WO2002038533A1 - Novel coupling components for oxidation dyes - Google Patents

Abstract

The invention relates to 4,5-dialkoxy-1,2-diaminobenzenes of the formula (I), and the salts thereof that are suitable for use as coupling agents for producing oxidation colorations with known developer components. Oxidation dyes for dyeing keratin fibers, especially hair, that contain, in an aqueous carrier, at least one developer component and at least one 4,5-dialkoxy-1,2-diaminobenzene of the formula (I) as the coupler are evenly absorbed by the hair and produce intensive, yellow to brown shades with excellent fastness properties.

Description

 "New Coupler Components for Oxidation Colorants"

The invention relates to new 4,5-dialkoxy-l, 2-diaminobenzenes and their use as coupler components for producing oxidation colors with known developer compounds.

The so-called oxidation dyes play a special role in dyeing keratin fibers, especially hair, because of their intense colors and good fastness properties, which are achieved at a relatively low dyeing temperature and in short dyeing times. Such colorants contain in a suitable, usually aqueous carrier an oxidation base, which is also referred to as a developer component, and which forms a dye under the influence of atmospheric oxygen or oxidizing agents through oxidative polymerization. This dye can be intensified by coupling with another developer compound or with so-called coupler compounds, which cannot form any dyes themselves, and the shade can be modified.

Good oxidation dye precursors are primarily intended to meet the following requirements: They have to develop the desired color shades with sufficient intensity and authenticity in the oxidative coupling. They must also have a good ability to draw onto the fiber, whereby there must be no noticeable differences between stressed and freshly regrown hair, especially with human hair (leveling ability). They should be resistant to light, heat, friction and the influence of chemical reducing agents, e.g. B. perm fluids. After all, if they are used as a hair dye, they should not stain the scalp too much, and above all they should be harmless from a toxicological and dermatological point of view. Furthermore, the coloration obtained should be easily removed from the hair again by bleaching, if it does not correspond to the individual wishes of the individual and should be reversed. Primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-amino-pyrazolone derivatives and 2,4,5, 6-tetraaminopyrimidine and the like are usually used as developer components 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 '-Diaminopheny l) -ethanol, 2- (2', 5 '-diaminophenoxy) -ethanol, 1 -phenyl-3-car-boxyamido-4-amino-pyrazol-5-one, 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.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components. 1-Naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomino methyl ether, m-phenylenediamine, l-phenyl are particularly suitable as coupler substances -3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, l, 3-bis (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2-methyl-4-chloro-5-aminophenol, 2,4-diaminophenoxyethanol and 2-amino-3-hydroxypyridine.

With a developer component or a special coupler / developer combination alone, it is usually not possible to obtain a color shade that looks natural on the hair. In practice, therefore, combinations of different developer components and coupler components are usually used. There is therefore a constant need for new, improved dye precursors. The use of orthophenylenediamines to produce oxidation colors is known from German patent DE 213 581 and published patent application DE 2 461 910 AI, their use as a coupler for. B. from DE 43 44488 AI known.

However, the couplers disclosed there do not yet make all the desired color nuances accessible. They also do not have the required authenticity properties. The task was therefore to find new coupler compounds which, with the common developer components, lead to particularly intense oxidation colors with high thermal stability and good leveling capacity.

The invention relates to 4,5-dialkoxy-1,2-diaminobenzenes of the formula I.

independently in which R ¹ and R ² represents a _Cι-C4 alkyl group or a C ₂ -C - hydroxyalkyl group, and R ³ is hydrogen, a _Cι-C4 alkyl group or a Cι-C ₄ - hydroxyalkyl group, and water soluble salts thereof ,

Examples of C 1 -C ₄ alkyl groups are the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl and the tert-butyl group. Examples of CrC ₄ - hydroxyalkyl groups according to the invention are the 2-hydroxyethyl, the 3-hydroxypropyl or the 2,3-dihydroxypropyl group.

It has been found that these new 4,5-dialkoxy-l, 2-diaminobenzenes or their salts are particularly advantageously suitable as coupler compounds for producing oxidation colors with known developer components. They deliver intense, yellow to brown shades of high fastness and temperature stability and with an even draw-up on keratin fibers. A particularly preferred one The invention relates to 4,5-dimethoxy-3-methyl-1,2-diaminobenzene, which has the stated coloring properties in a particularly high degree.

