DE102010040508A1 - Agent for coloring keratinic fibers with cationic derivatives of 1- (2,5-dihydroxyphenyl) pyridinium - Google Patents

Abstract

The present application relates to agents for coloring keratinic fibers, in particular human hair, which are in a cosmetically acceptable carrier as developer component at least one cationic derivative of 1- (2,5-dihydroxyphenyl) pyridinium of the general formula (I) in R1, R2 independently of one another for a hydrogen atom, a C1-C6-alkyl group, a C2-C6-alkenyl group, a C1-C6-alkoxy group, a halogen atom (Cl, Br, F or J), a C1-C6-hydroxyalkyl group, a C2-C6 -Polyhydroxyalkyl group, a hydroxy-C2-C6-alkyloxy group, an aryl group, an aryl-C1-C6-alkyl group or an aryl-C1-C6-alkyloxy group, X- stands for a monovalent anion, preferably for halide, hydrogen sulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate.

Description

The present invention relates to keratin fiber coloring agents characterized by containing cationic derivatives of 1- (2,5-dihydroxyphenyl) pyridinium as novel developers for oxidative hair coloring. Furthermore, the invention relates to the use of these agents for dyeing keratinic fibers and a corresponding method.

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

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

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

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

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

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

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

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

Surprisingly, it has now been found that cationic derivatives of 1- (2,5-dihydroxyphenyl) pyridinium fulfill the requirements placed on developer components to a high degree. The developer components according to the invention allow the production of rich and intense nuances, especially in the field of natural tones, which are characterized by very good fastness properties.

• [1] A new class of developing agents. Kumetat, K. Zeitschrift fuer Wissenschaftliche Photographie, Photophysik und Photochemie (1948), 43 113–19. CODEN

The use of the substances according to the invention as developers in color photography is described in disclosure [1]. So far, no indications have been found in the literature that this substance class is also very suitable for the coloring of keratinic fibers.

• [1] A new class of developing agents. Kumetat, K. Journal of Scientific Photography, Photophysics and Photochemistry (1948), 43 113-19. CODEN

in der
R¹, R² stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Alkoxygruppe, ein Halogenatom (Cl, Br, F oder J), eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine Hydroxy-C₂-C₆-alkyloxygruppe, eine Arylgruppe, eine Aryl-C₁-C₆-alkylgruppe oder eine Aryl-C₁-C₆-alkyloxygruppe,
X^– steht für ein einwertiges Anion, vorzugsweise für Halogenid, Hydrogensulfat, ½ Sulfat, Benzolsulfonat, p-Toluolsulfonat, Acetat, Citrat, Lactat, Tetrafluoroborat, Trifluormethansulfonat, Hexafluorophosphat, Methansulfat oder Methansulfonat,
enthalten.A first subject of the present invention are therefore agents for coloring keratinic fibers, which in a cosmetically acceptable carrier as the developer component at least one cationic derivative of 1- (2,5-dihydroxyphenyl) pyridinium of the general formula (I)

in the
R ¹ , R ² independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -alkoxy group, a halogen atom (Cl, Br, F or J) , a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a hydroxy C ₂ -C ₆ alkoxy group, an aryl group, an aryl C ₁ -C ₆ alkyl group or an aryl C ₁ - C ₆ alkyloxy group,
X ^- is a monovalent anion, preferably halide, hydrogensulfate, ½ sulfate, benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate,
contain.

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

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 C ₁ -C ₆ alkyl groups. The vinyl group and the allyl group have been found to be particularly suitable C ₂ -C ₆ alkenyl groups. Preferred C ₁ to C ₆ alkoxy groups are the methoxy and ethoxy groups.

Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. Furthermore, as preferred examples of a C ₁ to C ₆ monohydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₆ polyhydroxyalkyl group is the 1,2-dihydroxyethyl group.

The 2- (hydroxy) ethoxy group and the 3- (hydroxy) propoxy group are examples of particularly preferred hydroxy-C ₂ -C ₆ alkoxy groups. Particularly suitable aryl groups may be mentioned the naphthyl group and in particular the phenyl group.

The benzyl group is an example of a particularly suitable aryl-C ₁ -C ₆ -alkyl group, and the benzyloxy group can be named as a particularly advantageous aryl-C ₁ -C ₆ -alkyloxy group. The other terms used are derived from the definitions given here.

