WO2006108458A1

WO2006108458A1 - Agents for simultaneously dying and lightening keratin fibers

Info

Publication number: WO2006108458A1
Application number: PCT/EP2006/000666
Authority: WO
Inventors: Horst Höffkes; Thomas Mucha
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2005-03-21
Filing date: 2006-01-26
Publication date: 2006-10-19
Also published as: DE102005013488A1

Abstract

The invention relates to agents for simultaneously dying and lightening human hairs. These dyes contain at least one specified direct-dying hair dye and at least one carbonate and/or one carbonate precursor.

Description

"Means for Simultaneous Dyeing and Lightening of Keratinous Fibers"

The present invention relates to a novel means for the simultaneous dyeing and whitening of keratin fibers, in particular human hair hair dyes based on direct dyes and / or oxidation dye precursors, which compared to conventional hair dyes both a more brilliant coloring and a better lightening of the hair causes ,

Conventional hair dyes usually consist of at least one developer and at least one coupler substance and possibly even contain direct dyes as Nuanceure. Coupler and developer components are also referred to as oxidation dye precursors.

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

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraminopyrimidine, 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-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4- aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used. Suitable coupler substances are in particular α-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol , 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-diol chloro-3-aminophenol, 1, 3-bis- (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5- Methylresorcinol, 3-amino-6-methoxy-2-methylaminopyridine and 3,5-diamino-2,6-dimethoxypyridine.

For temporary dyeings usually dyeing or tinting agents are used which contain so-called direct drawers as a coloring component. These are dye molecules that raise directly onto the hair and do not require an oxidative process to form the dye. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable change in shade or even a visible "discoloration" occurs much faster.

Prior to their application to human hair, hair dye with oxidation dye precursors are mixed with dilute aqueous hydrogen peroxide solution. The duration of exposure to the hair to achieve complete coloration is between about 30 and 40 minutes. It is obvious that users of these hair dyes have a need to reduce this exposure time.

At the same time there is often the desire to achieve, together with the hair coloring, a whitening of the hair to be dyed, which is also noticeable as increased gloss.

Means for the simultaneous dyeing and whitening of keratin-containing fibers are known from DE 43 31 136 A1. The disclosed therein agents contain at least one developing agent and at least one coupler substance and at least one ammonium compound selected from the group consisting of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate and ammonium carbamate, and, after mixing with an oxidizing agent, in the ready-to-use mixture has a pH between 8 and 11.

There was also a need to improve hair dyeing and whitening agents so that more intense, vivid and brilliant colors are obtained and at the same time the exposure time is shortened, for example by the oxidation reaction is accelerated.

It has now been found that the use of certain substantive dyes in combination with carbonates in hair-dyeing and lightening agents offers the advantages mentioned.

The present invention is in a first embodiment, a means for simultaneous dyeing and whitening of human hair, comprising at least one substantive hair dye and at least one carbonate and / or a carbonate precursor, characterized in that it comprises at least one substantive hair dye from the group

3,4,5,6-Tetrabromphenolsulfonaphthalein

sulfobromophthalein

bromocresol

Bromthymolblau

tetrabromophenol

Acid Red 37 (CM 7045)

Acid Orange 52 (Cl 13025)

Acid Orange 6 (Cl 14270)

Acid Red 26 (Cj 16150)

Disperse Blue 106 (Cl 111935)

Disperse Red 1 (Cl 1110)

Disperse Orange 3 (Cl 11005)

Disperse Red 17 (Cl 11210)

Disperse Red 179 (Cl 112290)

Acid Red 337 Cl 17102)

Disperse Red 167 (Cl 11338)

Basic Red 18 (Cl 11085)

Acid Orange 8 (Cl 15575)

Disperse Red 118 (CM 1152: 2)

Thionin (Cl 52000)

Basic Blue 17 (Cl 52040)

Basic Blue 24 (Cl 52030)

Basic Green 5 (Cl 52020) 4-nitro-o-phenylenediamine

2-nitro-p-phenylenediamine

4-amino-2-nitrophenol

Acid Yellow 24 (Cl 10315)

Disperse Red 17

3-diethylamino-7- (4-dimethylaminophenylazo) -5-phenyl-phenazinium chloride

(Cl 11050)

Acid Orange 5 (Cl 13080)

HC Red No. 8th

Basic Blue 77

Acid Red 51 (Cl 45430)

Acid Yellow 24 (Cl 10315)

1, 5-diphenylthiocarbazone

HC Yellow 13

N- (2-hydroxyethyl) -4-nitroaniline

4-Chloro-N- (2,3-dihydroxypropyl) -2-nitroaniline

3- (2 ', 6'-Diaminopyridyl-3-azo) pyridine

4- (2-thiazolylazo) resorcinol

dithizone

2-amino-1,4-naphthalenedione

3 ', 3 ", 5', 5" -Tetrabrom m-cresolsulfonaphthalein

Disperse Blue 102

Disperse Blue 148

Resolin Blue K-FBL

Resolin Blue K-2GLS

Disperse Blue 154

Disperse Blue 281

Disperse Blue 291

Disperse Blue 321

Disperse Blue 347

Disperse Red 338

Disperse Red 54

Disperse Red 258

Disperse Orange 66

Disperse Yellow 241 Disperse Blue 7 (Cl 62500) Disperse Blue 14 (CI 61500) Disperse Blue 26 (CI 63305) Disperse Blue 35 Disperse Blue 55 Disperse Blue 56 (Cl 63285) Disperse Blue 60 (Cl 61104) Disperse Blue 62 Disperse Blue 64 Disperse Blue 72 (CI 60725) Disperse Blue 77 Disperse Blue 79 (CI 11345) Disperse Blue 87 Disperse Blue 94 Disperse Blue 109 Disperse Blue 153 Disperse Blue 180 Disperse Blue 183 Disperse Blue 287 Disperse Blue 326 Disperse Blue 333 Disperse Blue 337 (Cl 11337) Disperse Disperse Blue 367 Disperse Green 9 Disperse Violet 8 (Cl 62030) Disperse Violet 17 (Cl 60712) Disperse Violet 26 (Cl 62025) Disperse Violet 28 (Cl 61102) Disperse Violet 33 (Cl 11218) Disperse Violet 3 Disperse Violet 36 Disperse Violet 40 Disperse Violet 48 Disperse Violet 60 Disperse Violet 63

Disperse Violet 72 Cl 60725)

Disperse Violet 91

Basic Blue 54 CM 1052)

Basic Blue 67 Cl 45175)

Basic Brown 1 (Cl 21000)

Basic Brown 4 (Cl 21010)

Basic Orange 2 (Cl 11270)

Basic Red 46 "

Basic Red 104

Basic Violet 35

Basic Yellow 45

Basic Yellow 67

HC Yellow 4

3-nitro-4- (3'-hydroxypropyl) aminopheno

4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene

1-Amino-4-bis (2'-hydroxyethyl) amino-2-nitrobenzene

4-amino-3-nitrophenol

HC Blue 2

Direct Violet 51

Solvent Violet 12

Disperse Blue 1

2'-methyl-4 '- (N-ethyl-N-m-sulfobenzyl) -amino-4 "- (N, N-diethyl) amino-2-methyl-N-ethyl-N-m-sulfobenzyl-fuchsoneimonium (CI 42735)

1, 5-di- (4'-methyl-2'-sulfophenylamino) -anthraquinone (CI 67710)

Disperse Violet 4 (Cl 61105)

1, 4-diamino-2-nitrobenzene (Cl 76070)

HC Red 13

HC Violet 1, 4 D (1, 4-bis (2'-hydroxyethyl) amino-2-nitrobenzene)

HC Yellow 5

HC Orange 1

HC Red 1

1-Amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene

(4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene)

1-amino-4- (2'-hydroxyethyl) amino-2-nitrobenzene 4-amino-3-nitrophenol HC Red B 54

(1-Hydroxy-4- (2'-hydroxyethyl) amino-3-nitrobenzene) HC Red BN

(1-Hydroxy-4- (3'-hydroxypropyl) amino-3-nitrobenzene) 1-Hydroxy-4-bis (3'-hydroxypropyl) amino-3-nitrobenzene 1- (2'-Ureidoethyl) amino-4- Nitrobenzene HC Red 7 HC Red 10 HC Red 11 HC Red 13

2- (2'-Hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene HC Blue H HC Blue 12 HC Yellow 13 HC Yellow 6

1- (2'-Hydroxyethyl) amino-4-methyl-2-nitrobenzene HC Yellow 12

4-Ethylamino-3-nitrobenzoic acid 4-Amino-2-nitrodiphenylamine-2'-carboxylic acid 4-Dimethylamino-2-nitrodiphenylamine-2'-carboxylic acid 6-Nitro-1,2,3,4-tetrahydroquinoxaline Basic Violet 2 Basic Violet 14 Acid Red 52 Disperse Blue 3

1-Propen- (4'-amino-2'-nitrophenyl) amine Basic Blue 77 Basic Blue 124 Basic Blue 151 contains.