The 4,5-dialkoxy-1,2-diaminobenzenes of the formula I are particularly suitable for the preparation of oxidation colorants for keratin fibers, in particular for hair. The invention therefore furthermore relates to oxidation colorants for dyeing keratin fibers, in particular hair, which contain in an aqueous carrier at least one developer component and at least one 4,5-dialkoxy-1,2-diaminobenzene of the formula I as a coupler. Keratin fibers are wool, feathers, furs, animal and especially human hair.

The new coupler compounds of formula I can be used as free bases or in the form of their water-soluble acid addition salts, e.g. B. as hydrochlorides, sulfates, phosphates, lactates, acetates or glycolates.

Suitable developer compounds for the preparation of the hair colorants according to the invention can, for example, preferably be p-phenylenediamine derivatives or one of its physiologically tolerable salts. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

in which

- G ¹ represents a hydrogen atom, a C ₄ -C ₄ -alkyl radical, a dC ₄ - monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄ ) alkoxy- (C ₁ - C ₄ ) - alkyl radical, a 4'-aminophenyl radical or a -Gralkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical, - G ² represents a hydrogen atom, a _Cι-C4 alkyl group, a C_-C ₄ - monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄₎ alkoxy (C ₁ - C ₄ ) -alkyl radical or a C 1 -C ₄ -alkyl radical which is substituted by 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 -C alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a C 1 -C ₄ -hydroxyalkoxy, a C ₁ -C ₄ - acetylaminoalkoxy, a Cι-C mesylaminoalkoxy or a C_-C ₄ - carbamoylaminoalkoxy,

- G ⁴ represents a hydrogen atom, a halogen atom or a -CC ₄ alkyl radical or

- If G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-alkylenedioxo group, such as an ethylenedioxy group.

Examples of nitrogen-containing groups of the formula (E1) are in particular the amino groups, Ci-Cf-monoalkylamino groups, -CC ₄ -dialkylamino groups. C_-C - trialkylammonium groups, CrC ^ monohydroxyalkylamino groups, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 - Amino-3-methyl- (N, N-diethyl) - aniline, N, N-bis- (ß-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (ß-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N - (ß-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, ß-hydroxyethyl) -p-phenylenediamine, N - (ß, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß-hydroxyethyloxy) -p-phenylenediamine, 2- (ß - Acetylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-l, 4-dioxane and their physiologically tolerable salts.

According to the invention, particularly preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

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

Among the binuclear developer components which can be used in the coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical, which is optionally substituted by a C 1 -C ₄ -alkyl radical, by a C 1 -C ₄ - monohydroxyalkyl radical and / or by a bridging Y or the optional part of a bridging ring system, the bridging Y represents an alkylene group having 1 to 14 carbon atoms, such as, for example, a linear or branched alkylene chain or an alkylene ring which is composed of one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or Nitrogen atoms interrupted or may have ended and may be substituted by one or more hydroxyl or -Cs alkoxy radicals, or a direct bond,

- G ^s and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ -C alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a C _! -C ₄ -aminoalkyl radical or a direct connection to the 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 bridging Y or a C 1 -C ₄ -alkyl radical, with the provisos that the compounds of the formula ( E2) contain only one bridging Y per molecule and the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred two-core developer components of the formula (E2) are in particular: N, N ^, -Bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -l, 3-diamino-propan-2-ol, N, N'- bis (ß-hydroxyethyl) -N, N'-bis- (4 ^, -aminophenyl) -ethylenediamine, N, N'-bis- (4-aminophenyl) -tetra-methylenediamine, N, N ' -Bis- (ß-hydroxyethyl) -N, N'-bis- (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N ¹ -Bis- (ethyl ) -N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,4-bis (4'-aminophenyl) - diaza-cycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and l, 10-bis (2 ', 5'-diaminophenyl ) -l, 4,7,10-tetraoxadecane and their physiologically tolerable salts.

Very particularly preferred dinuclear developer components of the formula (E2) are N, N'-bis (ß-hydroxyethyl) -N, N ^, -bis- (4'-aminophenyl) -l, 3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and l, 10-bis- (2 ', 5'-diaminophenyl) -l, 4,7,10-tetraoxadecane or one of its physiologically tolerable salts.

Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as developer component. P-Aminophenol derivatives of the formula (E3) are particularly preferred

in which

1 part

- G represents a hydrogen atom, a halogen atom, a _Cι-C4 alkyl group, a Ci- C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a _(Cι-C4) alkoxy- (Cι-C) alkyl group, a Cι-C ₄ aminoalkyl radical, a hydroxy (C_-C) - alkylamino, a Cι-C ₄ -Hydroxyalkoxyrest, a C ₁ -C ₄ hydroxyalkyl (Cι-C ₄₎ - aminoalkyhest or ( Di-C-C ₄ alkylamino) - (-C-C ₄ ) alkyl, and

- G ¹⁴ represents a hydrogen or halogen atom, a Cι-C ₄ alkyl, C ₁ -C ₄ - hydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl radical, a _(Cι-C4) alkoxy (Cι- C ₄ ) - alkyl radical, a Cι-C ₄ aminoalkyl radical or a - C ₄ cyanoalkyl radical,

- G ¹⁵ is hydrogen, a _Cι-C4 alkyl group, a Cι-C ₄ hydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

- G ¹⁶ represents hydrogen or a halogen atom.

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

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4- amino-3-hydroxymethylphenol, 4- amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4- Amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro -4-aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol and their physiologically tolerable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2-

((Diethylamino) methyl) phenol.

The developer component can also be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts. According to the invention, pyrimidine or pyrazole derivatives are preferred.

Preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open patent publication JP 02019576 A2 or in laid-open publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740931 and DE 195 43 988, such as 4,5- Diamino-l-methylpyrazole, 4,5-diamino-1 - (β-hydroxyethyl) -pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 - (4'-chlorobenzyl) -pyrazole, 4,5-diamino -l, 3-dimethylpyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, 4,5-diamino-l-methyl-3-phenylpyrazole, 4-amino-l, 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 - (ß- hydroxyethyl) -3-methylpyrazole, 4,5-diamino-l-ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3- (4'-methoxyphenyl) -pyrazole, 4,5-diamino-l- ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethylI-l-methylpyrazole, 4,5-diamino-3-hydroxymethyl-l - isopropylpyrazole, 4,5-diamino-3-methyl-l-isopropylpyrazole, 4- Amino-5- (2'-aminoethyl) amino-l, 3-dimethylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5-triaminopyrazole, 3,5-diamino-l-methyl-4- methylaminopyrazole and 3,5-diamino-4 (β-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyridine derivatives are, in particular, the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4-methoxyphenyl) amino-3-amino-pyridine, 2 , 3-diamino-6-methoxy-pyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrazole-pyrimidine derivatives are in particular the derivatives of pyrazole- [1,5-a] -pyrimidine of the following formula (E4) and its tautomeric forms, provided that there is a tautomeric equilibrium:

in which:

- G ^17, G ^18, G ¹⁹ and G ²⁰ are independently a hydrogen atom, a Cι-C ₄ alkyl radical, an aryl radical, a -C ₄ hydroxyalkyl radical, a C ₂ -C ₄ - polyhydroxyalkyl a

a -C-C - aminoalkyl radical, which may optionally be protected by an acetyl-ureide or sulfonyl radical, a (Ci-C ^ alkylamino ^ rC ^ alkyl radical, a di - [(CrC ₄ ) - alkylj- ^ rC ^ aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a C 1 -C ₄ -hydroxyalkyl or a di- (C ₁ -C ₄ ) - [hydroxyalkyl] - (C ₁ - C ₄ ) aminoalkyl radical,

- the X radicals are each independently a hydrogen atom, a Cι-C ₄ - alkyl group, an aryl group, a Cι-C ₄ hydroxyalkyl radical, a C ₂ -C ₄ - Polyhydroxyalkyl radical, a C ₁ -C ₄ aminoalkyl radical, a (-C-C ₄ ) alkylamino (C.- C ₄ ) alkyl radical, a di - [(C ₁ -C) alkyl] - (C ₁ -C) aminoalkyl, wherein the dialkyl residues optionally form a carbocycle or a heterocycle with 5 or 6 chain links, a Cι-C ₄ hydroxyalkyl or a di- (Cι-C ₄ - hydroxyalkyl) aminoalkyl group, an amino group, a Cι- C ₄ alkyl or di (-C ₄ - hydroxyalkyl) amino radical, 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 is 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

- if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

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

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

Among the pyrazole [1,5-a] pyrimidines of the above formula (E4), one can mention in particular:

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

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

- pyrazole (1,5-a) pyrimidine-3,5-diamine;

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

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

- 3-amino pyrazol- [1,5-a] pyrimidin-5-ol;

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

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

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

- 2 - [(7-Amino pyrazol- [l, 5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;

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

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

- 2,5, N7, N7-tetramethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine; as well as their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