The (2,5-dihydroxyphenyl) pyridinium salts of the formula (I) according to the invention can be prepared by means of conventional organic methods. For example, reference is made at this point to the experimental procedures in the context of the embodiments.

It has been found according to the invention as being preferred when the radicals R ¹ and R ^{2 are} independently a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group or a halogen atom (Cl, Br, F or I) represent.

In this case, it is particularly preferred if at least one of the two radicals R ¹ or R ^{2 is} a hydrogen atom. Compounds of the general formula (I) in which both the radical R ¹ and the radical R ^{2 represent} a hydrogen atom have proven to be most suitable in the course of the work leading to this invention.

• – Salzen des 1-(2,5-Dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(2,5-Dihydroxy-4-methylphenyl)pyridiniums
  
• – Salzen des 1-(2,5-Dihydroxy-3-melhylphenyl)pyridiniums
  
• – Salzen des 1-(3,6-Dihydroxy-2-methylphenyl)pyridiniums
  
• – Salzen des 1-(4-Chlor-2,5-dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(3-Chlor-2,5-dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(2-Chlor-3,6-dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(4-Brom-2,5-dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(3-Brom-2,5-dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(2-Brom-3,6-dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(2,5-Dihydroxy-4-methoxyphenyl)pyridiniums
  
• – Salzen des 1-(2,5-Dihydroxy-3-methoxyphenyl)pyridiniums
  
• – Salzen des 1-(3,6-Dihydroxy-2-methoxyphenyl)pyridiniums
  
• – Salzen des 1-(4-Ethoxy-2,5-dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(3-Ethoxy-2,5-dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(2-Ethoxy-3,6-dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(2,5-Dihydroxy-3,4-dimethylphenyl)pyridiniums
  
• – Salzen des 1-(3,4-Dichlor-2,5-dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(3,4-Dibrom-2,5-dihydroxyphenyl)pyridiniums
  
• – Salzen des 1-(2,5-Dihydroxy-3,4-dimethoxyphenyl)pyridiniums
  
• – Salzen des 1-(3,4-Diethoxy-2,5-dihydroxyphenyl)pyridiniums
  

In a particularly preferred embodiment, the compositions according to the invention for dyeing keratinic fibers contain at least one new development molecule selected from

• - Salts of 1- (2,5-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (2,5-dihydroxy-4-methylphenyl) pyridinium
  
• - Salts of 1- (2,5-dihydroxy-3-melhylphenyl) pyridinium
  
• - Salts of 1- (3,6-dihydroxy-2-methylphenyl) pyridinium
  
• - Salts of 1- (4-chloro-2,5-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (3-chloro-2,5-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (2-chloro-3,6-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (4-bromo-2,5-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (3-bromo-2,5-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (2-bromo-3,6-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (2,5-dihydroxy-4-methoxyphenyl) pyridinium
  
• - Salts of 1- (2,5-dihydroxy-3-methoxyphenyl) pyridinium
  
• - Salts of 1- (3,6-dihydroxy-2-methoxyphenyl) pyridinium
  
• - Salts of 1- (4-ethoxy-2,5-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (3-ethoxy-2,5-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (2-ethoxy-3,6-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (2,5-dihydroxy-3,4-dimethylphenyl) pyridinium
  
• - Salts of 1- (3,4-dichloro-2,5-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (3,4-dibromo-2,5-dihydroxyphenyl) pyridinium
  
• - Salts of 1- (2,5-dihydroxy-3,4-dimethoxyphenyl) pyridinium
  
• - Salts of 1- (3,4-diethoxy-2,5-dihydroxyphenyl) pyridinium
  

• – 1-(2,5-Dihydroxyphenyl)pyridiniumchlorid
• – 1-(2,5-Dihydroxyphenyl)pyridiniumbromid
• – 1-(2,5-Dihydroxyphenyl)pyridiniumhydrogensulfat
• – 1-(2,5-Dihydroxyphenyl)pyridinium-p-toluolsulfonat
• – 1-(2,5-Dihydroxyphenyl)pyridiniumbenzolsulfonat
• – 1-(2,5-Dihydroxyphenyl)pyridiniumacetat

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

• - 1- (2,5-Dihydroxyphenyl) pyridinium chloride
• - 1- (2,5-Dihydroxyphenyl) pyridinium bromide
• - 1- (2,5-dihydroxyphenyl) pyridinium hydrogen sulfate
• - 1- (2,5-Dihydroxyphenyl) pyridinium p-toluenesulfonate
• - 1- (2,5-Dihydroxyphenyl) pyridinium benzene sulphonate
• - 1- (2,5-dihydroxyphenyl) pyridinium acetate

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

In the context of a further preferred embodiment of the present invention, the agents according to the invention contain at least one further oxidation dye precursor of the developer and / or coupler type.