The compositions according to the invention contain at least one carbonate and / or one carbonate precursor. "Carbonates" within the meaning of the present application Compounds containing the carbonate group -0-C (O) -O- or ^~ 0-C (O) -O ^~ or a carbonate-analogous group with elements of IV. Main group of the Periodic Table (especially -0-Si (O) -O - or ^"... 0-Si (O) -O ^~) comprise carbonates may therefore be both salts and esters of carbonic acid or of the analogous acids of the elements of the IV main group of the Periodic Table" carbonate precursor "in the sense of the present Registration are substances that can form carbonates under the conditions of use. In this group fall mainly organic carbonic acid derivatives which form carbonates in the hydrolysis, in particular the carbamates.

For example, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or ammonium carbonate and mixtures thereof can be used as carbonates in the context of the present invention. However, the use of "organic carbonates" is preferred.

Agents preferred according to the invention are characterized in that the carbonate is selected from carbonic acid mono- and / or diesters, preferably from methyl carbonate, ethyl carbonate, propyl carbonate, their salts and / or mixtures thereof.

Thus, carbonates according to the invention esters of carbonic acid can be used. Both carbonic acid monoesters and carbonic acid diesters are suitable here. Agents preferred according to the invention comprise at least one carbonic acid monoester of the formula (I)

R-O-C (O) -O-H (I),

in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

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

Particularly preferred agents according to the invention are characterized in that the radical R in formula (I) is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, terf-butyl as well as hydroxymethyl and hydroxyethyl radicals.

The acidic carbon atom of the carbonic monoester may also be present in neutralized form, i. it is also possible according to the invention to use salts of carbonic acid monoesters. Here, agents according to the invention are preferred which comprise the carbonic acid monoester carbonic acid monoamide in completely or partially neutralized form, preferably in the form of its alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt.

Carbonic acid diesters according to the invention can be used as further preferred esters of carbonic acid. Agents preferred according to the invention therefore contain at least one carbonic acid diester of the formula (II)

R-O-C (O) -O-R '(II),

in which R and R 'each independently represent a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (II), R and R 'are each, independently of one another, preferably a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents , Further preferred radicals R and R 'are phenyl and benzyl radicals and further substituted representatives. Particularly preferably R or R ^'is a C _1-6 alkyl group. Examples of C ₁ -C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl. Particularly preferred agents according to the invention are characterized in that the radical R and R ^' in formula (II) are each independently selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl , tert-butyl and hydroxymethyl and hydroxyethyl radicals.

Instead of carbonic acid monoesters and / or their physiologically acceptable salts and / or carbonic acid diesters, the compositions according to the invention may also contain esters of orthocarbonic acid. As further preferred esters of carbonic acid can therefore be used according to the invention Orthokohlensäureester. Agents preferred according to the invention therefore contain at least one carbonic diester of the formula (III)

O-R '

I R-O-C-O-R '"(III),

I

O-R "

in which R, R ', R "and R'" each independently represent a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (III), R, R ', R "and R'" each independently of one another preferably represent a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, as substituents. , Sulfonic acid groups or halogens in question. Further preferred radicals R, R ', R "and R'" are phenyl and benzyl radicals and further substituted representatives. Particularly preferably R or R 'is a C _1-6 alkyl group. Examples of C _r C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Particularly preferred agents according to the invention are characterized in that the radicals R, R ', R "and R"' in formula (III) are each independently selected from methyl, ethyl, n-propyl, iso-propyl, n Butyl, iso-butyl, terf-butyl and Hydroxymethyl and hydroxyethyl residues. Particularly preferred representatives are tetramethyl and tetraethyl orthocarbonate.

Also preferred according to the invention is the use of cyclic carbonic acid esters. These cyclic esters of carbonic acid are referred to as 1, 3-dioxolan-2-ones and can be described by the following structure:

In the main body of the 1, 3-dioxolan-2-ones are each bound in the 4- and 5-position two H atoms. It is possible and preferred within the scope of the present invention to use also derivatives of this basic structure, ie 1, 3-dioxolan-2-ones substituted in 4- or 4- and 5-position. There are no limits to the structural diversity, so that mono-, di-, tri- and tetra-substituted 1, 3-dioxolan-2-ones are suitable for use in the context of the present invention.

Agents preferred according to the invention are therefore characterized in that they contain at least one carboxylic ester from the group of substituted or unsubstituted 1,3-dioxolan-2-ones

r °

contain.

Particularly preferred are in addition to the unsubstituted 1, 3-dioxolan-2-one in particular the monosubstituted in the 4-position derivatives, the following formula

where R is a substituted or unsubstituted alkyl, alkenyl or alkylaryl radical. Preferred radicals R are methyl, ethyl, n-propyl, isopropyl and hydroxymethyl and hydroxyethyl radicals.

Particularly preferred agents according to the invention are therefore characterized in that they contain at least one monosubstituted 1-substituted 3-dioxolan-2-one derivative of the following formula (IV)

in which R is a substituted or unsubstituted alkyl, alkenyl or alkylaryl radical, wherein in further preferred agents of the invention the radical R in formula (III) is selected from methyl, ethyl, n-propyl, iso-propyl - As well as hydroxymethyl and hydroxyethyl radicals.

Particularly preferred 1, 3-dioxolan-2-ones are from the group ethylene carbonate (R = H), propylene carbonate (R = CH ₃ ) and glycerol carbonate (R = CH ₂ OH).

Ethylene carbonate is a colorless crystalline compound that melts at 39 ° C and boils at 238 ° C. The readily soluble in water, alcohols and organic solvents ethylene carbonate can be prepared by large-scale synthesis of ethylene oxide and liquid CO ₂ . Propylene carbonate is a water-bright, easily mobile liquid, with a density of 1, 2057 like ^'3 , the melting point is -49 ° C, the boiling point at 242 ⁰ C. Also propylene carbonate is industrially by reaction of propylene oxide and CO ₂ at 200 ⁰ C. and 80 bar accessible. Glycerol carbonate is accessible by transesterification of ethylene carbonate or dimethyl carbonate with glycerol, as by-products of ethylene glycol or methanol incurred. Another synthetic route is based on glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to glycerol carbonate. Glycerol is a clear, mobile liquid with a density of 1, 398 ^{gcm -3,} boiling at 125-130 ⁰ C (0.15 mbar). Particularly preferred in the context of the present invention is the use of glycerol carbonate, for example, in amounts of 1, 0 to 15.0 wt .-%, preferably from 2.0 to 13.5 wt .-% and in particular from 3.5 to 11, 5 wt .-%, each based on the agent is used.

As mentioned above, salts of carbonic acid monoesters or "carbonate precursors" which can form carbonates under the conditions of use can also be used according to the invention.

Here, agents according to the invention are particularly preferred in which the carbonate is selected from carbonate monoester salts and / or carbonic acid monoamides and / or their salts, silyl carbonates and / or silyl carbamates and mixtures thereof.

Carbon monoxide salts preferred according to the invention satisfy the abovementioned formula (I), the acidic hydrogen being exchanged for a physiologically compatible cation, preferably Na ⁺ , K ⁺ , NH ₄ ⁺ , etc.

The compositions according to the invention may also contain carbonic acid monoamides as carbonate precursors. Here, preferred agents according to the invention are characterized in that they contain at least one carbonic acid monoamide of the formula (IV)

R-NH-C (O) -O-X (IV)

in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle and X is H or a physiologically compatible cation.

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

Particularly preferred agents according to the invention are characterized in that the radical R in formula (IV) is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, fe / τf Butyl and hydroxymethyl and hydroxyethyl radicals.

The acidic H atom of the carbonic acid monoester or monoamide may also be in neutralized form, i. According to the invention, it is also possible to use salts of carbonic monoethylenes or carbonic acid monoamides. Here, agents according to the invention are preferred which contain the carbonic acid monoester or the carbonic acid monoamide in completely or partially neutralized form, preferably in the form of its alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt.

According to the invention, a compound which contains, instead of carbon, another element of main group IV of the periodic table can also be used as the carbonate or carbonate precursor. In particular, the silyl carbonates and / or silyl carbamates should be mentioned as preferred. These substances are described in detail below.

Agents preferred according to the invention are characterized in that they contain at least one silyl carbonate of the formula (V)

R ¹ -Si-OC (O) -OR ⁴ (V)

IR ³

in which the radicals R ¹ , R ² and R ^{3 are} independently of one another a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or for a Trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino, imino groups and the radical R ^{4 is} a chemical bond to Si - atom or to one of the radicals R ¹ , R ² or R ³ , a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or for a substituted or unsubstituted SiIyI or Aluminylgruppe or for a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (V) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among these, the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred agents according to the invention are characterized in that the radicals R ¹ , R ² and R ³ in formula (I) are selected from methyl, ethyl, n Propyl, iso-propyl, n-butyl, iso-butyl, ferf-butyl, hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ in the abovementioned formula (V) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.