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

All customary developer compounds are suitable as developer components, of which the aforementioned examples have been listed. In a preferred embodiment, the oxidation colorants according to the invention contain, as developer compounds, at least one aromatic amino compound with a hydroxy or A-amino group in para position. Preferred developer components are p-phenylenediamines, p-aminophenols and aminopyrimidines and their salts. Particularly preferred developer components are selected according to the invention from p-phenylenediamine, p-toluenediamine, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 2,5-diaminophenoxyethanol, N, N-bis (2'-hydroxyethyl) -p -phenylenediamine, p-aminophenol, 3 -methyl-4-aminophenol, 2-hydroxyethylaminomethyl 1-4-aminophenol, 4-amino-2- ((diethylamino) methyl) phenol, 2-aminomethyl-4-aminophenol, 2- (2 '-hydroxy ethoxy) - 4-aminophenol, 2-hydroxymethyl-4-aminophenol, bis (2-hydroxy-5- aminophenyl) methane, N, N'-bis (2'-hydroxyethyl) -N, N '-bis- (4' -aminophenyl) -1,3-diaminopropan-2-ol, l-phenyl-3 -carboxyamido-4-amino-pyrazolone, 4,4'-diamino-diphenylamine, 1,4-bis- (4'-aminophenyl) -diazycloheptane, 4,5-diamino-l (2'-hydroxyethyl) -pyrazole, 2 , 4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, o-aminophenols and o-phenylenediamines. p-Toluenediamine and 2,4,5,6-tetraaminopyrimidine are very particularly preferred developer components.

In a special embodiment, the hair colorants according to the invention contain developer substances which are selected from z. B. p-phenylenediamine, p-toluenediamine, 1 - (2'-hydroxyethyl) -2,5-diaminobenzene, 2,5-diaminophenoxyethanol, N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, p- Aminophenol, 3-methyl-4-aminophenol, 2-hydroxyethylaminomethyl-4-aminophenol, 2-aminomethyl-4-aminophenol, 2- (2 '-hydroxyethoxy) -4-aminophenol, 2-hydroxymethyl-4-aminophenol, bis - (2-Hydroxy-5-aminophenyl) methane, N, N'-bis (2'-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1, 3-diaminopropan-2-ol , l-phenyl-3-carboxyamido-4-aminopyrazolone, 4,4'-diamino-di-phenylamine, l, 4-bis (4'-aminophenyl) diazycloheptane, 4,5-diamino-l (2nd '-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5 , 6-diaminopyrimidine, o-aminophenols and o-phenylenediamines.

For shading purposes, the oxidation colorants according to the invention can contain further conventional coupler compounds and, if appropriate, also direct dyes.

Typical examples of known coupler compounds have already been listed above. In addition, others are preferred according to the invention

Coupler components selected from:

- m-Aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl -3 -aminophenol, 3 -trifluoroacetylamino-2-chloro- 6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol .

N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3-

Ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4-

Diaminophenoxyethanol, 1, 3-bis (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2', 4 ' -diaminophenyl) propane, 2,6-

Bis- (2'-hydroxyethylamino) -l-methylbenzene and l-amino-3-bis- (2'-hydroxyethyl) -aminobenzene, o-diaminobenzene and their derivatives such as 3,4-diaminobenzoic acid and 2,3- diamino-l-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol,

Resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-

Dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-

trihydroxybenzene,

Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4 -dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-

Diamino-2,6-dimethoxy,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-

Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene,

1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-

Dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-l, 2,3,4-tetrahydroquinoxaline,

Pyrazole derivatives such as, for example, l-phenyl-3-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 1-

hydroxyindole, - Pyrimidine derivatives, such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino -4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or

Methylenedioxybenzene derivatives such as l-hydroxy-3,4-methylenedioxybenzene, l-amino-3,4-methylenedioxybenzene and l- (2'-hydroxy ethyl) - amino-3, 4-methylenedioxybenzene.

Coupler compounds which are particularly preferred according to the invention are 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m -Phenylenediamine, l-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis- (2 \ 4'-diamino-phenoxy) -propane, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2,6- Dihydroxy-3,4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluene, 2,6-bis (2'-hydroxyethylamino) toluene, 2- 12 ', 4' -Diaminophenoxy-ethanol, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) -benzene, 2-methyl-4-chloro-5-amino-phenol, 6-methyl, 2,3,4-tetrahydro- quinoxaline, 3,4-methylene-dioxyphenol, 3,4-methylenedioxyaniline, 2,6-dimethyl-3-aminophenol, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxyethanol, 2- Methyl-5 - (2 '- hydroxy thylamino) phenol and 2,6-dihydroxy-3,4-dimethylpyridine.