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts.

Particularly preferred p-phenylenediamines are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine and N-phenyl-p-phenylenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine and their physiologically acceptable salts.

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

Preferred binuclear developer components are in particular N, N'-bis (2-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol and bis (2-hydroxy 5-aminophenyl) methane and their physiologically acceptable salts.

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Preferred p-aminophenols are in particular p-aminophenol, N-methyl-p-aminophenol, and 4-amino-3-methyl-phenol and their physiologically tolerated salts.

Further, the developer component may be selected from o-aminophenol and its derivatives, such as 2-amino-5-methylphenol and its physiologically acceptable salts.

Furthermore, the developer component may be selected from heterocyclic developer components, such as the pyridine, pyrimidine, pyrazole, pyrazolo-pyrimidine derivatives and their physiologically acceptable salts.

Preferred pyrimidine derivatives are in particular 2,4,5,6-tetraaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine and their physiologically acceptable salts.

A preferred pyrazole derivative is 4,5-diamino-1- (2-hydroxyethyl) pyrazole and its physiologically acceptable salts.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Suitable coupler substances are in particular 1-naphthol, 1,5- and 2,7-dihydroxynaphthalene, 1-acetoxy-2-methoxynaphthalene, resorcinol, 4-chloro-resorcinol and 2-amino-3-hydroxypyridine and their physiologically tolerated salts.

• (A) m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, 3-Amino-2-chlor-6-methylphenol, 5-Amino-4-chlor-2-methylphenol, 5-(2'-Hydroxyethyl)-amino-2-methylphenol und 2,4-Dichlor-3-aminophenol,
• (B) o-Aminophenol und dessen Derivate, beispielsweise 2-Amino-5-ethylphenol, (C) m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxy-ethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol, 2-({3-[(2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol und 2-({3-[(2-Hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol,
• (D) o-Diaminobenzol und dessen Derivate,
• (E) Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise 2-Methylresorcin und 1,2,4-Trihydroxybenzol,
• (F) Pyridinderivate wie beispielsweise 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Diaminopyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2-Amino-3-hydroxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• (G) Naphthalinderivate wie beispielsweise 1-Naphthol und 2-Methyl-1-naphthol,
• (H) Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin,
• (I) Chinoxalinderivate,
• (J) Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• (K) Indolderivate wie beispielsweise 6-Hydroxyindol,
• (L) Pyrimidinderivate oder
• (M) Methylendioxybenzolderivate wie beispielsweise 1-(2'-Hydroxyethyl)-amino-3,4-methylendioxybenzol

sowie deren physiologisch verträgliche Salze.According to preferred coupler components are

• (A) m-Aminophenol and its derivatives such as 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5- (2'-hydroxyethyl ) -amino-2-methylphenol and 2,4-dichloro-3-aminophenol,
• (B) o-aminophenol and its derivatives, for example 2-amino-5-ethylphenol, (C) m-diaminobenzene and its derivatives such as 2,4-diaminophenoxy-ethanol, 1,3-bis- (2 ', 4' -diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 2,6-bis (2'-hydroxyethylamino) -1- methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol and 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5- methylphenyl} amino) ethanol,
• (D) o-diaminobenzene and its derivatives,
• (E) di- or trihydroxybenzene derivatives such as, for example, 2-methylresorcinol and 1,2,4-trihydroxybenzene,
• (F) pyridine derivatives such as 3-amino-2-methylamino-6-methoxypyridine, 2,6-diaminopyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2-amino-3-hydroxypyridine and 3,5-diamino 2,6-dimethoxy,
• (G) naphthalene derivatives such as 1-naphthol and 2-methyl-1-naphthol,
• (H) morpholine derivatives such as 6-hydroxybenzomorpholine,
• (I) quinoxaline derivatives,
• (J) pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• (K) indole derivatives such as 6-hydroxyindole,
• (L) pyrimidine derivatives or
• (M) Methylenedioxybenzene derivatives such as 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene

and their physiologically acceptable salts.

Particularly preferred coupler components according to the invention are 1-naphthol, 1,5- and 2,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-methylresorcinol and 2,6- Dihydroxy-3,4-dimethylpyridine and its physiologically acceptable salts.