Particularly preferred silyl carbonates of the general formula (V) are reproduced with respect to their radicals R ¹ , R ² , R ³ and R ⁴ in the following Table 1:

Table 1: preferred silyl carbonates

>

The acidic H atom of the silyl carbonate (R ⁴ = -H in formula V) can also be present in neutralized form, ie according to the invention it is also possible to use salts of silyl carbonates. Here, agents according to the invention are preferred which comprise at least one silyl carbonate in completely or partially neutralized form, preferably in the form of its alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt.

In addition to the silylcarbonates or in their place, the compositions of the invention may contain silyl carbamates.

Agents preferred according to the invention are characterized in that they contain a silyl carbamate of the formula (VI)

R ²

R ¹ -Si-OC (O) -NR ⁴ R ⁵ (VI)

I

R ³

containing, in which the radicals R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or for a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino groups and the radicals R ⁴ and R ⁵ independently of one another for a chemical bond to the Si atom or to a the radicals R ¹ , R ² or R ³ , a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or for a substituted or unsubstituted SiIyI or Aluminylgruppe or for a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (VI) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among these, the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred agents according to the invention are characterized in that the radicals R ¹ , R ² and R ³ in formula (VI) are selected from methyl, ethyl, n Propyl, iso-propyl, n-butyl, iso-butyl, fe / f-butyl and hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ and R ⁵ in the abovementioned formula (VI) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.

Particularly preferred silyl carbamates of the general formula (VI) are reproduced with respect to their radicals R ¹ , R ² , R ³ and R ⁴ in the following Table 2:

Regardless of which carbonate or which carbonate precursor contain the agents according to the invention, agents according to the invention are preferred, the carbonate (s) in amounts of 0.5 to 15 wt .-%, preferably from 1 to 12 wt .-%, especially preferably from 2 to 9 wt .-% and in particular from 3 to 7 wt .-%, each based on the total agent included.

The direct dyes mentioned are preferably used in specific amounts. In this case, agents according to the invention are preferred, the substantive (s) Dye (s) from the above list in amounts of 0.01 to 10 wt.%, Preferably from 0.05 to 8 wt.%, Particularly preferably from 0.1 to 5 wt.% And in particular from 0.5 to 3.5% by weight, based in each case on the total agent,

In addition to the direct dye (s) mentioned, the agents according to the invention may contain further dyes and / or dye precursors. Compositions according to the invention which additionally comprise at least one oxidation-type dye precursor of the developer type and / or optionally at least one coupler-type oxidation dye precursor are preferred.

With regard to the further dye precursors which can be used in the agents according to the invention, the present invention is not subject to any restrictions. The agents according to the invention can be used as further dye precursors - oxidation dye precursors of the developer and / or coupler type, and

Precursors of natural analog dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups.

In a first preferred embodiment, the agent further contains at least one developer component. 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-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used ,

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

in which G ¹ is a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

Monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) -

AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -

Alkyl radical containing a nitrogen-containing group, a phenyl or a 4'-

Aminophenylrest is substituted;

G ² is a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

Alkoxy (C ₁ to C ₄ ) alkyl or a C ₁ to C ₄ alkyl substituted with a nitrogen containing group;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or

Fluorine atom, a C ₁ - to C ₄ -alkyl radical, a d- to C ₄ monohydroxyalkyl radical, a

C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to

C ₄ -acetylaminoalkoxy, C ₁ - to C ₄ -mesylaminoalkoxy or C ₁ - to C ₄ -carbamoylaminoalkoxy;

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and buty). Ethyl and methyl are preferred alkyl radicals. Preferred Cr to C ₄ -alkoxy radicals according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C 1 to C ₄ hydroxyalkyl group, there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are in particular the amino groups, C ₁ to C ₄ monoalkylamino groups, C ₁ to C ₄ dialkylamino groups, C ₁ to C ₄ trialkylammonium groups, C ₁ to C ₄ monohydroxyalkylamino groups, Imidazolinium and 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 (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-S-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy ) -p-phenylenediamine, 2- (β-acetylam inoethyloxy) -p-phenylenediamine, N- (.beta.-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

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

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.

Among the binuclear developer components which can be used in the compositions according to the invention, mention may be made in particular of the compounds which correspond to the following formula (E2) and their physiologically tolerated 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 - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen , Sulfur or nitrogen atoms may be interrupted or terminated and may optionally be substituted by one or more hydroxyl or C ₁ - to C ₈ alkoxy radicals, or a direct bond, G ⁵ and G ⁶ are each independently a hydrogen or halogen atom , a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -hydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ to C ₄ alkyl radical, with the provisos that

the compounds of the formula (E2) contain only one bridge Y per molecule and

- The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - (ß-hydroxyethyl) -N, N'-bis (4-aminophenyl) - tetramethylenediamine, N, N'-bis (4-methyl-aminophenyl) -tetramethy endiamin, N ₁ N'-diethyl-N,! N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propane-2 -ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-Aminophenyl) -p-phenylenediamine and 1, 10-bis (2 ', 5'-diaminophenyl) -1, 4, 7, 10-tetraoxadecane and their physiologically acceptable salts.

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4, 7, 10-tetraoxadecane or one of 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. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) - Alkoxy (C _r to C ₄ ) alkyl, a C ₁ - to C ₄ -Aminoalkylrest, a hydroxy (C _r to C ₄ ) alkylamino, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - C ₄ hydroxyalkyl aminoalkyl (C Crbis ₄₎ or (di-C _r to C ₄ alkylamino) - alkyl - (C ₁ to C _4), and

G ¹⁴ is a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) - Alkoxy (C _r to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ -cyanoalkyl radical,

G ¹⁵ is hydrogen, C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ is hydrogen or a halogen atom. The substituents used in formula (E3) are defined according to the invention analogously to the above statements.

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

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

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

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

Preferred pyridine derivatives are in particular the compounds 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxypyridine, 2- (β-methoxyethyl ) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are in particular 2,4,5,6-tetraaminopyrimidine, A-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, 4,5-diamino-i-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'- chlorobenzyl) - pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1, 3 dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl 3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4 '-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4 , 5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (D-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-

Triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

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

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl a (C ₁ - to C ₄₎ alkoxy -, alkyl (Ci to _C4) a C ₁ - to C ₄ -aminoalkyl radical, which may be optionally protected by an acetyl ureide or a sulfonyl radical a (C ₁ - to C ₄₎ alkylamino (Cr to C ₄₎ - alkyl group, a di - aminoalkyl (C _r to C _4), wherein the dialkyl - [(C _r to C ₄₎ alkyl] - residues optionally form a carbocycle or a heterocycle with 5 or 6 chain links, a C ₁ - to C ₄ hydroxyalkyl or a di (Cr to C ₄₎ - [hydroxyalkyl] - (C _r to C ₄₎ aminoalkyl radical, the X radicals are each independently a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, a (C ₁ - to C ₄₎ alkylamino (C ₁ - to C ₄₎ alkyl, a di - [(C _r to C ₄₎ alkyl] - (Cr to _C4) aminoalkyl radical, wherein the dialkyl residues optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, a C ₁ - to C ₄ -alkyl or di- (C ₁ - to 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 is 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

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

Among the pyrazolo [1, 5-a] -pyrimidines of the above formula (E4) may be mentioned in particular:

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

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

Pyrazolo [1,5-a] pyrimidine-3,5-diamine;

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

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

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

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

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

2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) amino] -ethanol;

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

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

3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1, 5-a] -pyrimidine; and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

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

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

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, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethylether, m-phenylenediamine, 1-phenyl 3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1, 3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2 Chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Preferred coupler components according to the invention are m-aminophenol and its derivatives, such as, for example, 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) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as, for example, resorcinol, resorcinomonomethyl 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-dimethoxypyridine,

Naphthalene derivatives such as, for example, 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-1,2,3,4-tetrahydroquinoxaline,

- Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-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 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly preferred coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3 hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

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. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the agents contain at least one indole and / or indoline derivative.

Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IIIa),

(purple) in the independently

R ¹ is hydrogen, a C _r C ₄ -alkyl group or a C _r C ₄ -hydroxy-alkyl group,

R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation, R ³ is hydrogen or a C _r C ₄ alkyl group,

R ⁴ is hydrogen, a C 1 -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C _r C ₄ -alkyl group, and R ⁵ is one of the groups mentioned under R ⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

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

in the independently of each other

R ¹ is hydrogen, a C _r C ₄ -alkyl group or a C _r C ₄ -hydroxyalkyl group,

R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,

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

R ⁴ is hydrogen, a C _r C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C 1 -C ₄ -alkyl group, and

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

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.

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

The indoline and indole derivatives can be used in the agents used in the process according to the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. The hydrochloric acid de, the sulfates and hydrobromides used. The indole or indoline derivatives are usually contained therein in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.

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

Preferred agents according to the invention are characterized in that they contain at least one dye precursor from the groups of the aromatic and heteroaromatic diamines, aminophenols, naphthols, polyphenols CH-acidic coupler components and their derivatives in amounts of from 0.01 to 25% by weight, preferably 0.5 to 10 wt.%, In particular from 1 to 5 wt .-%, each based on the total agent included.