Direct dyes can also be used to achieve certain coloring effects. In a preferred embodiment, the hair colorants according to the invention contain, in addition to the oxidation dye precursors, customary direct dyes for further modification of the color shades

In a preferred embodiment, the hair colorants according to the invention contain, in addition to the oxidation dye precursors, customary direct dyes for further modification of the color shades. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are selected from the group consisting of is formed from the dyes known under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Basic Yellow 87, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 51, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17, as well as from Compounds 4-amino-2-nitrodiphenylamine-2 '-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol 4 -Ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene are selected.

The agents according to the invention can also contain a cationic direct dye. Are particularly preferred

(a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems which are substituted with a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and

(c) substantive dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as are mentioned, for example, in EP-A2-998 908, to which reference is expressly made here, in claims 6 to 11.

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

CH ₃ SO ₄ ^"

Cl ^"

The compounds of the formulas (DZ1), (DZ3) and (DZ5) are very particularly preferred cationic direct dyes of the group (c). The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention particularly preferred substantive dyes.

In a special embodiment, the direct dyes are selected, e.g. B. from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as. B. under the international names or trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Nitro Blue, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Picramic Acid and Rodol 9 R known compounds. 4-Amino-2-nitro-diphenylamine-2'-carboxylic acid, 6-nitro-l, 2,3,4-tetrahydroquinoxaline, Rodol 9 R and HC Red BN are particularly preferred direct dyes according to the specific embodiment. Furthermore, the preparations according to the invention can also contain naturally occurring dyes, such as those contained in henna red, neutral henna, black henna, chamomile flowers, sandalwood, black tea, rotten bark, sage, blue wood, madder root, catechu, sedre and alkanna root.

The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

A natural-looking hair color can result from a dyeing process if indole or indoline derivatives are additionally used as precursors of nature-analogous dyes in the applied hair dye.

In a further embodiment, indoles and / or indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are therefore additionally preferably used. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group.

Derivatives of 5,6-dihydroxyindoline of the formula (Ha) are particularly suitable as precursors of nature-analogous hair dyes,

in the independently of each other

R ¹ is hydrogen, a Cι-C ₄ -Alkylgmppe, a C ₃ -C ₆ cycloalkyl group, a C -C ₄ alkenyl group or a _C. -C ₄ hydroxyalkyl group, R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,

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

R ⁴ represents hydrogen, a C ₁ -C 4 alkyl group or a group -CO-R ⁶ , in which

R ⁶ represents a -CC ₄ alkyl group, and

R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N ~ propyl-5,6-dihydroxyindoline, N-butyl-5 , 6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially that 5,6-Dihydroxyindolin.

Derivatives of 5,6-dihydroxyindole of the formula (IIb) are also outstandingly suitable as precursors of naturally analogous hair dyes,

in the independently of each other

R ¹ is hydrogen, a _Cι-C4 alkyl group, a C ₃ -C ₆ -Cycloalkylgmppe, a C -C ₄ alkenyl group or a C ₁ -C ₄ -Hydroxyalkylgmppe,

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation, R ³ represents hydrogen or a C 1 -C ₄ alkyl group,

R ⁴ stands for hydrogen, a C_-C4-alkyl group or a group -CO-R ⁶ , in which

R ⁶ represents a -CC ₄ alkyl group, and

R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5 , 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Of particular note within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially 5,6 -Dihydroxyindol.

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

It is not necessary that the oxidation dye precursors or the substantive dyes are in each case uniform compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, further components may be present in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

With regard to the dyes which can be used in the hair colorants and tints according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European inventory of cosmetic raw materials" , published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicines, Reformed Products and Personal Care Products, Mannheim.

To produce the oxidation colorants according to the invention, the oxidation dye precursors are incorporated into a suitable aqueous carrier. Such carriers are e.g. B. thickened aqueous solutions, creams (emulsions), gels or surfactant-containing, foaming preparations, for. B. shampoos or aerosols or other preparations that are suitable for use on the hair.

Preferred carrier components are preferred

- wetting and emulsifying agents

- thickener

- reducing agents (antioxidants)

- hair care additives

- fragrances and

- Solvents such as. As water, glycols or lower alcohols

used.

As wetting and emulsifying agents are, for. B. anionic, zwitterionic, ampholytic and nonionic surfactants. Cationic surfactants can also be used to achieve certain effects.

In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule may contain glycol or polyglycol ether groups, ester, ether and amide groups as well as hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon 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 -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids with 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 with 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 hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 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 with 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 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 1 -C 4 -carboxylic acids, such as oleic acid, stearic acid, Isostearic acid and palmitic acid.

