) _n -Y 1 - (CH ₂ ) _m -Y ₂ - (CH ₂ ) _o -, wherein

• Y1 and Y2 independently of one another represent an oxygen atom or a group -NR3-,
• - n, m and o independently represent an integer from 1 to 3, with the proviso that the sum of n + m + o is at least 4 and
• R 3 represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkylene group or a C ₂ -C ₆ -hydroxyalkyl group.

in the Within the scope of this embodiment, it is preferred according to the invention when the radicals Y1 and Y2 are all for an oxygen atom or all stand for one group -NR3-.

Further it is inventively preferred if n, m and o stand for an identical number. Compounds of the formula (I) where n = m = o = 2 or n = m = o = 3, are particularly preferred according to the invention. Links, where n = m = o = 2 are very particularly preferred.

Farther are in the context of this embodiment compounds of Formula (I), in which R 3 is a hydrogen atom, a methyl group or a hydroxyalkyl group.

Further compounds of the formula (I) are preferred in which the radical R1 represents a 1,4,7-dioxazonan-7-yl ring.

• – 6-(1,4,7-Dioxazonan-7-yl)pyridin-2-ol
  
• – 6-(1,4,7-Dioxazonan-7-yl)-4-methyl-pyridin-2-ol
  
• – 4-Chlor-6-(1,4,7-dioxazonan-7-yl)-pyridin-2-ol
  

Particularly preferred compounds of this embodiment of the present invention are

• - 6- (1,4,7-dioxazonan-7-yl) pyridin-2-ol
  
• - 6- (1,4,7-dioxazonan-7-yl) -4-methylpyridin-2-ol
  
• 4-Chloro-6- (1,4,7-dioxazonan-7-yl) -pyridin-2-ol
  

• – 6-(Pyrrolidin-1-yl)pyridin-2-ol
• – 6-(Piperidin-1-yl)pyridin-2-ol
• – 6-(Morpholin-4-yl)pyridin-2-ol
• – 6-(Piperazin-1-yl)pyridin-2-ol sowie
• – 6-(4-Methylpiperazin-1-yl)pyridin-2-ol

sind erfindungsgemäß besonders bevorzugte 6-Amino-2-hydroxypyridinderivate der Formel (I). 6-(Morpholin-4-yl)pyridin-2-ol ist eine ganz besonders bevorzugte Verbindung der Formel (I).The connections

• - 6- (pyrrolidin-1-yl) pyridin-2-ol
• - 6- (piperidin-1-yl) pyridin-2-ol
• - 6- (morpholin-4-yl) pyridin-2-ol
• - 6- (piperazin-1-yl) pyridin-2-ol and
• - 6- (4-methylpiperazin-1-yl) pyridin-2-ol

are particularly preferred according to the invention 6-amino-2-hydroxypyridine derivatives of the formula (I). 6- (morpholin-4-yl) pyridin-2-ol is a most preferred compound of formula (I).

Next the 6-amino-2-hydroxypyridine derivatives of the formula (I) can the colorants of the invention further contain at least one 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 radical, or
• When G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Especially Preferred p-phenylenediamines of formula (E1) are selected one or more compounds of the group that is formed p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino 2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine, 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

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

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

wobei:

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

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

in which:

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

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

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

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

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

wobei:

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

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

in which:

• G ¹³ represents a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl, (C ₁ to C ₄ ) aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, (C ₁ to C ₄ ) hydroxyalkoxy radical, a (C ₁ to C ₄ ) hydroxyalkyl (C ₁ to C ₄ ) aminoalkyl radical or a (di - [(C ₁ to C ₄ ) alkyl] amino) - (C ₁ to C ₄ ) alkyl radical , and
• G ¹⁴ is a hydrogen or halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -aminoalkyl radical or a (C ₁ to C ₄ ) -cyanoalkyl radical,
• G ¹⁵ is hydrogen, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

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

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

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

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

Farther For example, the developer component may be selected from heterocyclic Developer components, such as pyrimidine derivatives, Pyrazole derivatives, pyrazolopyrimidine derivatives or their physiological compatible salts.

worin

• – G¹⁷, G¹⁸ und G¹⁹ unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁ bis C₄)-Alkoxygruppe oder eine Aminogruppe steht und
• – G²⁰ 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.

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

worin

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

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

wherein

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

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

Especially 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, as well 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 used in formula (E7) substituents are analogous to the invention defined to the above statements.

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

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

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

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

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

The Pyrazolo [1,5-a] pyrimidines of the above formula (E6) can as described in the literature by cyclization starting 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 for halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.

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

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

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

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

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

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

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

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

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

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

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

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

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

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.

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

In a further preferred embodiment include the Colorants according to the invention at least another coupler component.

Coupler components according to the invention allow at least one substitution of a chemi 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,

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 group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, an aryl (C ₁ to C ₆ ) alkyl group, an 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.

Especially preferred m-aminophenol coupler components are selected from at least one compound from the group that is formed from m-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol and the physiological compatible salts of all the compounds mentioned above.

worin
G⁵, G⁶, G⁷ und G⁸ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (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 G¹⁹ 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 ¹⁹ 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.

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

worin
G¹¹, G¹², G¹³ und G¹⁴ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (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.

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

Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group formed from resorcinol, resorcinol monomethyl ether, 2-methylre sorcinol, 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.

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

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

worin
G²³ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, 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 tolerated salts of the aforementioned compounds.

worin
G²⁸ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, 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.

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

preferred Pyrimidine derivatives are selected from at least one Compound of the group formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-o-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-o-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 for halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.

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

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

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

Examples of (C ₁ to C ₄ ) 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 according to the invention preferred coupler components 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-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxy-ethoxy) -5-methyl-phenylamine, 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-hydroxyindoline, 7-hydroxyindoline or mixtures these compounds or the physiologically acceptable Salts of the aforementioned compounds.

• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/p-Phenylendiamin
• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/p-Toluylendiamin
• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/2-Methoxymethyl-p-phenylendiamin
• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/p-Aminophenol
• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/4-Amino-3-methylphenol
• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Pyrrolidin-1-yl)pyridin-2-ol/2,4,5,6-Tetraaminopyrimidin

• – 6-(Piperidin-1-yl)pyridin-2-ol/p-Phenylendiamin
• – 6-(Piperidin-1-yl)pyridin-2-ol/p-Toluylendiamin
• – 6-(Piperidin-1-yl)pyridin-2-ol/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Piperidin-1-yl)pyridin-2-ol/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Piperidin-1-yl)pyridin-2-ol/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Piperidin-1-yl)pyridin-2-ol/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Piperidin-1-yl)pyridin-2-ol/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Piperidin-1-yl)pyridin-2-ol/2-Methoxymethyl-p-phenylendiamin
• – 6-(Piperidin-1-yl)pyridin-2-ol/p-Aminophenol
• – 6-(Piperidin-1-yl)pyridin-2-ol/4-Amino-3-methylphenol
• – 6-(Piperidin-1-yl)pyridin-2-ol/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Piperidin-1-yl)pyridin-2-ol/2,4,5,6-Tetraaminopyrimidin

• – 6-(Morpholin-4-yl)pyridin-2-ol/p-Phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/p-Toluylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Morpholin-4-yl)pyridin-2-ol/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methoxymethyl-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/p-Aminophenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/4-Amino-3-methylphenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2,4,5,6-Tetraaminopyrimidin

• – 6-(Piperazin-1-yl)pyridin-2-ol/p-Phenylendiamin
• – 6-(Piperazin-1-yl)pyridin-2-ol/p-Toluylendiamin
• – 6-(Piperazin-1-yl)pyridin-2-ol/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Piperazin-1-yl)pyridin-2-ol/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Piperazin-1-yl)pyridin-2-ol/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Piperazin-1-yl)pyridin-2-ol/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Piperazin-1-yl)pyridin-2-ol/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Piperazin-1-yl)pyridin-2-ol/2-Methoxymethyl-p-phenylendiamin
• – 6-(Piperazin-1-yl)pyridin-2-ol/p-Aminophenol
• – 6-(Piperazin-1-yl)pyridin-2-ol/4-Amino-3-methylphenol
• – 6-(Piperazin-1-yl)pyridin-2-ol/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Piperazin-1-yl)pyridin-2-ol/2,4,5,6-Tetraaminopyrimidin

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

• - 6- (pyrrolidin-1-yl) pyridin-2-ol / p-phenylenediamine
• - 6- (pyrrolidin-1-yl) pyridin-2-ol / p-toluenediamine
• - 6- (pyrrolidin-1-yl) pyridin-2-ol / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (pyrrolidin-1-yl) pyridin-2-ol / N, N-bis (β-hydroxyethyl) -p-phenylenediamine
• - 6- (pyrrolidin-1-yl) pyridin-2-ol / N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine
• - 6- (pyrrolidin-1-yl) pyridin-2-ol / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (pyrrolidin-1-yl) pyridin-2-ol / 1,3-bis (2,5-diaminophenoxy) -propan-2-ol
• - 6- (pyrrolidin-1-yl) pyridin-2-ol / 2-methoxymethyl-p-phenylenediamine
• - 6- (pyrrolidin-1-yl) pyridin-2-ol / p-aminophenol
• - 6- (pyrrolidin-1-yl) pyridin-2-ol / 4-amino-3-methylphenol
• - 6- (pyrrolidin-1-yl) pyridin-2-ol / 4,5-diamino-1- (β-hydroxyethyl) pyrazole
• - 6- (pyrrolidin-1-yl) pyridin-2-ol / 2,4,5,6-tetraaminopyrimidine

• - 6- (piperidin-1-yl) pyridin-2-ol / p-phenylenediamine
• - 6- (piperidin-1-yl) pyridin-2-ol / p-toluenediamine
• - 6- (piperidin-1-yl) pyridin-2-ol / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (piperidin-1-yl) pyridin-2-ol / N, N-bis (β-hydroxyethyl) -p-phenylenediamine
• - 6- (piperidin-1-yl) pyridin-2-ol / N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine
• - 6- (piperidin-1-yl) pyridin-2-ol / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (piperidin-1-yl) pyridin-2-ol / 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol
• - 6- (piperidin-1-yl) pyridin-2-ol / 2-methoxymethyl-p-phenylenediamine
• - 6- (piperidin-1-yl) pyridin-2-ol / p-aminophenol
• - 6- (piperidin-1-yl) pyridin-2-ol / 4-amino-3-methylphenol
• - 6- (piperidin-1-yl) pyridin-2-ol / 4,5-diamino-1- (β-hydroxyethyl) pyrazole
• - 6- (piperidin-1-yl) pyridin-2-ol / 2,4,5,6-tetraaminopyrimidine

• - 6- (morpholin-4-yl) pyridin-2-ol / p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / p-toluenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / N, N-bis (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine
• - 6- (morpholin-4-yl) pyridin-2-ol / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,5-diaminophenoxy) -propan-2-ol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methoxymethyl-p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / p-aminophenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 4-amino-3-methylphenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 4,5-diamino-1- (β-hydroxyethyl) pyrazole
• - 6- (morpholin-4-yl) pyridin-2-ol / 2,4,5,6-tetraaminopyrimidine

• - 6- (piperazin-1-yl) pyridin-2-ol / p-phenylenediamine
• - 6- (piperazin-1-yl) pyridin-2-ol / p-toluenediamine
• - 6- (piperazin-1-yl) pyridin-2-ol / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (piperazin-1-yl) pyridin-2-ol / N, N-bis (β-hydroxyethyl) -p-phenylenediamine
• - 6- (piperazin-1-yl) -pyridin-2-ol / N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) -propyl] -amine
• - 6- (piperazin-1-yl) pyridin-2-ol / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (piperazin-1-yl) pyridin-2-ol / 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol
• - 6- (piperazin-1-yl) pyridin-2-ol / 2-methoxymethyl-p-phenylenediamine
• - 6- (piperazin-1-yl) pyridin-2-ol / p-aminophenol
• - 6- (piperazin-1-yl) pyridin-2-ol / 4-amino-3-methylphenol
• - 6- (piperazin-1-yl) pyridin-2-ol / 4,5-diamino-1- (β-hydroxyethyl) pyrazole
• - 6- (piperazin-1-yl) pyridin-2-ol / 2,4,5,6-tetraaminopyrimidine

• – 6-(Morpholin-4-yl)pyridin-2-ol/m-Aminophenol/p-Phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/m-Aminophenol/p-Toluylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/m-Aminophenol/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/m-Aminophenol/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/m-Aminophenol/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Morpholin-4-yl)pyridin-2-ol/m-Aminophenol/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Morpholin-4-yl)pyridin-2-ol/m-Aminophenol/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Morpholin-4-yl)pyridin-2-ol/m-Aminophenol/2-Methoxymethyl-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/m-Aminophenol/p-Aminophenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/m-Aminophenol/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Morpholin-4-yl)pyridin-2-ol/m-Aminophenol/2,4,5,6-Tetraaminopyrimidin

• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/p-Phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/p-Toluylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/2-Methoxymethyl-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/p-Aminophenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/4-Amino-3-methylphenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Morpholin-4-yl)pyridin-2-ol/5-Amino-2-methylphenol/2,4,5,6-Tetraaminopyrimidin

• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/p-Phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/p-Toluylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/2-Methoxymethyl-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/p-Aminophenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/4-Amino-3-methylphenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-(2,4-Diaminophenoxy)ethanol/2,4,5,6-Tetraaminopyrimidin

• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/p-Phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/p-Toluylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/2-Methoxymethyl-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/p-Aminophenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/4-Amino-3-methylphenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Morpholin-4-yl)pyridin-2-ol/1,3-Bis(2,4-diaminophenoxy)propan/2,4,5,6-Tetraaminopyrimidin

• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol/p-Phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-ydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol/p-Toluylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-Hydroxyethynamino]-4-methoxy-5-methylphenyl}amino)ethanol/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol/2-Methoxymethyl-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol/p-Aminophenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol/4-Amino-3-methylphenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-({3-[(2-Hydroxyethynamino]-4-methoxy-5-methylphenyl}amino)ethanol/2,4,5,6-Tetraaminopyrimidin

• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/p-Phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/p-Toluylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/2-Methoxymethyl-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/p-Aminophenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/4-Amino-3-methylphenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Morpholin-4-yl)pyridin-2-ol/Resorcin/2,4,5,6-Tetraaminopyrimidin

• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/p-Phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/p-Toluylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/2-Methoxymethyl-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/p-Aminophenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/4-Amino-3-methylphenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Methylresorcin/2,4,5,6-Tetraaminopyrimidin

• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/p-Phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/p-Toluylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/N,N-Bis-([3-hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/2-Methoxymethyl-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/p-Aminophenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/4-Amino-3-methylphenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Morpholin-4-yl)pyridin-2-ol/2-Amino-3-hydroxypyridin/2,4,5,6-Tetraaminopyrimidin

• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/p-Phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/p-Toluylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/2-(β-Hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/N,N-Bis-(β-hydroxyethyl)-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/N-(4-Amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/Bis-(2-hydroxy-5-aminophenyl)-methan
• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/1,3-Bis-(2,5-diaminophenoxy)-propan-2-ol
• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/2-Methoxymethyl-p-phenylendiamin
• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/p-Aminophenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/4-Amino-3-methylphenol
• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/4,5-Diamino-1-(β-hydroxyethyl)-pyrazol
• – 6-(Morpholin-4-yl)pyridin-2-ol/1-Naphthol/2,4,5,6-Tetraaminopyrimidin

Particularly preferred combinations according to the invention of at least one coupler component according to the invention and at least one further coupler component and at least one further developer component are:

• - 6- (morpholin-4-yl) pyridin-2-ol / m-aminophenol / p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / m-aminophenol / p-toluenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / m-aminophenol / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / m-aminophenol / N, N-bis (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / m-aminophenol / N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine
• - 6- (morpholin-4-yl) pyridin-2-ol / m-aminophenol / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (morpholin-4-yl) pyridin-2-ol / m-aminophenol / 1,3-bis (2,5-diaminophenoxy) -propan-2-ol
• - 6- (morpholin-4-yl) pyridin-2-ol / m-aminophenol / 2-methoxymethyl-p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / m-aminophenol / p-aminophenol
• - 6- (morpholin-4-yl) pyridin-2-ol / m-aminophenol / 4,5-diamino-1- (β-hydroxyethyl) -pyrazole
• - 6- (morpholin-4-yl) pyridin-2-ol / m-aminophenol / 2,4,5,6-tetraaminopyrimidine

• - 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / p-toluenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / N, N-bis (β-hydroxyethyl) -p-phenylenediamine
• 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) amine propyl]
• - 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / 1,3-bis (2,5-diaminophenoxy) -propan-2-ol
• - 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / 2-methoxymethyl-p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / p-aminophenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / 4-amino-3-methylphenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / 4,5-diamino-1- (β-hydroxyethyl) -pyrazole
• - 6- (morpholin-4-yl) pyridin-2-ol / 5-amino-2-methylphenol / 2,4,5,6-tetraaminopyrimidine

• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / p-toluenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / N, N-bis- (β-hydroxyethyl) -p-phenylenediene min
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole-1 -yl) propyl] amine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / 2-methoxymethyl-p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / p-aminophenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / 4-amino-3-methylphenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / 4,5-diamino-1- (β-hydroxyethyl) pyrazole
• - 6- (morpholin-4-yl) pyridin-2-ol / 2- (2,4-diaminophenoxy) ethanol / 2,4,5,6-tetraaminopyrimidine

• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / p-toluenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / N, N-bis (β-hydroxyethyl) -p-phenylenediamine
• 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / N- (4-amino-3-methylphenyl) -N- [3- (1H- imidazol-1-yl) propyl] amine
• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / 1,3-bis (2,5-diaminophenoxy) -propan-2-ol
• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / 2-methoxymethyl-p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / p-aminophenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / 4-amino-3-methylphenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / 4,5-diamino-1- (β-hydroxyethyl) pyrazole
• - 6- (morpholin-4-yl) pyridin-2-ol / 1,3-bis (2,4-diaminophenoxy) propane / 2,4,5,6-tetraaminopyrimidine

• - 6- (morpholin-4-yl) pyridin-2-ol / 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol / p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2 - ({3 - [(2-ydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol / p-toluenediamine
• - 6- (morpholin-4-yl) -pyridin-2-ol / 2 - ({3 - [(2-hydroxyethynamino) -4-methoxy-5-methylphenyl} amino) ethanol / 2- (β-hydroxyethyl) -p phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol / N, N-bis ( β-hydroxyethyl) -p-phenylenediamine
• 6- (morpholin-4-yl) pyridin-2-ol / 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol / N- (4-amino) 3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine
• 6- (morpholin-4-yl) pyridin-2-ol / 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol / bis (2-hydroxy) 5-aminophenyl) -methane
• - 6- (morpholin-4-yl) pyridin-2-ol / 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol / 1,3-bis ( 2,5-diaminophenoxy) -propan-2-ol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol / 2-methoxymethyl-p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol / p-aminophenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol / 4-amino-3-methylphenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol / 4,5-diamino-1 - (β-hydroxyethyl) pyrazole
• - 6- (morpholin-4-yl) -pyridin-2-ol / 2 - ({3 - [(2-hydroxyethynamino) -4-methoxy-5-methylphenyl} amino) ethanol / 2,4,5,6-tetraaminopyrimidine

• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / p-toluenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / N, N-bis (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine
• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / 1,3-bis (2,5-diaminophenoxy) -propan-2-ol
• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / 2-methoxymethyl-p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / p-aminophenol
• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / 4-amino-3-methylphenol
• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / 4,5-diamino-1- (β-hydroxyethyl) -pyrazole
• - 6- (morpholin-4-yl) pyridin-2-ol / resorcinol / 2,4,5,6-tetraaminopyrimidine

• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / p-toluenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / N, N-bis (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) -propyl] amine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / 2-methoxymethyl-p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / p-aminophenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / 4-amino-3-methylphenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / 4,5-diamino-1- (β-hydroxyethyl) -pyrazole
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-methylresorcinol / 2,4,5,6-tetraaminopyrimidine

• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / p-toluenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / N, N-bis - ([3-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) amine propyl]
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / 1,3-bis (2,5-diaminophenoxy) -propan-2-ol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / 2-methoxymethyl-p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / p-aminophenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / 4-amino-3-methylphenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / 4,5-diamino-1- (β-hydroxyethyl) -pyrazole
• - 6- (morpholin-4-yl) pyridin-2-ol / 2-amino-3-hydroxypyridine / 2,4,5,6-tetraaminopyrimidine

• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / p-toluenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / 2- (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / N, N-bis (β-hydroxyethyl) -p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) -propyl] amine
• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / bis (2-hydroxy-5-aminophenyl) -methane
• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / 1,3-bis (2,5-diaminophenoxy) -propan-2-ol
• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / 2-methoxymethyl-p-phenylenediamine
• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / p-aminophenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / 4-amino-3-methylphenol
• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / 4,5-diamino-1- (β-hydroxyethyl) -pyrazole
• - 6- (morpholin-4-yl) pyridin-2-ol / 1-naphthol / 2,4,5,6-tetraaminopyrimidine

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 proved to be useful, so is a certain excess of individual oxidation dye precursors not disadvantageous, 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 another embodiment of the present invention For example, the colorants can be at least one precursor a nature analog dye included.

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

in der unabhängig voneinander

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

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

in the independently of each other

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

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

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

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

in der unabhängig voneinander

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

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (RN2),

in the independently of each other

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

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

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

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

The Indoline or the indole derivatives can both as free bases as well as in the form of their physiologically acceptable Salts with inorganic or organic acids, e.g. B. the hydrochlorides, sulfates and hydrobromides.

The Indoline and indole derivatives can be used in the inventive Colorants 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. The indole or indoline derivatives are in these usually in amounts of 0.05-10 Wt .-%, preferably 0.2-5 wt .-%.

In According to another embodiment, it may be preferred according to the invention be the indoline or Indolderivat in colorants in Combination with at least one amino acid or one Use oligopeptide. The amino acid is advantageous an α-amino acid; very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular Arginine.

Next the 6-amino-2-hydroxypyridine derivatives according to the invention of formula (I), the inventive Colorant in a further preferred embodiment of the present invention for shading one or more substantive Dyes contain. These are dyes that directly put on hair and no oxidative process for training need the color. Direct dyes are common Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or Indophenole.

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

Anionic substantive dyes:

Particularly suitable anionic direct dyes are 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (CI 15.985, Food Yellow No. 3, FD & C Yellow No. 6), 2,4-dinitro-1 naphthol-7-sulfonic acid disodium salt (CI 10,316, Acid Yellow 1, Food Yellow No. 1), 2- (indan-1,3-dion-2-yl) quinoline-x, x-sulfonic acid (mixture of mono- and di-sodium Disulfonic acid) (CI 47,005, D & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10), 4 - ((4-amino-3-sulfophenyl) azo) benzenesulfonic acid disodium salt (CI 13,015, Acid Yellow 9 ), 5-Hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenylazo] pyrazole-3-carboxylic acid trisodium salt (CI 19.140, Food Yellow No. 4, Acid Yellow 23), 3 - [(4- Phenylamino) phenyl] azobenzenesulfonic acid sodium salt (CI 13.065, Ki406, Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthen-3-one (CI 45.350, Acid Yellow 73, D & C Yellow No. 8), 5 - [(2,4-dinitrophenylamino] -2-phenylaminobenzenesulfonic acid, sodium salt (CI 10,385; Acid Orange 3), 4 - [(2,4-dihydroxyphenylazo) -b sulfonic 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-naphthalene-disulfonic 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); (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-on-9-yl) -benzoic acid disodium salt (CI 45,430, Acid Red 51), N- [6- (D iethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethylethanammonium hydroxide, inner salt, sodium salt (CI 45, 100; Acid red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1,3-disulfonic acid disodium salt (CI 27.290; Acid Red 73), 2 ', 4', 5 ', 7'-tetrabromo-3', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one disodium salt (CI 45.380; Acid Red 87), 2 ', 4', 5 ', 7'-tetrabromo-4,5,6,7-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) xanthene] - 3-one disodium salt (CI 45425, Acid Red 95), 2-hydroxy-3 - ((2-hydroxynaphth-1-yl) azo) -5-nitrobenzenesulfonic acid, sodium salt (CI 15,685, Acid Red 184), 3-hydroxy -4- (3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-ylazo) -naphthalene-1-sulfonic acid, sodium salt, chromium complex (Acid Red 195), 3- Hydroxy-4 - [(4-methyl-2-sulfonphenyl) -azo] -2-naphthalenecarboxylic acid calcium salt (CI 15.850: 1; Pigment Red 57: 1), 3 - [(2,4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid disodium salt (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- (d imethylamino) phenyl] - (3,7-disulfo-2-hydroxynaphth-1-yl) carbenium inner salt, sodium salt (CI 44,090; Food Green No. 4; Acid Green 50), bis [4- (diethylamino) -phenyl] (2,4-disulfophenyl) carbenium inner salt, sodium salt (2: 1) (CI 42.045, Food Blue No. 3, Acid Blue 1), Bis [ 4- (diethylamino) phenyl] (5-hydroxy-2,4-disulfophenyl) carbenium inner salt, calcium salt (2: 1) (CI 42,051; Acid Blue 3), N- [4 - [(2,4-) Disulfophenyl) [4- [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5-cyclohexadien-1-ylidene] -N-ethylbenzene methanaminium hydroxide, 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) - 9,10-anthraquinone-2-sulfonic acid (CI 62.055, Acid Blue 25), 1-amino-4- (cyclohexylamino) -9,10-anthraquinone-2-sulfonic acid sodium salt (CI 62045; Acid Blue 62), 2- (1 , 3-Dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene) -2,3-dihydro-3-oxo-1H-indole-5-sulfonic acid disodium salt (CI 73.015; Acid Blue 74), 9- (2-carboxyphenyl) -3 - [(2-methylphenynamino] -6 - [(2-methyl-4-sulfophenyl) amino] xanthylium internal 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 among the international ones Designations or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds.