According to the invention, at least one particular substantive dye from the list mentioned above is contained in the agents according to the invention. In addition, the compositions according to the invention may contain further substantive dyes. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis- (β-hydroxyethyl) amino-2-nitrobenzene, 3-islitro-4- (β-hydroxyethyl) aminophenol, 2- 2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2 -nitrobenzene, 4-amino-3-nitrophenol, 1 - (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-car Bonsäure, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, picramic acid and their Salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Corresponding agents according to the invention, which are characterized in that they contain at least one substantive dye from the group of cationic (basic) dyes, preferably Basic Blue 6, CI-No. 51, 175; Basic Blue 7, CI- No. 42.595; Basic Blue 9, Cl-No. 52.015; Basic Blue 26, Cl-No. 44.045; Basic Blue 41, Cl-No. 11, 154; Basic Blue 99, Cl-No. 56.059; Basic Brown 4, Cl-No. 21, 010; Basic Brown 16, Cl-No. 12.250; Basic Brown 17, Cl-No. 12,251; Basic Green 1, Cl-No. 42.040; Basic Orange 31; Basic Red 2, Cl-No. 50.240; Basic Red 22, Cl-No. 11, 055; Basic Red 46; Basic Red 51; Basic Red 76, Cl-No. 12.245; Basic Violet 1, Cl-No. 42.535; Basic Violet 2; Basic Violet 3, Cl-No. 42.555; Basic Violet 10, Cl-No. 45.170; Basic Violet 14, Cl-No. 42.510; Basic Yellow 57, Cl-No. 12.719; Basic Yellow 87 and / or the anionic (acidic) dyes, and / or the nonionic dyes, preferably Acid Black 1, Cl-No. 20.470; Acid Black 52; Acid Blue 7; Acid Blue 9, Cl-No. 42.090; Acid Blue 74, Cl-No. 73.015, Acid Red 18, Cl-No. 16.255; Acid Red 23; Acid Red 27, Cl-No. 16.185; Acid Red 33; Acid Red 52; Acid Red 87, Cl-No. 45,380; Acid Red 92, Cl-No. 45,410; Acid Orange 3; Acid Orange 7; Acid Violet 43, Cl- No. 60.730; Acid Yellow 1, Cl-No. 10.316; Acid Yellow 10; Acid Yellow 23, Cl-No. 19,140; Acid Yellow 3, Cl-No. 47.005; Acid Yellow 36; D & C Brown no. 1, Cl-No. 20.170 (Acid Orange 24); D & C Green no. 5, Cl-No. 61, 570 (Acid Green G); D & C Orange No. 4, Cl-No. 15.510 (Acid Orange II); D & C Orange No. 10, CI-No. 45.425: 1 (Solvent Red 73); D & C Orange No. 11, Cl-No. 45.425 (Acid Red 95); D & C Red No. 21, Cl-No. 45.380: 2 (Solvent Red 43); D & C Red No. 27, Cl-No. 45.410: 1 (Solvent Red 48); D & C Red No. 33, Cl-No. 17,200 (Acid Red 2A, Acid Red B); D & C Yellow No. 7, CI-No. 45.350: 1 (Solvent Yellow 94); D & C Yellow No. 8, Cl-No. 45,350 (Acid Yellow 73); FD & C Red No. 4, Cl-No. 14,700 (Food Red 4); FD & C Yellow No. 6, Cl-No. 15,985 (Food Yellow 3); Food Green 3; Pigment Red 57-1; Disperse Black 9; Disperse Blue 1; Disperse Blue 3; Disperse Violet 1; Disperse Violet 4; HC Orange 1; HC Red 1; HC Red 3; HC Red 13; HC Yellow 2; HC Yellow 4; Na-Pikramat; 1, 4-bis (2'-hydroxyethyl) amino-2-nitro-p-phenylenediamine; HC Yellow 5; HC Blue 2; HC Blue 12; 4-amino-3-nitrophenol; HC Yellow 6; HC Yellow 12; 2-nitro-1- (2'-hydroxyethyl) amino-4-methylbenzene; 2-nitro-4-amino-diphenylamine-2-carboxylic acid ^'; 2-amino-6-chloro-4-nitrophenol; HC Red BN; 6-nitro-1,2,3,4-tetranitroquinoxaline; o-nitro-p-phenylenediamine; p-nitro-m-phenylenediamine; HC Red B 54; HC Red 10; HC Red 11; HC Red 13; 2- (2'-hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene; 4-ethylamino-3-nitrobenzoic acid; 2 Chloro-6-ethylamino-4-nitrophenol; 2-hydroxy-1,4-naphthoquinone; 1-propene- (4-amino-2-nitrophenyl) amine; isatin; N-methylylisatin; HC Violet 1; HC Violet 2; 4-Nitrophenyl aminoethyl urea in amounts of 0.01 to 25 wt.%, Preferably from 0.5 to 10 wt.%, In particular from 1 to 5 wt .-%, each based on the total agent, are preferred embodiments of the present invention.

Among the above-mentioned dyes, some representatives are particularly preferred, for which reason further preferred agents according to the invention, characterized in that they comprise at least one direct drawler selected from Basic Blue 7, Basic Blue 99, Basic Violet 14, Basic Brown 16, Basic Brown 17, Basic Orange 31, Basic Red 46, Basic Red 51, Basic Red 76, Basic Yellow 57, Basic Yellow 87, Acid Black 1, Acid Blue 7, Acid Violet 43, Acid Red 23, Acid Red 52, Acid Orange 7, Acid Yellow Disperse Blue 1, Disperse Blue 3, Disperse Violet 1, Disperse Violet 4, HC Orange 1, HC Red 1, HC Red 1, Acid Yellow 10, Acid Yellow 36, Food Green 3, Pigment Red 57-1, Disperse Black 9, Disperse Blue 1 3, HC Red 13, HC Yellow 2, HC Yellow 4, Na-Pikramat, 1, 4-bis (2 ^{'-hydroxyethyl)} amino-2-nitro-p-phenylenediamine, HC Yellow 5, HC Blue 2, HC Blue 12, 4-amino-3-nitrophenol, HC Yellow 6, HC Yellow 12, 2-nitro-1- (2 ^{'hydroxyethyl)} amino-4-methyl benzene, 2-nitro-4-amino-diphenylamine-2-carboxylic acid, 2 amino-6-chl or-4-nitrophenol, HC Red BN; 6- Nitro-1,2,3,4-tetranitroquinoxaline, o-nitro-p-phenylenediamine, p-nitro-m-phenylenediamine, HC Red B 54, HC Red 10, HC Red 11, HC Red 13, 2- 2'-hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene, 4-ethylamino-3-nitrobenzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-hydroxy-1,4-naphthoquinone, 1-propene - (4-amino-2-nitrophenyl) amine, isatin, N-Methylylisatin, HC Violet 1, HC Violet 2, 4-nitrophenyl-aminoethyl urea in amounts of 0.01 to 25 wt.%, Preferably from 0.5 to 10 % By weight, in particular from 1 to 5% by weight, in each case based on the total agent, are preferred.

Furthermore, the agents according to the invention may contain a cationic substantive dye. Particularly preferred are

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

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

(c) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, such as For example, in EP-A2-998 908, to which reference is explicitly made at this point, may be mentioned in claims 6 to 11.

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

CH ₃ SO ₄ ^"

Cl ^"

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c). The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention also very particularly preferred cationic direct dyes.

The agents according to the invention according to this embodiment contain the remaining, i. not directly in the above list substantive dyes preferably in an amount of 0.01 to 20 wt .-%, based on the total agent.

Furthermore, the preparations of the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

Furthermore, it has proved to be advantageous if the agents according to the invention contain nonionic surfactants. Such surfactants having an HLB of 5.0 and greater are preferred. For the definition of the HLB value, explicit reference is made to the statements in Hugo Janistyn, Handbuch der Kosmetika und Riechstoffe, III. Volume: The personal care products, 2nd edition, Dr. med. Alfred Hüthig Verlag Heidelberg, 1973, pages 68-78 and Hugo Janistyn, Paperback of modern perfumery and cosmetics, 4th edition, Scientific Publishing Company m.b.H. Stuttgart, 1974, pages 466-474, as well as the original works cited therein.