Non-ionic surfactants contain e.g. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such connections are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group , -C ₂ -C ₂₂ fatty acid monoesters and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol, C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues and

- Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula RO- (Z) _χ . These connections are characterized by the following parameters.

The alkyl radical R contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R ¹ . Usually, however, these compounds are made 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 respective working up of these compounds. Particularly preferred are those alkyl polyglycosides in which R consists essentially of C ₈ - and Cio-alkyl groups, essentially from C ₁₂ - and Cπ-alkyl groups, essentially from C ₈ -C ₆ alkyl groups or essentially from C ₂ -C ₆ Alkyl groups.

Any mono- or oligosaccharides can be used as sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, Fmctose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, Fmctose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain an average of 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.

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

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

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one in the molecule -COO ^H - or -SO ₃ ^w group. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammomum glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group as well as the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₈ -alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C ₁₂ -_ ₈ acyl sarcosine.

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

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammomium chloride, distearyldimethylammonium chloride and 27 83 known imidazolium compounds. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms. Ester quats 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 sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethyl-ammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A inventions dx gsgemäß particularly suitable compound from this group is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine.

The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), 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 commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride". The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are the starting products of ethylene 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. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. In contrast, narrow homolog distributions are obtained if, 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 a narrow homolog distribution can be preferred.

The water-soluble high-molecular polysaccharide derivatives or polypeptides, for. As cellulose or starch ether, gelatin, vegetable gums, biopolymers (xanthan gum) or water-soluble synthetic polymers such as. B. polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene oxides, polyacrylamides, polyurethanes, polyacrylates xmd others. On the other hand, surfactant-containing preparations can also be thickened by solubilizing or emulsifying polar lipids. Such lipids are e.g. B. fatty alcohols with 12 - 18 carbon atoms, (free) fatty acids with 12 - 18 carbon atoms, fatty acid partial glycerides, sorbitan fatty acid esters, fatty acid alkanolamides, low-ethoxylated fatty acids or fatty alcohols, lecithins, sterols. Finally, gel-like carriers can also be based on aqueous soap gels, e.g. B. of ammonium oleate. Thickening agents such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellxilose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, Amylopectin and dextrins, clays such as e.g. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol are preferably used,

Reducing agents (antioxidants) which are added to the carrier in order to prevent premature oxidative development of the dye before use on the hair are e.g. As sodium sulfite or sodium ascorbate.

Hair care additives can e.g. B. fats, oils or waxes in emulsified form, structural additives such as. As glucose or pyridoxine, advancing components such. B. water-soluble proteins, protein degradation products, amino acids, water-soluble cationic polymers, silicones, vitamins such as panthenol, or plant extracts.

Finally, fragrances and solvents such as. B. glycols such as 1,2-propylene glycols, glycerol, glycol ethers such as. As butyl glycol, ethyl diglycol or lower monohydric alcohols such as ethanol or isopropanol may be included.

In addition, other auxiliaries can be included which improve the stability and application properties of the oxidation colorants, for. B. complexing agents such as EDTA, NTA or organophosphonates, swelling and penetrating agents such. B. urea, guanidine, hydrogen carbonates, buffer salts such as. B. ammonium chloride, ammonium citrate, ammonium sulfate or alkanolammonium salts xmd optionally propellants.

Furthermore, the agents according to the invention can preferably also contain a conditioning agent selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils.

Cationic polymers can be preferred as conditioning agents. These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. polymeric dimethyldiallylammonium salts xmd their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonixxmchlorid)), Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer commercially available products copolymers are examples of such cationic polymers. Of vinylpyrrolidone acrylate with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, quaternized with diethyl sulfate vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. such compounds are available under the names Gafquat ^® 734 xmd Gafquat ^® 755 commercially. vinylpyrrolidone methoimidazolinium chloride copolymers, as xxnter the name Luviquat ^® are offered, quaternized polyvinyl alcohol and those under the names Polyquaternium 2, Polyquateπύum 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Cationic polymers of the first four groups are particularly preferred; polyquaternium-2, polyquaternium-10 and polyquaternium-22 are very particularly preferred.

Also suitable as conditioning agents are silicone oils, in particular dialkyl-xmd alkylarylsiloxanes, such as dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated xmd quaternized analogs. Examples of such silicones are those from Dow Coming under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 and the commercial products Q2- 7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning ^® 929 emulsion (containing a hydroxylamino-modified silicone, which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

Paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents.