The compositions according to the invention contain the compound (s) of the formula (I) in amounts of from 0.001 to 5% by weight, preferably from 0.0025 to 2.5% by weight, particularly preferably from 0.005 to 1.5% by weight. % and in particular from 0.01 to 1 wt .-%, each based on the total agent.

The other developer components optionally contained in the agent according to the invention and also the coupler components are preferably used in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on their total weight. In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is 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 a further embodiment of the present invention, the agents according to the invention comprise at least one precursor of a naturally-analogous dye. As precursors of naturally-analogous dyes such indoles and indolines are preferably used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline and 2,3-dioxoindoline (isatin) and their physiologically acceptable salts. A particularly preferred derivative of indole is the 5,6-dihydroxyindole and its physiologically acceptable salts.

The agents according to the invention preferably contain the indole or indoline derivatives in an amount of 0.05-10% by weight, preferably 0.2-5% by weight, in each case based on their total weight.

In a further preferred embodiment, the agents according to the invention comprise at least one substantive dye. Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes. The substantive dyes are preferably selected from the nitrophenylenediamines, the nitroaminophenols, the azo dyes, the anthraquinones or the indophenols and their physiologically compatible salts.

Particularly suitable anionic direct dyes are 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (CI 10,316, Add Yellow 1, Food Yellow No. 1), 2- (indan-1,3-dione-2). yl) quinoline-x, x-sulfonic acid (mixture of mono- and disulfonic acid) (CI 47,005, D & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10), 5-hydroxy-1- (4- sulfophenyl) -4 - [(4-sulfophenyl) -azo] pyrazole-3-carboxylic acid trisodium salt (CI 19,140, Food Yellow No. 4, Acid Yellow 23), 3 - [(4-phenylamino) phenyl] azobezenesulfonic acid, sodium salt ( CI 13.065; Ki406; Acid Yellow 36), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid, sodium salt (CI 15.510, Acid Orange 7), 6-hydroxy-5 - [(4-sulfonaphth-1 -yl) azo] -2,4-naphthalenedisulfonic acid trisodium salt (CI 16,255; Ponceau 4R; Acid Red 18); 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalene-disulfonic acid disodium salt (CI 17.200; Acid Red 33; Red 33), N- [6- (diethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene-N-ethylethanammonium hydroxide, inner salt, sodium salt (CI 45,100; Acid Red 52), 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-hydroxy-4 - [(4-methyl-2-sulfonphenyl) azo] -2-naphthalenecarboxylic acid calcium salt (CI 15, 850: 1, Pigment Red 57: 1), 1,4-bis [( 2-sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (CI 61.570, Acid Green 25), bis [4- (dimethylamino) phenyl] - (3,7-disulfo-2-hydroxynaphth-1) yl) carbenium inner salt, sodium salt (CI 44.090, Food Green No. 4, Acid Green 50), N- [4 - [(2,4-disulfophenyl) [4- [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5-cyclohexadien-1-ylidene] -N-ethylbenzenemethanamine 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- (cyclohexylamino) -9,10-anthraquinone-2-sulfonic acid, sodium salt (CI 62045, Acid Blue 62), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone sodium salt (CI 60.730, D & C Violet No. 2, Acid Violet 43), 5-amino-4 -hydroxy-6 - [(4-nitrophenyl) azo] -3- (phenylazo) -2,7-naphthalene-disulphonic acid-d inatrium salt (CI 20,470; Acid Black 1), 3-hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7-nitro-1-naphthalene-sulfonic acid-chromium complex (3: 2) (CI 15,711, Acid Black 52), 3 ', 3'',4,5,5', 5 '', 6,7-Octabromphenolsulfonphthalein (tetrabromophenol blue).

Preferred anionic substantive dyes are those having the international designations or trade names Acid Yellow 1, Acid 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.