Particularly preferred nonionic surfactants are because of the ease of processing substances that are commercially available as solids or liquids in pure form. The definition of purity in this context does not refer to chemically pure compounds. Rather, especially when it comes to natural-based products, mixtures of different homologs can be used, for example, with different alkyl chain lengths, such as those obtained with products based on natural fats and oils. Even with alkoxylated products, mixtures of different degrees of alkoxylation are usually present. The term purity in this context refers rather to the fact that the selected substances should preferably be free from solvents, adjuvants and other impurities. Preferred nonionic surfactants are

- Alkoxylated fatty alcohols having 8 to 22, in particular 10 to 16, carbon atoms in the fatty alkyl group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty alkyl groups are, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl groups. Particularly preferred compounds of this class are, for example, lauryl alcohol with 2 to 4 ethylene oxide units, oleyl and cetyl alcohol with 5 to 10 ethylene oxide, cetyl alcohol and stearyl alcohol and mixtures thereof with 10 to 30 ethylene oxide units and the commercial product Aethoxal ^® B (Henkel), a Lauryl alcohol with 5 ethylene oxide and 3 propylene oxide units. In addition to the usual alkoxylated fatty alcohols, it is also possible to use so-called "end-capped" compounds according to the invention In these compounds, the alkoxy group has no OH group at the end but is "closed" in the form of an ether, in particular a C 1 -C 4 -alkyl ether. , An example of such a compound is the commercially available product ^® Dehypon LT 054, a C-8 _12-1 Fettalkoholol + 4.5 ethylene oxide-butyl ether.

- alkoxylated fatty acids having 8 to 22, in particular 10 to 16, carbon atoms in the fatty acid group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty acids are, for example, lauric, myristic, palmitic, stearic, isostearic and oleic acids.

- alkoxylated, preferably propoxylated and especially ethoxylated, mono-, di- and triglycerides. Examples of preferred compounds are glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide.

Polyglycerol esters and alkoxylated polyglycerol esters. Preferred compounds of this class are for example poly (3) glycerindiisostearat (commercial product: Lame form ^® TGI (Henkel)) and poly (2) glycerinpolyhydroxy- stearate (commercial product: Dehymuls ^® PGPH (Henkel)).

Sorbitan fatty acid esters and alkoxylated sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monolaurate + 20 ethylene oxide (EO). - Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15, carbon atoms in the alkyl chain and 0 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 4 EO, nonylphenol + 9 EO, octylphenol + 3 EO and octylphenol + 8 EO.

Particularly preferred classes of nonionic surfactants are the alkoxylated fatty alcohols, the alkoxylated fatty acids and the alkylphenols and alkylphenol alkoxylates.

Agents according to the invention which contain non-ionic surface-active substances in amounts of 1 to 5% by weight have proved to be particularly advantageous.

Furthermore, the compositions according to the invention may contain all known in such preparations active ingredients, additives and excipients. In many cases, the agents contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, cationic or nonionic surfactants. Anionic surfactants may be very particularly preferred.

Preferred anionic surfactants are alkyl sulfates, ether carboxylic acid salts having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule such as C ₁₂ H ₂₅ - (C ₂ H ₄ O) _S -CH ₂ -COONa and in particular salts of saturated and especially unsaturated C8-C22 carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.

These anionic surfactants should preferably be present in solid, in particular powder form. Very particular preference is given to solid soaps, especially sodium stearate, at room temperature. These are preferably present in amounts of from 5 to 20% by weight, in particular from 10 to 15% by weight.

Particularly suitable nonionic surfactants are C 8 -C 22 -alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated compounds have been found to be particularly suitable. Examples of the cationic surfactants which can be used in the agents according to the invention are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

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

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

The compounds containing alkyl groups used as surfactants 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.

As a further constituent, the compositions according to the invention may comprise at least one ammonium compound from the group consisting of ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or

Ammonium carbamate in an amount of 0.5 to 10, preferably 1 to 5 wt .-%, based on the total composition of the composition.

Furthermore, the agents according to the invention may contain further active ingredients, auxiliaries and additives, such as - Nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl ammonium chloride copolymers, dimethylaminoethyl methacrylate quaternized with diethyl sulfate 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-hydroxypropyl methacrylate copolymers, anionic Polymers such as 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 arabicum, karaya gum, locust bean gum, linseed gums, dextrans, celulose derivatives, e.g. For example, methyl cellulose, hydroxyalkyl cellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. Bentonite or fully synthetic hydrocolloids such as e.g. 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, dimethyl isosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,

fiber-structure-improving active substances, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,

quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methanesulfate defoamers such as 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 also 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, lime blossom, 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,

Stabilizers for hydrogen peroxide and other oxidizing agents, propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,

- Antioxidants, included

With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced. The compositions according to the invention may contain the ingredients 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 possible to provide a powdery or tablet-like formulation, which is preferred for Blondiermittel.

Under aqueous-alcoholic solutions of the present invention are aqueous solutions containing, to understand 3 to 70 wt .-% of a C _r C ₄ -alcohol, in particular ethanol or isopropanol in a sense. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.

Preferred agents according to the invention are characterized in that they additionally contain a nonaqueous solvent, with particularly preferred agents according to the invention the solvent in a concentration of 0.1 to 30 weight percent, preferably in a concentration of 1 to 20 weight percent, most preferably in a concentration of 2 - 10 weight percent, each based on the agent included.

In further preferred agents according to the invention, the solvent is selected from ethanol, n-propanol, isoropanol, n-butanol, propylene glycol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, phenoxyethanol and benzyl alcohol and their mixtures.

In addition, the compositions according to the invention may contain further ingredients. For example, use of certain metal ions or complexes may be preferred to obtain intense colorations. Agents according to the invention which additionally contain Cu, Fe, Mn, Ru ions or complexes of these ions are preferred here.

Preferred agents according to the invention comprise from 0.0001 to 2.5% by weight, preferably from 0.001 to 1% by weight, based on the total composition of the composition, of at least one compound from the group consisting of copper chloride (CuCl ₂ ), copper sulfate (CuSO ₄ ), Iron (II) sulfate, manganese (II) sulfate, manganese (II) chloride, cobalt (II) chloride, cerium sulfate, cerium chloride, vanadium sulfate, potassium iodide, sodium iodide, lithium chloride, potassium dichromate, magnesium acetate, calcium chloride, calcium nitrate, barium nitrate, manganese dioxide ( MnO ₂ ) and / or hydroquinone.

The pH of the compositions according to the invention can be adjusted within a wide range by suitable ingredients such as acidifying agent or alkalizing agent. Preferred agents according to the invention are characterized in that the pH of the composition is 6 to 11, preferably 7.5 to 10 and particularly preferably 8 to 9.

Oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen in the presence of oxidation dye precursors. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. This lightening effect may be desired regardless of the staining method. Accordingly, the presence of oxidation dye precursors is not a mandatory requirement for the use of oxidizing agents in the compositions according to the invention. Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate.

However, according to the invention, the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

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

Suitable enzymes include peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes 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, eg

Pyranose oxidase and e.g. 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.

In an application of oxidants, the actual colorant is conveniently prepared immediately prior to use by mixing the preparation of the oxidizing agent with the preparation containing the compounds of formula I and optionally 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 be in a range between 15 and 40 ⁰ 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 omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.

In particular, in the case of hair that is difficult to dye, an agent according to the invention may optionally be applied to the hair with additional dye precursors but also without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After another The reaction time of 10 to 20 minutes is then rinsed and, if desired, post-sonicated. 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 object of the present invention is a process for the simultaneous dyeing and whitening of human hair comprising adding to an aqueous-based composition containing hydrogen peroxide an agent comprising at least one substantive hair dye and at least one carbonate and / or carbonate precursor homogeneous composition is mixed, and this is applied to the hair, characterized in that at least one direct-acting dye contained in the medium is selected from

3,4,5,6-Tetrabromphenolsulfonaphthalein

sulfobromophthalein

bromocresol

Bromthymolblau

tetrabromophenol

Acid Red 37 (Cl 17045)

Acid Orange 52 (Cl 13025)

Acid Orange 6 (Cl 14270)

Acid Red 26 (Cl 16150)

Disperse Blue 106 (Cl 111935)

Disperse Red 1 (CM 110)

Disperse Orange 3 (Cl 11005)

Disperse Red 17 (Cl 11210)

Disperse Red 179 (Cl 112290)

Acid Red 337 CM 7102)

Disperse Red 167 (CM 1338)

Basic Red 18 (Cl 11085)

Acid Orange 8 (Cl 15575)

Disperse Red 118 (CM 1152: 2) Thionin (Cl 52000)

Basic Blue 17 (Cl 52040)

Basic Blue 24 (Cl 52030)

Basic Green 5 (Cl 52020)

4-nitro-o-phenylenediamine

2-nitro-p-phenylenediamine

4-amino-2-nitrophenol

Acid Yellow 24 (Cl 10315)

Disperse Red 17

3-diethylamino-7- (4-dimethylaminophenylazo) -5-phenyl-phenazinium chloride

(Cl 11050)

Acid Orange 5 (Cl 13080)

HC Red No. 8th

Basic Blue 77

Acid Red 51 (Cl 45430)

Acid Yellow 24 (Cl 10315)