Cationic direct dyes:

Particularly suitable cationic direct dyes are 9- (dimethylamino) benzo [a] phenoxazine-7-ium chloride (CI 51.175; Basic Blue 6), di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl]. carbenium chloride (CI 42,595; Basic Blue 7), di (4- (dimethylamino) phenyl) - (4- (methylphenylamino) -naphthalen-1-yl) carbenium chloride (CI 42,563, Basic Blue 8), 3,7-Di (dimethylamino) phenothiazine-5-ium chloride (CI 52.015 Basic Blue 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (CI 44.045, Basic Blue 26 ), 2 - [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methylbenzothiazolium methylsulfate (CI 11.154, Basic Blue 41), 8-amino-2-bromo 5-hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (CI 56.059; Basic Blue No. 99), bis [4- (dimethylamino) phenyl] - [4- (methylamino) phenyl] carbenium chloride (CI 42,535, Basic Violet 1), tri (4-amino-3-methylphenyl) carbenium chloride (CI 42,520, Basic Violet 2), tri [4- (dimethylamino) -phenyl] carbenium chloride (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-methoxyphenynazo) -7- (trimethylammonio) -naphthalene chloride (CI 12,245; Basic Red 76), di [4- (dimethylamino) phenyl] iminomethane hydrochloride (CI 41,000, Basic Yello w 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indol-1-ium chloride (CI 48.055; Basic Yellow 11), 3-methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (CI 12.719; Basic Yellow 57), bis [4- (diethylamino) phenyl] phenylcarbenium hydrogensulfate (1: 1) (CI 42.040, Basic Green 1), di (4- (dimethylamino) phe nyl) -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 direct dyes containing a heterocycle having at least one quaternary nitrogen atom.

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

Preferred cationic substantive dyes are included

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

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

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

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

Nonionic substantive dyes:

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

In another classification is the substantive dyes divided 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-hydroxyethylamino] -2-nitrobenzene hydrochloride (HC Blue 12), 2 - ((4-amino-2-nitrophenyl) amino) -5-dimethylaminobenzoic acid (HC Blue 13), 1-amino-3-methyl 4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet 1), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet 2), 1- (2-aminoethylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene, 4- (di (2-hydroxyethyl) amino) -2-nitro-1-phenylaminobenzene.

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

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

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

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

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

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

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

Farther can as direct dyes and natural dyes be used. As natural dyes in the context of the invention Understanding dyes derived from parts of plants. For this purpose, preferably different parts of plants, depending on the desired Dye. It is understood, however, that one dye is more can be obtained as a plant part.

The are preferred plant parts for the production of natural dyes contained in the group, which is formed from root, stems, Bark, heartwood, resin, blossom, leaf, fruit and sap. For the purposes of the invention, it is still for natural dyes it is not necessary that the funds obtained from the plant parts Dyes represent as such, but that they may be also represent dye precursors, which are characterized by subsequent chemical Reactions form the actual dye. Called here in particular the oxidation with atmospheric oxygen to form the Chromophore.

It is in particular for the purposes of the invention not required that the dyes or dye precursors in each case uniform Represent connections. Due to different, not uniform Extraction methods such as different extraction or fermentation conditions or by using different, regional subspecies and various plant parts or partially also from culture-historical tradition contain some mentioned Natural dyes deliberately no uniform compounds, but Mixtures of dyes, dye precursors and other components, especially tannins.

in the The meaning of the invention as a natural dye is understood also a discrete color-giving isolated from such a mixture Compound or optionally also several, from such a mixture isolated, discrete, coloring compounds understood. 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, Proof, H. Schweppe, Ecomed Publishing Company, 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, α-Lapachon, β-Lapachon, Melchinon I, Lapachononund Dehydro-α-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), Aloe-emodin, Physcion, Rhéin, 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 – braziletto, jeweils als Kernholz Haematoxylum (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-methylsantarubin, 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, α-lapachone, β-lapachone, melchinone I, lapachonone and dehydro-α- 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), Aloe-emodin, Physcion, Rhéin, the heterodianthrones Rhéidine 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-Hy 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 foster tinctoria (Indigofera argentea), dyer - Isatis tinctoria, dyer oleander - 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., braziletto wood - braziletto, each as heartwood haematoxylum (CI Natural Red 24), with the dye precursor Brasilin, which is oxidative 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., Narrowwood - Pterocarpus indicus L., Barwood - Pterocarpus soyauxii L., Camwood - Bahia nitida (CI Natural Red 22) with the dye the ingredients santalin A, santalin B, tetra-O-methylsantarubin, hompterocarpine, pterocarpine, maackiain, the isoflavionides formononetin and santal, as well as the chalcone isoliquiritigenin and the flavone 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, for example in the bark of stalk or summer areas - Quercus robur L. with the main coloring constituents from the group of gallotannins and ellagannins (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:
  

Especially contain the cosmetic compositions of the invention 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 according to the invention preferred natural dyes are those obtained from a plant, which is selected from the group that is formed Indigofera tinctoria, Curcuma longa, Lawsonia inermis, Chamomilla recutita, Quercus robur, Rosmarinus officinalis, Rheum undulatum and Beta vulgaris.

All in this case, the group which is formed is particularly preferred Diaryloylmethane dyes, naphthoquinone dyes and indigoids Dyes.

All are particularly preferred in the inventive Cosmetic products contain natural dyes of plants that are selected from the group consisting of turmeric longa (turmeric, C.I. Natural Yellow 3), Lawsonia inermis (Henna, red; C. I. Natural Orange 6) and Indigofera tinctoria (Henna, black; C. I. Natural Blue 1).

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

The Colorants according to the invention can all active substances, additives known to and auxiliaries. 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 proven to be advantageous the surfactants from anionic, zwitterionic or nonionic Select surfactants.

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

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

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface active hydroxysulfonates according to DE-A-37 25 030 .
• - Sulfated 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 in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid ,

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

Nonionic surfactants contain as hydrophilic group z. B. a polyol group, a polyalkylene glycol Kolethergruppe or a combination of polyol and Polyglykolethergruppe. 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 ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, and
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil.