Particularly suitable cationic substantive dyes are di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium chloride (CI 42,595, Basic Blue 7), di [4- (dimethylamino) phenyl] [4- (phenylamino ) naphthyl] carbenium chloride (CI 44.045; Basic Blue 26), 8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) - naphthalene chloride (CI 56.059, Basic Blue No. 99), tri (4-amino-3-methylphenyl) carbenium chloride (CI 42.520, Basic Violet 2), di (4-aminophenyl) (4-amino-3-methylphenyl ) carbenium chloride (CI 42.510 Basic Violet 14), 1 - [(4-aminophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (CI 12.250, Basic Brown 16), 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-trimethylbenzeneamine chloride (CI 12.605, Basic Orange 69), 2 - [((4-dimethylamino) phenyl) azo] -1,3-dimethyl-1H-imidazolium chloride (Basic Red 51), 2-hydroxy-1 - [(2- methoxyphenyl) azo] -7- (TriMeth ylammonio) naphthalene chloride (C. I. 12,245; Basic Red 76), 2- [4-aminophenyl] azo] -1,3-dimethyl-1H-imidazolium chloride (Basic Orange 31), 3-methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl ) azo] pyrazol-5-one chloride (CI 12,719, Basic Yellow 57), 1-methyl-4 - ((methylphenylhydrazono) methyl) pyridinium methyl sulfate (Basic Yellow 87), 1- (2-morpholinium propylamino) - 4-hydroxy-9,10-anthraquinone methylsulfate, 4-formyl-1-methylquinolonium p-toluenesulfonate and substantive dyes containing a heterocycle having at least one quaternary nitrogen atom.

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

Suitable blue nitro dyes are, in particular, 1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet BS), 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] -benzene (HC Blue 2), 4- [di (2-hydroxyethyl) amino] -1 - [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue 11), 4- [ethyl- (2- hydroxyethyl) amino] -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 12), 1- (2-hydroxyethyl) amino-2-nitro-4-N-ethyl-N- ( 2-hydroxyethyl) aminobenzene (HC Blue 15), 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).

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 salts thereof, 1,4-diamino 2-nitrobenzene (CI 76.070), 4-amino-2-nitro-diphenylamine (HC Red 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red 13) , 1-Amino-4 - [(2-hydroxyethyl) amino] -5-chloro-2-nitrobenzene, 4-Amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 3), 4 - [(2-hydroxyethyl) amino] -3-nitrotoluene, 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), 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 (HC Red 11), 2 - [(2-hydroxyethyl ) amino] -4,6-dinitrophenol and its salts, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amine o-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol (HC Red BN), 1,2,3,4-tetrahydro-6-nitroquinoxaline, 6-hydroxy-5- ((2-methoxy-5-methyl-4-sulfophenyl) azo) -2-naphthalenesulfonic acid (Curry Red).

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 - [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene, 2-amino-4-nitrophenol, 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 trifluoromethyl-benzene (HC Yellow 13).

Suitable quinone dyes are, in particular, 1 - [(2-hydroxyethyl) amino] -4-methylamino-9,10-anthraquinone (CI 61,505, Disperse Blue 3), mixtures of 1,4-bis [(2-hydroxyethyl) amino] anthraquinone 9,10-quinone with 1 - [(2-hydroxyethyl) amino] -4 - [(3-hydroxypropyl) amino] anthra-9,10-quinone and 1,4-bis [(3-hydroxypropyl) amino] anthracene 9,10-quinone (Disperse Blue 377), 1,4-diamino-9,10-anthraquinone (CI 61.100, Disperse Violet 1), 1-amino-4- (methylamino) -9,10-anthraquinone (CI 61.105, Disperse Violet 4, Solvent Violet No. 12), 2-hydroxy-1,4-naphthoquinone (Lawsone, CI 75,480, Natural Orange 6), 1,4-bis [(2,3-dihydroxypropyl) amino] -9,10 -anthracenedione (HC Blue 14).

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, 4 - [(4-nitrophenyl) azo] -aniline (CI 11.005, Disperse Orange 3).

Furthermore, the agents of the invention may also include naturally occurring dyes such as indigo (Indigoferia tinctoria), henna red (Lawsonia inermis), henna neutral or henna black. Other preferred natural dyes are included, for example, in chamomile flower, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, sedre and alcano root.

The agents according to the invention preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on their total weight.