Likewise suitable hair-conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephalins.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone xmd vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammoxymixolymers / acrylamides 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, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl malyl vinyl ether / isyl malyl vinyl acetate / malyl malyl vinyl acetate acid anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl-acrylamide terpolymers,

Structurants such as maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,

Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, Perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, fiber structure-improving agents, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fmctose, cargo sugar and lactose, quaternized amines such as methyl-l-alkylamido -2-alkylimidazolinixιm methosulfate defoamers such as silicones, dyes for coloring the agent,

Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives xmd triazines,

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

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

Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, white dome, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root. Cholesterol,

Consistency generators such as sugar esters, polyol esters or polyol alkyl ethers, fats xmd waxes such as walrus, beeswax, montan wax and paraffins, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, ß-alaninediacetic acid xmd phosphonic acids, swelling and penetration substances such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP- xmd styrene / acrylamide copolymers pearlescent agents such as ethylene glycol mono-xmd -distearate and PEG-3 distearate, pigments

Stabilizing agent for hydrogen peroxide and other oxidizing agents,

Propellants such as propane-butane mixtures, NO, dimethyl ether, CO ₂ xmd air,

- antioxidants.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, e.g. K. Schrader, Fundamentals and Recipes for Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

In principle, the oxidative development of the coloring can take place with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents. However, the oxidation coloring agent can also be applied to the hair together with a catalyst which prevents the oxidation of the dye precursors, e.g. activated by atmospheric oxygen. Such catalysts are e.g. Transition metal compounds, iodides, quinones or certain enzymes. Suitable enzymes are e.g. Peroxidases, which can significantly increase the effects of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as for example the laccases, or generate small amounts of hydrogen peroxide in situ and in this way 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 substrates specific for this, e.g.

Pyranose oxidase and e.g. D-glucose or galactose,

Glucose oxidase xmd D-glucose,

- glycerin oxidase xmd glycerin,

Pyruvate oxidase and pyruvic acid or its salts,

- alcohol oxidase and alcohol (MeOH, EtOH), Lactate oxidase xmd lactic acid xmd its salts,

Tyrosinase oxidase xmd tyrosine,

Uricase and uric acid or salts thereof,

Choline oxidase and choline,

- Amino acid oxidase and amino acids.

The invention therefore furthermore relates to a process for dyeing keratin fibers, in particular hair, in which an oxidation dye according to the invention is applied to the fiber together with an oxidizing agent and / or with a catalyst for activating the oxidation and, after an exposure time, again with water or rinsed with an aqueous surfactant preparation.

The preparation of the oxidizing agent is expediently mixed with the preparation from the oxidation dye pre-products directly before hair coloring. The resulting ready-to-use hair color preparation should preferably have a pH in the range from 6 to 10. The use of hair colorants in a weakly alkaline environment is particularly preferred. The application temperatures can range between 15 and 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.

The following examples are intended to explain the subject of the invention in more detail.

Examples

1. Synthesis example

4,5-dimethoxy-3-methyl-1,2-diaminobenzene-2 HC1

5 g of 4,5-dimethoxy-3-methyl-1,2-dinitiObenzene (Ber. 49, (1916), 1493) were in 100 ml of ethanol in the presence of 0.5 g of palladium (5%) on carbon at room temperature and 1 atü hydrogen hydrogenated. After the H ₂ uptake had ended, the catalyst was filtered off and the filtrate was acidified with concentrated hydrochloric acid. After concentration to dryness, the residue was recrystallized from ethanol.

3 g of beige-pink crystals with a melting point above 215 ° C. (with decomposition) were obtained.

2. Discolorations

A base cream of the following composition was produced:

Taig fatty alcohol (C ₁₆ -Cι ₈ ) 17.0 g

Coconut fatty alcohol (Cι ₂ -C_ ₈₎ 4.0 g

Natrix unlauryl ether sulfate (28% solution) 40.0 g

Cocosamidopropyl betaine (30% solvent) 25.0 g

Cetyl / stearyl alcohol ρoly (20EO) glycol ether 1.5 g

Water 12.5 g

Coloring creams of the following composition were produced:

Basic cream 50.0 g

Developer component (El to E10) 7.5 mmol

4,5-dimethoxy-3-methyl-1,2-diaminobenzene ^• 2 HC1 7.5 mmol

Na ₂ SO ₃ (inhibitor) 1.0 g

(NH4) ₂ SO ₄ 1.0 g conc. NH ₃ solution ad pH = 10 water ad 100 g

The following developer compounds were used for the coloring:

In the examples with developer combinations, 3.75 mmol of each of the developers were used so that the total amount of developer in the coloring cream was 7.5 mmol / 100 g. The ingredients were mixed together in order. After the oxidation dye precursors, the inhibitor and the (NH ₄ ) ₂ SO _{4 had been added} , the pH of the emulsion was adjusted to 10 using concentrated ammonia solution, and the mixture was then made up to 100 g with water.