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

The alkyl radical R ¹ contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl.

Especially preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. Using so-called "oxo-alcohols" as starting materials predominate Compounds with an odd number of carbon atoms in the alkyl chain.

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.

When Sugar building block Z can be any mono- or oligosaccharides be used. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides 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 special prefers.

The Alkylpolyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkylpolyglykoside with x values of 1.1 to 1.6 are preferred. Very particularly preferred are alkyl glycosides in which x is 1.1 to 1.4.

The Alkyl glycosides can be used in addition to their surfactant effect serve to improve the fixation of fragrance components on the hair. The expert will be so in the event that one over the duration of the hair treatment beyond effect of the perfume oil is desired on the hair, preferably to this class of substance as a further ingredient of the invention Resort to preparations.

Also the alkoxylated homologs of said alkyl polyglycosides can used according to the invention. These homologs can average up to 10 ethylene oxide and / or Propylene oxide units per Alkylglykosideinheit included.

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 cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. 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 as cationic surfactants, especially those of the quaternary type Ammonium compounds, the esterquats and the amidoamines used.

preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, Dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, z. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants mentioned 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 represent 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".

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

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 restricted homologs 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-, Kerstin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• – quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• – Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• – Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,.
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien,

enthaltenFurthermore, the 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,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• - active substances such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• Fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizer for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants,

contain

In terms of additional optional components and the quantities used These components are expressly referred to the person skilled in the art known relevant manuals, z. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

The agents according to the invention contain the dye precursors preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose the hair coloring are such carriers, for example Creams, emulsions, gels or surfactant-containing foaming Solutions, such as shampoos, foam aerosols or other preparations for use on the hair are suitable. But it is also conceivable, the dye precursors in a powdered or tablet-shaped To integrate 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 staining of the fibers can basically done with atmospheric oxygen. However, preference is given to a chemical Oxidizing agent used, especially if in addition to the staining a whitening effect on human hair is desired. When Oxidizing agents include persulfates, chlorites and especially hydrogen peroxide or its addition products of urea, melamine and sodium borate in Question. However, according to the invention, the oxidation colorant also be applied to the hair together with a catalyst, the oxidation of the dye precursors, eg. B. by atmospheric oxygen, activated. Such catalysts are z. As metal ions, iodides, Quinones or certain enzymes.

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

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

Suitable enzymes are z. As peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, for. B.

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

The actual hair dye is conveniently immediately before use by mixing the preparation of the Oxidizing agent with the preparation containing the dye precursors, produced. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Particularly preferred is the application of the hair dye in a slightly alkaline environment. The application temperatures can range between 15 and 40 ° C. To an exposure time of 5 to 45 minutes becomes the hair dye by rinsing away from the hair to be dyed. The washing with a shampoo is eliminated if a strong surfactant-containing carrier, for. B. a dyeing shampoo, has been used.

Especially with hair that is difficult to dye, however, the preparation with the dye precursors can 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.

One second subject of the present invention is a method for coloring keratinous fibers, in which an inventive Hair dye is applied to the fibers and after an exposure time is rinsed off again.

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

wobei

• – der Rest R1 steht für einen gesättigten, 5- bis 15-gliedrigen Heterocyclus, der mindestens ein Stickstoffatom und gegebenenfalls bis zu 3 weitere Heteroatome, ausgewählt aus einem Sauerstoffatom oder der Gruppe -NR3-, aufweist, wobei der Heterocyclus über ein Stickstoffatom an das aromatische Ringsystem gebunden ist, und R3 steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine C₁-C₆-Hydroxyalkylgruppe, und
• – der Rest R2 steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, eine Aminogruppe, eine Di-(C₁-C₆-Alkyl)aminogruppe, ein Halogenatom oder eine Hydroxygruppe

als Kupplerkomponente zur oxidativen Färbung keratinischer Fasern.A third aspect of the present invention is the use of a 6-amino-2-hydroxypyridine derivative of the formula (I)

in which

• - the radical R 1 is a saturated, 5- to 15-membered heterocycle having at least one nitrogen atom and optionally up to 3 further heteroatoms selected from an oxygen atom or the group -NR 3 -, wherein the heterocycle via a nitrogen atom to the R3 is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl or C ₁ -C ₆ hydroxyalkyl, and
• The radical R ₂ is 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 C ₁ -C ₆ alkoxy, amino, di- (C ₁ -C ₆ alkyl) amino, halogen or hydroxy

as a coupler component for the oxidative dyeing of keratinic fibers.

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

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

embodiments

1 Synthesis examples

1.1 Synthesis of 6- (morpholin-4-yl) pyridin-2-ol

A mixture of 39.6 g (0.305 mol) of 2-chloro-6-hydroxypyridine and 250 ml of morpholine was stirred for 72 hours at 90 ° C. In the course of the reaction, the reaction solution turned dark green. After cooling, the precipitated solid (morpholine hydrochloride) was filtered off, the filtrate was subjected to rotary evaporation in vacuo freed from excess morpholine. The residual dark green oil was stirred in the heat with 100 ml of toluene and then cooled to 0 ° C. After some time a light green solid began to precipitate, which was filtered, washed with a little cold toluene and dried in vacuo.
Yield: 30.0 g (54.6%)
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 3.29 (t, 4H); 3.64 (t, 4H); 5.89 (d, 1H); 6.08 (d, 1H); 7.36 (dd, 1H)
¹³ C-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 45.9; 65.7; 96.0; 99.2; 140.7; 157.3; 162.5

2 colorations

2.1 Experimental procedure

• ¹ C_1-18-Fettalkohol (INCI-Bezeichnung: Cetearyl alcohol) (Cognis)
• ² C_12-18-Fettalkohol (INCI-Bezeichnung: Coconut alcohol) (Cognis)
• ³ Laurylethersulfat, Natriumsalz (ca. 27,5% Aktivsubstanz; INCI-Bezeichnung: Sodium Laureth Sulfate) (Cognis)
• ⁴ N,N-Dimethyl-N-(C_8-18-kokosamidopropyl)ammoniumacetobetain (ca. 30% Aktivsubstanz; INCI-Bezeichnung: Aqua (Water), Cocamidopropyl Betaine) (Cognis)
• ⁵ Cetylstearylalkohol mit ca. 20 EO-Einheiten (INCI-Bezeichnung: Ceteareth-20) (Cognis)

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 sodium 1.0% by weight ammonium sulfate 1.0% by weight developer component 3 mmol Kupplerkomponente 3 mmol water ad 100% by weight

• ¹ C _1-18 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 together with Texapon NSO-UP, Dehyton K. and Eumulgin B2 melted at 80 ° C. Then the Melt with the sodium sulfite dissolved in a part of the water and Emulsified ammonium sulfate. The developer and the invention Couplers were added in a further portion of the indicated amount of water dissolved with heating and added with stirring. The coupler was also in part of the specified amount of water dissolved and added with stirring. Then it became the formulation is made up to 100% by weight with water and cold stirred.