1, 5-Diphenylthiocarbazόn

HC Yellow 13

N- (2-hydroxyethyl) -4-nitroaniline

4-Chloro-N- (2,3-dihydroxypropyl) -2-nitroaniline

3- (2 ', 6'-Diaminopyridyl-3-azo) pyridine

4- (2-thiazolylazo) resorcinol

dithizone

2-amino-1,4-naphthalenedione

3 ', 3 ", 5', 5" -Tetrabrom m-cresolsulfonaphthalein

Disperse Blue 102

Disperse Blue 148

Resolin Blue K-FBL

Resolin Blue K-2GLS

Disperse Blue 154

Disperse Blue 281

Disperse Blue 291

Disperse Blue 321

Disperse Blue 347

Disperse Red 338 Disperse Red 54 Disperse Red 258 Disperse Orange 66 Disperse Yellow 241 Disperse Biue 7 (Cl 62500) Disperse Blue 14 (Cl 61500) Disperse Blue 26 (Cl 63305) Disperse Blue 35 Disperse Blue 55 Disperse Blue 56 (Cl 63285) Disperse Blue 60 Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue 79 Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue Disperse Blue 337 Disperse Blue 337 Disperse Blue 369 Disperse Blue 34 Disperse Blue 36 Disperse Blue 9 Disperse Violet 8 (Cl 62030) Disperse Violet 17 (Cl 60712) Disperse Violet 26 (Cl 62025) Disperse Violet 28 (Cl 61102) Disperse Violet 33 (Cl 11218) Disperse Violet 3 Disperse Violet 36

Disperse Violet 40

Disperse Violet 48

Disperse Violet 60

Disperse Violet 63

Disperse Violet 72 Cl 60725)

Disperse Violet 91

Basic Blue 54 CM 1052)

Basic Blue 67 Cl 45175)

Basic Brown 1 (Cl 21000)

Basic Brown 4 (Cl 21010)

Basic Orange 2 (Cl 11270)

Basic Red 46 "

Basic Red 104

Basic Violet 35

Basic Yellow 45

Basic Yellow 67

HC Yellow 4

3-nitro-4- (3'-hydroxypropyl) aminopheno

4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene

1-Amino-4-bis (2'-hydroxyethyl) amino-2-nitrobenzene

4-amino-3-nitrophenol

HC Blue 2

Direct Violet 51

Solvent Violet 12

Disperse Blue 1

1, 5-di- (4'-methyl-2'-sulfophenylamino) -anthraquinone (CI 67710)

Disperse Violet 4 (Cl 61105)

1, 4-diamino-2-nitrobenzene (Cl 76070)

HC Red 13

HC Violet 1, 4 D (1, 4-bis (2'-hydroxyethyl) amino-2-nitrobenzene)

HC Yellow 5

HC Orange 1 HC Red 1

1-Amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene

(4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene)

1-amino-4- (2'-hydroxyethyl) amino-2-nitrobenzene

4-amino-3-nitrophenol

HC Red B 54

(1-hydroxy-4- (2'-hydroxyethyl) amino-3-nitrobenzene)

HC Red BN

(1-hydroxy-4- (3'-hydroxypropyl) amino-3-nitrobenzene)

1-hydroxy-4-bis (3'-hydroxypropyl) amino-3-nitrobenzene

1- (2'-Ureidoethyl) amino-4-nitrobenzene

HC Red 7

HC Red 10

HC Red 11

HC Red 13

2- (2'-Hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene

HC Blue H

HC BIue 12

HC Yellow 13

HC Yellow 6

1- (2'-Hydroxyethyl) amino-4-methyl-2-nitrobenzene

HC Yellow 12

4 ethylamino-3-nitrobenzoic acid

4-amino-2-nitrodiphenylamine-2'-carboxylic acid

4-dimethylamino-2-nitrodiphenylamine-2'-carboxylic acid

6-nitro-1,2,3,4-tetrahydroquinoxaline

Basic Violet 2

Basic Violet 14

Acid Red 52

Disperse Blue 3

1-propene (4'-amino-2'-nitrophenyl) amine

Basic Blue 77

Basic Blue 124

Basic Blue 151. In preferred processes of this type according to the invention, the aqueous-based composition contains from 1 to 20% by weight, preferably from 2 to 10% by weight and in particular from 3 to 6% by weight of hydrogen peroxide, calculated as 100% H ₂ O ₂ .

Alternatively, as mentioned above, a three-component system may also be used. Another object of the present invention is therefore a process for the simultaneous dyeing and whitening of human hair, comprising an aqueous-based composition containing hydrogen peroxide with an agent containing at least one substantive hair dye and an agent containing at least one carbonate and / or a Carbonate precursor mixed into a homogeneous composition, and this is applied to the hair.

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.

Another object of the present invention is the use of substantive dyes from the group

3,4,5,6-Tetrabromphenolsulfonaphthalein

sulfobromophthalein

bromocresol

Bromthymolblau

tetrabromophenol

Acid Red 37 (Cl 17045)

Acid Orange 52 (CM 3025)

Acid Orange 6 (Cl 14270)

Acid Red 26 (Cl 16150)

Disperse Blue 106 (Cl 111935)

Disperse Red 1 (Cl 1110)

Disperse Orange 3 (Cl 11005)

Disperse Red 17 (CM 1210)

Disperse Red 179 (CM 12290)

Acid Red 337 Cl 17102)

Disperse Red 167 (Cl 11338)

Basic Red 18 (Cl 11085) Acid Orange 8 (Cl 15575)

Disperse Red 118 (CI 11152: 2)

Thionin (Cl 52000)

Basic Blue 17 (Cl 52040)

Basic Blue 24 (Cl 52030)

Basic Green 5 (Cl 52020)

4-nitro-o-phenylenediamine

2-nitro-p-phenylenediamine

4-amino-2-nitrophenol

Acid Yellow 24 (CM 0315)

Disperse Red 17

3-diethylamino-7- (4-dimethylaminophenylazo) -5-phenyl-phenazinium chloride

(Cl 11050)

Acid Orange 5 (Cl 13080)

HC Red No. 8th

Basic Blue 77

Acid Red 51 (Cl 45430)

Acid Yellow 24 (CM 0315)

1, 5-diphenylthiocarbazone

HC Yellow 13

N- (2-hydroxyethyl) -4-nitroaniline

4-Chloro-N- (2,3-dihydroxypropyl) -2-nitroaniline

3- (2 ', 6'-Diaminopyridyl-3-azo) pyridine

4- (2-thiazolylazo) resorcinol

dithizone

2-amino-1,4-naphthalenedione

3 ^I , 3 ", 5 ^I , 5" -Tetrabrom m-cresolsulfonaphthalein

Disperse Blue 102

Disperse Blue 148

Resolin Blue K-FBL

Resolin Blue K-2GLS

Disperse Blue 154

Disperse Blue 281

Disperse Blue 291

Disperse Blue 321 Disperse Blue 34 Disperse Red 33 Disperse Red 54 Disperse Red 258 Disperse Orange 66 Disperse Yellow 241 Disperse Blue 7 (Cl 62500) Disperse Blue 14 (CI 61500) Disperse Blue 26 (CI 63305) Disperse Blue 35 Disperse Blue 55 Disperse Blue 56 Disperse Blue 60 (CI 61104) Disperse Blue 62 Disperse Blue 64 Disperse Blue 72 (CI 60725) Disperse Blue 77 Disperse Blue 79 (CI 11345) Disperse Blue 87 Disperse Blue 94 Disperse Blue 109 Disperse Blue 153 Disperse Blue 180 Disperse Blue Disperse Blue 337 Disperse Blue 337 (Cl 11337) Disperse Blue 360 Disperse Blue 367 Disperse Green 9 Disperse Violet 8 (Cl 62030) Disperse Violet 17 (Cl 60712) Disperse Violet 26 (Cl 62025) Disperse Violet 28 (Cl 61102) Disperse Violet 33 (Cl 11218)

Disperse Violet 3

Disperse Violet 36

Disperse Violet 40

Disperse Violet 48

Disperse Violet 60

Disperse Violet 63

Disperse Violet 72 Cl 60725)

Disperse Violet 91

Basic Blue 54 CM 1052)

Basic Blue 67 Cl 45175)

Basic Brown 1 (Cl 21000)

Basic Brown 4 (Cl 21010)

Basic Orange 2 (Cl 11270)

Basic Red 46 "

Basic Red 104

Basic Violet 35

Basic Yellow 45

Basic Yellow 67

HC Yellow 4

3-nitro-4- (3'-hydroxypropyl) aminopheno

4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene

1-Amino-4-bis (2'-hydroxyethyl) amino-2-nitrobenzene

4-amino-3-nitrophenol

HC Blue 2

Direct Violet 51

Solvent Violet 12

Disperse Blue 1

1, 5-di- (4'-methyl-2 ¹ -sulfophenylamino) anthraquinone (Cl 67710)

Disperse Violet 4 (Cl 61105)

1, 4-diamino-2-nitrobenzene (Cl 76070)

HC Red 13

HC Violet 1, 4 D (1, 4-bis (2'-hydroxyethyl) amino-2-nitrobenzene) HC Yellow 5

HC Orange 1

HC Red 1

1-Amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene

(4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene)

1-amino-4- (2'-hydroxyethyl) amino-2-nitrobenzene

4-amino-3-nitrophenol

HC Red B 54

(1-hydroxy-4- (2'-hydroxyethyl) amino-3-nitrobenzene)

HC Red BN

(1-hydroxy-4- (3'-hydroxypropyl) amino-3-nitrobenzene)

1-hydroxy-4-bis (3'-hydroxypropyl) amino-3-nitrobenzene

1- (2'-Ureidoethyl) amino-4-nitrobenzene

HC Red 7

HC Red 10

HC Red 11

HC Red 13

2- (2'-Hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene

HC Blue H

HC BIue 12

HC Yellow 13

HC Yellow 6

1- (2'-Hydroxyethyl) amino-4-methyl-2-nitrobenzene

HC Yellow 12

4 ethylamino-3-nitrobenzoic acid

4-amino-2-nitrodiphenylamine-2'-carboxylic acid

4-dimethylamino-2-nitrodiphenylamine-2'-carboxylic acid

6-nitro-1,2,3,4-tetrahydroquinoxaline

Basic Violet 2

Basic Violet 14

Acid Red 52

Disperse Blue 3

1-propene (4'-amino-2'-nitrophenyl) amine

Basic Blue 77

Basic Blue 124 Basic Blue 151 in carbonate and / or carbonate precursor-containing agents for the simultaneous dyeing and whitening of hair.