The oxidative development of the color was carried out with a 3% by weight hydrogen peroxide solution. For this purpose, 100 g of the emulsion are mixed with 50 g of H ₂ O ₂ solution (3%) xmd.

The ready-to-use dyeing batches were then applied to 5 cm long strands of standardized, 80% gray, but not specially pretreated human hair (Kerling). After 30 minutes of exposure at 32 ° C, the hair was with Rinsed water, washed out with a normal shampoo, rinsed again and dried. The results of the dyeing tests are shown in the table.

Claims

claims

4,5-dialkoxy-1,2-diaminobenzenes of the formula I.

in which R ¹ and R ² independently of one another are a CrC ₄ alkyl group or a C ₂ - C ₄ hydroxyalkyl group and R ^{3 is} hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group, xmd their water-soluble salts ,

2. 4,5-dimethoxy-3-methyl-1,2-diaminobenzene

3. Use of the 4,5-dialkoxy-l, 2-diaminobenzenes according to spoke 1 or 2 or their water-soluble salts as coupler compounds for producing oxidation colors with known developer components.

4. oxidation dye for dyeing keratin fibers, in particular hair, characterized in that they contain at least one developer component and at least one 4,5-dialkoxy-1,2-diaminobenzene of the formula I according to approach 1 as coupler in an aqueous carrier.

5. Oxidation dye according to spoke 4, characterized in that at least one aromatic amino compound with a para or hydroxy or amino group is contained as developer compound.

6. Oxidation dye according to one of claims 4 or 5, characterized in that further coupler compounds xmd optionally also contain direct dyes.

7. oxidation dye according to one of claims 4 to 6, characterized in that the developer compound is selected from p-phenylenediamine, p-toluenediamine, l- (2'-hydroxyethyl) -2,5-diaminobenzene, 2,5-diaminophenoxyethanol , N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, p-aminophenol, 3- Methyl-4-aminophenol, 2-hydroxyethylaminomethyl-4-aminophenol, 4-amino-2- ((diethylamino) methyl) phenol, 2-aminomethyl-4-aminophenol, 2- (2'-

Hydroxyethoxy) -4-aminophenol, 2-hydroxymethyl-4-aminophenol, bis- (2-hydroxy-5-aminophenyl) methane, N, N '-Bis- (2' -hydroxyethyl) -N, N '-bis- (4 '- aminophenyl) - 1, 3 -diaminopropan-2-ol, 1 -phenyl-3-carboxyamido-4-amino-pyrazolone, 4,4'-diamino-diphenylamine, 1,4-bis- (4'- aminophenyl) diazycloheptane, 4,5-diamino-l (2'-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2 , 5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, o-aminophenols and o-phenylenediamines.

8. Oxidation dye according to spoke 6, characterized in that the further coupler compounds are selected from 1-naphthol, pyrogallol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, lJ-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol , m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis- (2 ', 4'- diaminophenoxy) propane, 4-chlororesorcinol, 2-chloro-6-methy 1-3 -aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2- amino-3-hydroxypyridine, 2,6-dihydroxy-3, 4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluene, 2,6-bis- (2nd '- hydroxyethylamino) toluene, 2- (2', 4'-diaminophenoxy) ethanol, l-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 2-methyl-4-chloro-5- amino-phenol, 6-methyl, 2,3,4-tetrahydro-quinoxaline, 3,4-methylenedioxyphenol, 3,4-methylenedioxy aniline, 2,6-dimethyl-3-amino-phenol , 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxyethanol, 2-methyl-5- (2'-hydroxyethylamino) phenol and 2,6-dihydroxy-3,4-dimethylpyridine.

9. oxidation dye according to one of claims 4 to 8, characterized in that at least one indole and or indoline derivative is included.

10. A process for dyeing keratin fibers, in particular hair, characterized in that an oxidation coloring agent according to any one of claims 4 to 9, together with an oxidizing agent and / or with an on the fibers Applies catalyst to activate the air oxidation and after an exposure time rinsed again with water or an aqueous surfactant solution.