• ⁶ 1-Hydroxyethan-1,1-diphosphonsäure (ca. 58–61% Aktivsubstanzgehalt; INCI-Bezeichnung: Etidronic Acid, Aqua (Water)) (Solutia)
• ⁷ Laurylethersulfat-Natrium-Salz (mind. 26,5% Aktivsubstanzgehalt; INCI-Bezeichnung: Sodium Laureth Sulfate) (Cognis)
• ⁸ Acrylpolymer (ca. 29.5–30.5% Festkörper in Wasser; INCI-Bezeichnung: Acrylates/Steareth-20 Methacrylate Copolyme)

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 coloring of the strands was judged visually under the daylight lamp after drying. The staining results are summarized in the table below. 2.2 colorations with 6- (morpholin-4-yl) pyridin-2-ol as coupler component developer component obtained shade / color intensity p-toluenediamine dark brown / +++ 2- (β-hydroxyethyl) -p-phenylenediamine violet brown / ++ N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine green brown / ++ N, N-bis (β-hydroxyethyl) -p-phenylenediamine blue black / +++ 4,5-diamino-1 - ([3-hydroxyethyl) pyrazole red / +++

• +++ hohe Intensität ++ mittelere Intensität + niedrige Intensität

The color intensity was rated as follows:

• +++ high intensity ++ medium intensity + low intensity

3 Determination of the fastness properties

3.1 Determination of wash fastness as well as the leveling ability

3.1.1 Production of Leveling Strands

It were about 15 cm long, 80% gray hair strands of Company Kerling used. The lower part of the strand was for 30 minutes of a commercial cold wave and then for 10 minutes a commercial Subjected to fixation. After washing and drying was the lower stratum part for 30 minutes with a commercial product ultra-blonde, washed and dried. Then the bottom part became the strand of hair is again cold-curled after the above procedure and fixed. Subsequently, the entire strand was subjected to Ultrablondierung, washed and dried again. The treated hair strands have a high degree of damage in the lower part of the tress and a moderate injury in the upper part of the strand on.

3.1.2 colorations

Each 8.0 g of the ready-to-use coloring cream (corresponding to Item 2.1)) were applied to a leveling bar and leave it at 32 ° C for 30 minutes. To Termination of the exposure time, the hair was rinsed out and then dried.

3.1.3 Measurement of leveling power and wash fastness

To the dyeing process, the Egalisiersträhnen colorimetric with a colorimeter from Datacolor, Type Spectraflash 450 measured.

A Measurement took place in the upper part of the hair strand, another Measurement was made in the lower, severely damaged part of the tress carried out.

Subsequently The strands were hand-pulled 6 times with a 25% Texapon NSO-UP solution washed, rinsed and after each Washing process dried with a hair dryer. After the last one Drying was carried out a new colorimetric measurement after the procedure described above.

at For each measurement, an L value, A value and a b value were determined.

Of the L value stands for the brightness of the coloring (Black-white-axis); the larger the value for L, the lighter the coloration.

Of the a-value stands for the red-green axis of the system; the larger the value, the more the coloration in the Red shifted.

The b value stands for the yellow-blue axis of the system; the larger the value, the more the color moved to yellow.

Color differences are characterized by the ΔE value, which is calculated from the three determined values according to equation (I):

3.1.4 Evaluation of the wash fastness

Combination 1: p-toluenediamine / 6- (morpholin-4-yl) pyridin-2-ol L value a-value b-value AE value Upper part of the strand Before washing 19 4 0 3.7 After the 6 washing cycles 22 6 1 Lower part of the strand Before washing 17 2 -1 3.0 After the 6 washing cycles 19 4 0 Combination 2: 2- (β-hydroxyethyl) -p-phenylenediamine / 6- (morpholin-4-yl) pyridin-2-ol L value a-value b-value AE value Upper part of the strand Before washing 22 5 0 1.7 After the 6 washing cycles 23 6 1 Lower part of the strand Before washing 18 3 0 4.2 After the 6 washing cycles 22 4 1 Combination 3: N, N-bis (β-hydroxyethyl) -p-phenylenediamine / 6- (morpholin-4-yl) pyridin-2-ol L value a-value b-value AE value Upper part of the strand Before washing 22 1 -7 1.0 After the 6 washing cycles 23 1 -7 Lower part of the strand Before washing 17 1 -3 4.4 After the 6 washing cycles 20 0 -6

A good washfastness is present when received before the washout L values, a values and b values are only marginally different from those after differ from the values obtained in the washout procedure and the resulting ΔE values are accordingly small. This is for all investigated inventive combinations of the case, so that the wash fastness can be classified as very good.

3.1.5 Determination of leveling power before and after washing

Combination 1: p-toluenediamine / 6- (morpholin-4-yl) pyridin-2-ol L value a-value b-value AE value Before washing Upper part of the strand 19 4 0 3.0 Lower part of the strand 17 2 -1 After washing Upper part of the strand 22 6 1 3.7 Lower part of the strand 19 4 0 Combination 2: 2- (β-hydroxyethyl) -p-phenylenediamine / 6- (morpholin-4-yl) pyridin-2-ol L value a-value b-value AE value Before washing Upper part of the strand 22 5 0 4.5 Lower part of the strand 18 3 0 After washing Upper part of the strand 23 6 1 2.2 Lower part of the strand 22 4 1 Combination 3: N, N-bis (β-hydroxyethyl) -p-phenylenediamine / 6- (morpholin-4-yl) pyridin-2-ol L value a-value b-value AE value Before washing Upper part of the strand 22 1 -7 5.4 Lower part of the strand 17 1 -3 After washing Upper part of the strand 23 1 -7 3.3 Lower part of the strand 20 0 -6

One good leveling power is present when the upper stratum part and L, a, b values measured in the lower strand part only have small deviations from each other and the calculated ΔE value accordingly is small. For all three inventive Developer / coupler combinations give way to the L values, the a values and the b-values of the upper part of the strands only slightly from those of the lower strands part. This is true for the before washing as well as for the after values obtained six times. The leveling ability all measured nuances is therefore also very good classified.