• – 1-(2,5-Dihydroxyphenyl)pyridiniumchlorid/5-Amino-2-methylphenol
• – 1-(2,5-Dihydroxyphenyl)pyridiniumchlorid/3-Amino-2-chlor-6-methylphenol
• – 1-(2,5-Dihydroxyphenyl)pyridiniumchlorid/2,4-Dichlor-3-aminophenol
• – 1-(2,5-Dihydroxyphenyl)pyridiniumchlorid/2-(2,4-Diaminophenoxy)ethanol
• – 1-(2,5-Dihydroxyphenyl)pyridiniumchlorid/1,3-Bis(2,4-diaminophenoxy)propan
• – 1-(2,5-Dihydroxyphenyl)pyridiniumchlorid/2-Methylresorcin
• – 1-(2,5-Dihydroxyphenyl)pyridiniumchlorid/2-Amino-3-hydroxypyridin
• – 1-(2,5-Dihydroxyphenyl)pyridiniumchlorid/3-Amino-2-methylamino-6-methoxypyridin

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

• - 1- (2,5-Dihydroxyphenyl) pyridinium chloride / 5-amino-2-methylphenol
• - 1- (2,5-Dihydroxyphenyl) pyridinium chloride / 3-amino-2-chloro-6-methylphenol
• - 1- (2,5-dihydroxyphenyl) pyridinium chloride / 2,4-dichloro-3-aminophenol
• - 1- (2,5-dihydroxyphenyl) pyridinium chloride / 2- (2,4-diaminophenoxy) ethanol
• - 1- (2,5-dihydroxyphenyl) pyridinium chloride / 1,3-bis (2,4-diaminophenoxy) propane
• - 1- (2,5-dihydroxyphenyl) pyridinium chloride / 2-methylresorcinol
• - 1- (2,5-dihydroxyphenyl) pyridinium chloride / 2-amino-3-hydroxypyridine
• - 1- (2,5-dihydroxyphenyl) pyridinium chloride / 3-amino-2-methylamino-6-methoxypyridine

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

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

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

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• 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 carbon 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. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

• Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• C 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. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

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

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

Particular preference is given to those alkylpolyglycosides in which R ¹

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

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

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

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

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

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium 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, the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines.

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

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

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

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

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

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

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

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

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl-ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazolinium-methochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Malein-säureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• – Strukturanten wie Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cycodextrine,
• – 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, 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 cycodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Fiber-structure-improving active substances, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• Quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• Defoamers like silicones,
• Dyes for staining the agent,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• - active substances such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• Fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizer for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants,

contain

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

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

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

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

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

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

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

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

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

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

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

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

in der
R¹, R² stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Alkoxygruppe, ein Halogenatom (Cl, Br, F oder J), eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine Hydroxy-C₂-C₆-alkyloxygruppe, eine Arylgruppe, eine Aryl-C₁-C₆-alkylgruppe oder eine Aryl-C₁-C₆-alkyloxygruppe,
X^– steht für ein einwertiges Anion, vorzugsweise für Halogenid, Hydrogensulfat, ½ Sulfat, p-Benzolsulfonat, p-Toluolsulfonat, Acetat, Citrat, Lactat; Tetrafluoroborat, Trifluormethansulfonat, Hexafluorophosphat, Methansulfat oder Methansulfonat,
als Entwicklerkomponente zur oxidativen Färbung keratinischer Fasern.A third object of the present invention is the use of at least one 1- (2,5-dihydroxyphenyl) pyridinium salt of the general formula (I)

in the
R ¹ , R ² independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -alkoxy group, a halogen atom (Cl, Br, F or J) , a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a hydroxy C ₂ -C ₆ alkoxy group, an aryl group, an aryl C ₁ -C ₆ alkyl group or an aryl C ₁ - C ₆ alkyloxy group,
X ^- is a monovalent anion, preferably halide, hydrogen sulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate; Tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate,
as a developer component for the oxidative coloring of keratinic fibers.

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

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

Examples

1 syntheses

1.1. Synthesis of 1- (2,5-dihydroxyphenyl) pyridinium chloride (E1)

25.0 g (0.23 mol) of 1,4-benzoquinone were suspended in 70 ml of glacial acetic acid, then 17.8 g (0.23 mol) of pyridine were added dropwise with stirring. By adding the pyridine, the temperature of the mixture without external heat supply to 80 ° C and was maintained by cooling with ice / water at this temperature. After cooling to 70 ° C, a mixture of 19 ml of concentrated hydrochloric acid and 68 ml of dist. Water added. Then was stirred for 2 hours. Upon cooling, a yellow, crystalline solid precipitated, which was filtered off and dried in vacuo.
Yield: 36.2 g (69%), yellow, crystalline substance
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 7.02 (dd, 1H); 7.10 (d, 1H); 7.21 (dd, 1H); 8.29 (m, 2H); 8.75 (m, 1H); 9.19 (d, 2H); 9.88 (br., OH)
¹³ C-NMR (400 MHz, DMSO-d6): δ [ppm] = 112.9; 117.9; 119.2; 127.8; 129.9; 142.2; 146.0; 146.1; 150.2