With regard to preferred uses according to the invention, the mutated mutandis applies to the preferred agents.

Examples:

The following coloring creams were prepared:

Coloring cream 1 to 10

C _16- ia fatty alcohol 3.0% by weight

Ci _2- i8 coconut fatty alcohol 3.0% by weight

Eumulgin B1 * 1, 5% by weight

Eumulgin B2 ** 1, 5% by weight

PHB methyl ester 0.15% by weight

PHB propyl ester 0.15% by weight

Phenoxyethanol 0.5% by weight

Polydiol 400 2.5% by weight

Natrosol 250 HR *** 0.5% by weight

NaOH, solid 0.05% by weight

Ammonium hydrogencarbonate 4.0% by weight

Dye 1, 0% by weight

Water ad 100% by weight

* Cetylstearyl alcohol with 12 EO units (INCI name: Ceteareth-12)

(Cognis Germany) ** Cetylstearyl alcohol with 20 EO units (INCI name: Ceteareth-20)

(Cognis Germany) *** Hydroxyethylcellulose (Hercules)

The following dyes were used:

4-amino-3-nitrophenol

Acid Red 52

1, 4-diamino-2-nitrobenzene (Cl 76070)

HC Violet 1, 4 D (1, 4-bis (2'-hydroxyethyl) amino-2-nitrobenzene)

HC Yellow 5

HC Red B 54

HC Red BN

HC Red 7 4-Amino-2-nitrodiphenylamine-2'-carboxylic acid 6-nitro-1,2,3,4-tetrahydroquinoxaline

Formulations 1 to 10 were mixed in a weight ratio of 1: 1 with a hydrogen peroxide-containing emulsion of the following composition:

Fatty alcohol mixture C12-C18 5.0% by weight

Water-peroxide solution, 50% 12.0% by weight

Eumulgin B1 * 0.4% by weight

Eumulgin B2 ** 0.4% by weight

Aculyne 22 *** 0.5% by weight

Aculyne 33 **** 5.0% by weight

EDTA disodium salt 0.5% by weight

Water ad 100% by weight

* Cetylstearyl alcohol with 12 EO units (INCI name: Ceteareth-12)

(Cognis Germany)

*** Methacrylic acid (stearyl alcohol + 20 EO ester) acrylic acid copolymer

(Rohm & Haas) **** Acid-containing, cross-linked acrylic copolymer (INCI name: Acrylates

Copolymer, about 28% active ingredient) (Rohm & Haas)

Formulations 1 to 10 were dyed in a liquor ratio of 4: 1 for 30 minutes on natural white or dark blond hair strands (codes: Kerling natural white or Kerling dunkelblond 7/0). After the exposure time, the hair is rinsed, washed with a conventional shampoo and then dried.

The colorations were compared with formulations containing no ammonium hydrogencarbonate but 4% by weight more water. It was found that the natural white hair strands using the same dye have almost identical nuances, while the nuances with the same dye on the dark blond hair with use of ammonium bicarbonate significantly lighter and more brilliant.

Claims

claims:

1. A means for simultaneous dyeing and whitening of human hair, comprising at least one substantive hair dye and at least one carbonate and / or a carbonate precursor, characterized in that it comprises at least one substantive hair dye from the group

3,4,5,6-Tetrabromphenolsulfonaphthalein

sulfobromophthalein

bromocresol

Bromthymolblau

tetrabromophenol

Acid Red 37 (Cl 17045)

Acid Orange 52 (Cl 13025)

Acid Orange 6 (CM 4270)

Acid Red 26 (Cl 16150)

Disperse Blue 106 (Cl 111935)

Disperse Red 1 (Cl 1110)

Disperse Orange 3 (CM 1005)

Disperse Red 17 (Cl 11210)

Disperse Red 179 (Cl 112290)

Acid Red 337 Cl 17102)

Disperse Red 167 (Cl 11338)

Basic Red 18 (Cl 11085)

Acid Orange 8 (Cl 15575)

Disperse Red 118 (Cl 11152: 2)

Thionin (Cl 52000)

Basic Blue 17 (Cl 52040)

Basic Blue 24 (Cl 52030)

Basic Green 5 (Cl 52020)

4-nitro-o-phenylenediamine

2-nitro-p-phenylenediamine

4-amino-2-nitrophenol

Acid Yellow 24 (CM0315)

Disperse Red 17 3-diethylamino-7- (4-dimethylaminophenylazo) -5-phenyl-phenazinium chloride

(Cl 11050)

Acid Orange 5 (Cl 13080)

HC Red No. 8th

Basic Blue 77

Acid Red 51 (Cl 45430)

Acid Yellow 24 (Cl 10315)

1, 5-diphenylthiocarbazone

HC Yellow 13

N- (2-hydroxyethyl) -4-nitroaniline

4-Chloro-N- (2,3-dihydroxypropyl) -2-nitroaniline

3- (2 ', 6'-Diaminopyridyl-3-azo) pyridine

4- (2-thiazolylazo) resorcinol

dithizone

2-amino-1,4-naphthalenedione

3 ', 3 ", 5', 5" -Tetrabrom m-cresolsulfonaphthalein

Disperse Biue 102

Disperse Blue 148

Resolin Blue K-FBL

Resolin Blue K-2GLS

Disperse Blue 154

Disperse Blue 281

Disperse Blue 291

Disperse Blue 321

Disperse Blue 347

Disperse Red 338

Disperse Red 54

Disperse Red 258

Disperse Orange 66

Disperse Yellow 241

Disperse Blue 7 (Cl 62500)

Disperse Blue 14 (Cl 61500)

Disperse Blue 26 (Cl 63305) "

Disperse Blue 35

Disperse Blue 55 Disperse Blue 56 (CI 63285) Disperse Blue 60 (CI 61104) Disperse Blue 62 Disperse Blue 64 Disperse Blue 72 (CI 60725) Disperse Blue 77 Disperse Blue 79 (CI 11345) Disperse Blue 87 Disperse Blue 94 Disperse Blue 109 Disperse Blue 153 Disperse Blue Disperse Blue 183 Disperse Blue 287 Disperse Blue 326 Disperse Blue 333 Disperse Blue 337 (Cl 11337) Disperse Blue 360 Disperse Blue 367 Disperse Green 9 Disperse Violet 8 (Cl 62030) Disperse Violet 17 (Cl 60712) Disperse Violet 26 (Cl 62025 Disperse Violet 28 (Cl 61102) Disperse Violet 33 (Cl 11218) Disperse Violet 3 Disperse Violet 36 Disperse Violet 40 Disperse Violet 48 Disperse Violet 60 Disperse Violet 63 Disperse Violet 72 Cl 60725) Disperse Violet 91 Basic Blue 54 Cl 11052) Basic Blue 67 Cl 45175) Basic Brown 1 (Cl 21000)

Basic Brown 4 (Cl 21010)

Basic Orange 2 (Cl 11270)

Basic Red 46 "

Basic Red 104

Basic Violet 35

Basic Yellow 45

Basic Yellow 67

HC Yellow 4

3-nitro-4- (3'-hydroxypropyl) aminopheno

4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene

1-Amino-4-bis (2'-hydroxyethyl) amino-2-nitrobenzene

4-amino-3-nitrophenol

HC Blue 2

Direct Violet 51

Solvent Violet 12

Disperse Blue 1

2 ^1- Methyl-4 ^l - (N-ethyl-N-sulfon-sulfobenzyl) -amino-4 "- (N, N-diethyl) -amino-2-methyl-N-ethyl-N-sulfonyl-sulfobenzyl-fuchsoneimonium (CI 42735)

1, 5-di- (4'-methyl-2'-sulfophenylamino) -anthraquinone (CI 67710)

Disperse Violet 4 (Cl 61105)

1, 4-diamino-2-nitrobenzene (Cl 76070)

HC Red 13

HC Violet 1, 4 D (1, 4-bis (2'-hydroxyethyl) amino-2-nitrobenzene)

HC Yellow 5

HC Orange 1

HC Red 1

1-Amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene

(4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene)

1-amino-4- (2'-hydroxyethyl) amino-2-nitrobenzene

4-amino-3-nitrophenol

HC Red B 54

(1-hydroxy-4- (2'-hydroxyethyl) amino-3-nitrobenzene)

HC Red BN

(1-hydroxy-4- (3'-hydroxypropyl) amino-3-nitrobenzene) 1-Hydroxy-4-bis (3'-hydroxypropyl) amino-3-nitrobenzene 1- (2'-Ureidoethyl) amino-4-nitrobenzene HC Red 7 HC Red 10 HC Red 11 HC Red 13

1- (2'-Hydroxyethyl) amino-4-methyl-2-nitrobenzene HC Yellow 12

2. Composition according to claim 1, characterized in that the carbonate is selected from carbonic acid mono- and / or diesters, preferably from methyl carbonate, ethyl carbonate, propyl carbonate, their salts and / or mixtures thereof.