3.2 Determination of lightfastness

The dyed strands of hair were exposed next to textile lightfastness scales (1-6) in the xenon tester for 120 hours. A part of the tress was covered with a template, so that only the uncovered part of the hair was exposed to the exposure. The evaluation was made by a comparison the contrasts on the strands with those on the light fastness scales. A value of 1 means a very poor light fastness, at a value of 6, the coloring of the hair strand by the irradiation is not weakened at all. From a value of 4, the lightness of an oxidative coloration is classified as very good to good. Developer / coupler combination fastness p-toluenediamine / 6- (morpholin-4-yl) pyridin-2-ol 5 2- (β-hydroxyethyl) -p-phenylenediamine / 6- (morpholin-4-yl) pyridin-2-ol 4 N, N-bis (β-hydroxyethyl) -p-phenylenediamine / 6- (morpholin-4-yl) pyridin-2-ol 4

3.3 Determination of color removal by oxidative aftercare

The dyed streak was treated for 30 minutes at 32 ° C with a commercial Ultrablondierung. After rinsing and drying, the tresses were visually evaluated under the daylight lamp. The strength of the color proof was described by means of a score system from 1 to 5: Nuance unchanged Grade 1 (very poor color print) Nuance slightly lightened Grade 2 Nuance moderately lightened Note 3 Nuance brightened up a lot Grade 4 Nuance discolored Grade 5 (very good color proof) Developer / coupler combination Coloring after the color print p-toluenediamine / 6- (morpholin-4-yl) pyridin-2-ol 5 2- (β-hydroxyethyl) -p-phenylenediamine / 6- (morpholin-4-yl) pyridin-2-ol 5 N, N-bis (β-hydroxyethyl) -p-phenylenediamine / 6- (morpholin-4-yl) pyridin-2-ol 5

Of the by color oxidation caused by an oxidative after-treatment for all investigated inventive Developer / coupler combinations classified as very good.

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• - EP 998908 A2 [0136]
• - DE 3725030 A [0161]
• - DE 3723354 A [0161]
• - DE 3926344 A [0161]

Claims (14)

Agent for coloring keratinic fibers, in particular human hair, characterized in that it contains, in a cosmetically acceptable carrier as coupler component, at least one 6-amino-2-hydroxypyridine derivative of the formula (I)

wherein R1 is a saturated, 5- to 15-membered heterocycle having at least one nitrogen atom and optionally up to 3 further heteroatoms selected from an oxygen atom or the group -NR3-, wherein the heterocycle has a Nitrogen atom is bonded to the aromatic ring system, and R3 is a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group or a C ₁ -C ₆ hydroxyalkyl group, and - the radical R ₂ is a 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 C ₁ -C ₆ -alkoxy group, an amino group, a di (C ₁ -C ₆ alkyl) amino group, a halogen atom or a hydroxy group. Composition according to Claim 1, characterized in that R 2 represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ -alkyl group, in particular a hydrogen atom, a chlorine atom or a methyl group. Composition according to one of claims 1 or 2, characterized in that R1 is a group of formula (II)

wherein - X is one of the groups • - (CH ₂ ) _n -, • - (CH ₂ ) _n -Y 1 - (CH ₂ ) _m , • - (CH ₂ ) _n -Y 1 - (CH ₂ ) _m -Y 2 - (CH ₂ ) _o - or • - (CH ₂ ) _n -Y 1 - (CH ₂ ) _m -Y ₂ - (CH ₂ ) _o -Y 3 - (CH ₂ ) _p -, - Y 1, Y _{2 and} Y 3 are each independently R3 represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkylene group or a C ₂ -C ₆ -hydroxyalkyl group, and - n, m, o and p are each independently an integer between 1 and 7, with the proviso that the sum of n + m + p + o is at least 4 and at most 13. Composition according to one of claims 1 to 3, characterized in that R1 represents a radical of formula (II), wherein X is a group - (CH ₂ ) - and n is an integer from 4 to 6. Means according to claim 4, characterized in that the radical R1 represents a pyrrolidin-1-yl ring, a Piperidin-1-yl ring or an azepan-1-yl ring. Composition according to one of claims 1 to 3, characterized in that R1 represents a radical of formula (II), wherein X represents a group - (CH ₂ ) _n -Y1- (CH ₂ ) _m -, wherein - Y1 for an oxygen atom or a group -NR3, -n and m are independently an integer from 1 to 3, with the proviso that the sum of n + m is at least 4 and - R3 is a hydrogen atom, a C ₁ C ₆ alkyl group, a C ₂ -C ₆ alkylene group or a C ₂ -C ₆ hydroxyalkyl group. Means according to claim 6, characterized in that R1 represents a morpholin-4-yl ring, a piperazin-1-yl ring, a 4-methylpiperazin-1-yl ring or a 4- (2-hydroxyethyl) piperazin-1-yl ring. Composition according to one of claims 1 to 3, characterized in that R1 represents a radical of formula (II), wherein X is a group - (CH ₂ ) _n -Y1- (CH ₂ ) _m -Y ₂ - (CH ₂ ) _o -, where - Y1 and Y2 independently represent an oxygen atom or a group -NR3-, - n, m and o are independently an integer of 1 to 3, with the proviso that the sum of n + m + o is at least 4 and - R3 represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkylene group or a C ₂ -C ₆ hydroxyalkyl group. Means according to claim 8, characterized in that R1 represents a 1,4,7-dioxazonan-7-yl ring. Agent according to one of claims 1 to 9, characterized in that it comprises at least one developer component contains. Agent according to one of claims 1 to 10, characterized in that there is at least one further coupler component contains. Agent according to one of claims 1 to 11, characterized in that further at least one substantive Contains dye. Method for coloring keratinic fibers, in which an agent according to any one of claims 1 to 13 to the Fibers is applied and rinsed again after a contact time becomes. Use of a 6-amino-2-hydroxypyridine derivative of the formula (I)

wherein - the radical R 1 is a saturated, 5- to 15-membered heterocycle having at least one nitrogen atom and optionally up to 3 further heteroatoms selected from an oxygen atom or the group -NR 3 -, wherein the heterocycle via a nitrogen atom the aromatic ring system is bonded, and R 3 is a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₁ -C ₆ -hydroxyalkyl group, and - the radical R ₂ is 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 C ₁ -C ₆ alkoxy group, an amino group, a di - (C ₁ -C ₆ alkyl) amino group, a halogen atom or a hydroxy group as a coupler component for the oxidative dyeing of keratinic fibers.