2 colorations

2.1 Experimental procedure

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

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

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

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

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

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• DE 3725030 A [0054]
• DE 3723354 A [0054]
• DE 3926344 A [0054]

Cited non-patent literature

• A new class of developing agents. Kumetat, K. Journal of Scientific Photography, Photophysics and Photochemistry (1948), 43 113-19. CODES [0011]
• Kh. Schrader, Basics and Formulations of Cosmetics, 2nd Edition, Hüthig Buch Verlag, Heidelberg, 1989 [0077]

Claims (8)

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

in which R ¹ , R ² independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -alkoxy group, a halogen atom (Cl, Br, F or J), a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a hydroxy C ₂ -C ₆ alkyloxy group, an aryl group, an aryl C ₁ -C ₆ alkyl group or an aryl -C ₁ -C ₆ -alkyloxy, X ^- is a monovalent anion, preferably halide, hydrogen sulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate. Composition according to Claim 1, characterized in that it contains a developer component of the formula (I) in which the radicals R ¹ and R ² independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ - Alkoxy group or a halogen atom (Cl, Br, F or J). Agent according to one of claims 1 or 2, characterized in that it is used as developer component at least one of the compounds selected from the group Salts of 1- (2,5-dihydroxyphenyl) pyridinium - Salts of 1- (2,5-dihydroxy-4-methylphenyl) pyridinium Salts of 1- (2,5-dihydroxy-3-methylphenyl) pyridinium Salts of 1- (3,6-dihydroxy-2-methylphenyl) pyridinium - Salts of 1- (4-chloro-2,5-dihydroxyphenyl) pyridium - Salts of 1- (3-chloro-2,5-dihydroxyphenyl) pyridinium Salts of 1- (2-chloro-3,6-dihydroxyphenyl) pyridinium - Salts of 1- (4-bromo-2,5-dihydroxyphenyl) pyridinium Salts of 1- (3-bromo-2,5-dihydroxyphenyl) pyridinium Salts of 1- (2-bromo-3,6-dihydroxyphenyl) pyridinium - Salts of 1- (2,5-dihydroxy-4-methoxyphenyl) pyridinium Salts of 1- (2,5-dihydroxy-3-methoxyphenyl) pyridinium - Salts of 1- (3,6-dihydroxy-2-methoxyphenyl) pyridinium Salts of 1- (4-ethoxy-2,5-dihydroxyphenyl) pyridinium Salts of 1- (3-ethoxy-2,5-dihydroxyphenyl) pyridinium Salts of 1- (2-ethoxy-3,6-dihydroxyphenyl) pyridinium Salts of 1- (2,5-dihydroxy-3,4-dimethylphenyl) pyridinium - Salts of 1- (3,4-dichloro-2,5-dihydroxyphenyl) pyridinium Salts of 1- (3,4-dibromo-2,5-dihydroxyphenyl) pyridinium - Salts of 1-2,5-dihydroxy-3,4-dimethoxyphenyl) pyridinium Salts of 1- (3,4-diethoxy-2,5-dihydroxyphenyl) pyridinium contains. Agent according to one of claims 1 to 3, characterized in that it contains at least one coupler component. Composition according to claim 4, characterized in that the coupler component is selected from 1-naphthol, 1,5- and 2,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-methylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine and their physiologically acceptable salts. Keratin fiber coloring agent according to any one of Claims 1 to 5, characterized in that it contains the compound (s) of the formula (I) in amounts of from 0.001 to 5% by weight, preferably from 0.0025 to 2.5% by weight. -%, particularly preferably from 0.005 to 1.5 wt .-% and in particular from 0.01 to 1 wt .-%, each based on the total agent contains. A process for coloring keratinic fibers, wherein an agent according to any one of claims 1 to 6 is applied to the fibers and rinsed again after a contact time. Use of a 1- (2,5-dihydroxyphenyl) pyridinium salt of the general formula (I)

in the R ¹ , R ² independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -alkoxy group, a halogen atom (Cl, Br, F or J), a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a hydroxy C ₂ -C ₆ alkoxy group, an aryl group, an aryl C ₁ -C ₆ alkyl group or an aryl C ₁ -C ₆ -alkyloxy group, X ^- is a monovalent anion, preferably halide, hydrogen sulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate, as the developer component in agents for dyeing keratinic fibers.