3. Composition according to claim 1, characterized in that the carbonate is selected from carbonic acid monoester salts and / or carbonic acid monoamides and / or their salts, silyl carbonates and / or silyl carbamates and mixtures thereof.

4. Composition according to one of claims 1 to 3, characterized in that it contains carbonate (s) in amounts of 0.5 to 15 wt .-%, preferably from 1 to 12% by weight, particularly preferably from 2 to 9 wt .-% and in particular from 3 to 7% by weight, each based on the total agent contains.

5. Composition according to claim 4, characterized in that it directing (s) dye (s) in amounts of 0.01 to 10 wt.%, Preferably from 0.05 to 8 wt.%, Particularly preferably from 0.1 to 5 wt.% And in particular from 0.5 to 3.5 wt.%, Each based on the total agent contains.

6. Composition according to one of claims 1 to 5, characterized in that it additionally contains Cu, Fe, Mn ions or complexes of these ions.

7. Composition according to one of claims 1-6, characterized in that the pH of the composition is 6 - 11, preferably 7.5 - 10 and particularly preferably 8 -9.

8. A method for the simultaneous dyeing and whitening of human hair, in which an aqueous-based composition containing hydrogen peroxide mixed with an agent containing at least one substantive hair dye and at least one carbonate and / or a carbonate precursor to form a homogeneous composition, and is applied to the hair, characterized in that at least one direct dye contained in the middle is selected from

3,4,5,6-Tetrabromophenolsulfonaphthalene Sulfobromphthalein Bromocresol Green Bromothymol Blue Tetrabromophenol Blue Acid Red 37 (CI 17045) Acid Orange 52 (CI 13025) Acid Orange 6 (CI 14270) Acid Red 26 (CI 16150) Disperse Blue 106 (CI 111935) Disperse Red 1 (Cl 1110) Disperse Orange 3 (Cl 11005) Disperse Red 17 (Cl 11210)

Disperse Red 179 (Cl 112290)

Acid Red 337 CM 7102)

Disperse Red 167 (Cl 11338)

Basic Red 18 (Cl 11085)

Acid Orange 8 (Cl 15575)

Disperse Red 118 (Cl 11152: 2)

Thionin (Cl 52000)

Basic Blue 17 (Cl 52040)

Basic Blue 24 (Cl 52030)

Basic Green 5 (Cl 52020)

4-nitro-o-phenylenediamine

2-nitro-p-phenylenediamine

4-amino-2-nitrophenol

Acid Yellow 24 (Cl 10315)

Disperse Red 17

3-diethylamino-7- (4-dimethylaminophenylazo) -5-phenyl-phenazinium chloride

(Cl 11050)

Acid Orange 5 (Cl 13080)

HC Red No. 8th

Basic Blue 77

Acid Red 51 (Cl 45430)

Acid Yellow 24 (Cl 10315)

1, 5-diphenylthiocarbazone

HC Yellow 13

N- (2-hydroxyethyl) -4-nitroaniline

4-Chloro-N- (2,3-dihydroxypropyl) -2-nitroaniline

3- (2 ', 6'-Diaminopyridyl-3-azo) pyridine

4- (2-thiazolylazo) resorcinol

dithizone

2-amino-1,4-naphthalenedione

3 ', 3 ", 5', 5" -Tetrabrom m-cresolsulfonaphthalein

Disperse Blue 102

Disperse Blue 148

Resolin Blue K-FBL Resins Blue K-2GLS Disperse Blue 154 Disperse Blue 281 Disperse Blue 291 Disperse Blue 321 Disperse Blue 347 Disperse Red 338 Disperse Red 54 Disperse Red 258 Disperse Orange 66 Disperse Yellow 241 Disperse Blue 7 (Cl 62500) Disperse Blue 14 (Cl 61500) Disperse Blue 26 (CI 63305) "Disperse Blue 35 Disperse Blue 55 Disperse Blue 56 (CI 63285) Disperse Blue 60 (CI 61104) Disperse Blue 62 Disperse Blue 64 Disperse Blue 72 (CI 60725) Disperse Blue 77 Disperse Blue 79 (CI 11345) Disperse Blue 87 Disperse Blue 94 Disperse Blue 109 Disperse Blue 153 Disperse Blue 180 Disperse Blue 183 Disperse Blue 287 Disperse Blue 326 Disperse Blue 333 Disperse Blue 337 (Cl 11337) Disperse Blue 360 Disperse Blue 367 Disperse Green 9

Disperse Violet 8 (Cl 62030)

Disperse Violet 17 (Cl 60712)

Disperse Violet 26 (Cl 62025)

Disperse Violet 28 (Cl 61102)

Disperse Violet 33 (Cl 11218)

Disperse Violet 3

Disperse Violet 36

Disperse Violet 40

Disperse Violet 48

Disperse Violet 60

Disperse Violet 63

Disperse Violet 72 Cl 60725)

Disperse Violet 91

Basic Blue 54 Cl 11052)

Basic Blue 67 Cl 45175)

Basic Brown 1 (Cl 21000)

Basic Brown 4 (Cl 21010)

Basic Orange 2 (Cl 11270)

Basic Red 46 "

Basic Red 104

Basic Violet 35

Basic Yellow 45

Basic Yellow 67

HC Yellow 4

3-nitro-4- (3'-hydroxypropyl) aminopheno

4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene

1-Amino-4-bis (2'-hydroxyethyl) amino-2-nitrobenzene

4-amino-3-nitrophenol

HC Blue 2

Direct Violet 51

Solvent Violet 12

Disperse Blue 1

2'-Methyl-4 '- (N-ethyl-N-sulfon-sulfobenzyl) -amino-4 "- (N, N-diethyl) -amino-2-methyl-N-ethylNM-sulfobenzyl-fuchsonimonium (CI 42735) 1, 5-di- (4'-methyl-2'-sulfophenylamino) -anthraquinone (CI 67710)

Disperse Violet 4 (Cl 61105)

1, 4-diamino-2-nitrobenzene (Cl 76070)

HC Red 13

HC Violet 1, 4 D (1, 4-bis (2'-hydroxyethyl) amino-2-nitrobenzene)

HC Yellow 5

HC Orange 1

HC Red 1

1-Amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene

(4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene)

1-amino-4- (2'-hydroxyethyl) amino-2-nitrobenzene

4-amino-3-nitrophenol

HC Red B 54

(1-hydroxy-4- (2'-hydroxyethyl) amino-3-nitrobenzene)

HC Red BN

(1-hydroxy-4- (3'-hydroxypropyl) amino-3-nitrobenzene)

1-hydroxy-4-bis (3'-hydroxypropyl) amino-3-nitrobenzene

1- (2'-Ureidoethyl) amino-4-nitrobenzene

HC Red 7

HC Red 10

HC Red 11

HC Red 13

2- (2'-Hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene

HC BIue H

HC Blue 12

HC Yellow 13

HC Yellow 6

1- (2'-Hydroxyethyl) amino-4-methyl-2-nitrobenzene

HC Yellow 12

4 ethylamino-3-nitrobenzoic acid

4-amino-2-nitrodiphenylamine-2'-carboxylic acid

4-dimethylamino-2-nitrodiphenylannin-2'-carboxylic acid

6-nitro-1,2,3,4-tetrahydroquinoxaline

Basic Violet 2

Basic Violet 14 Acid Red 52 Disperse Blue 3

1-Propene (4'-amino-2'-nitrophenyl) amine Basic Blue 77 Basic Blue 124 Basic Blue 151.

9. The method according to claim 8, characterized in that the composition on an aqueous basis based on their weight 1 to 20 wt.%, Preferably 2 to 10 wt.% And in particular 3 to 6 wt.% Hydrogen peroxide, calculated as 100% H. ₂ O ₂ , contains.

10. A process for the simultaneous dyeing and whitening of human hair, characterized in that an aqueous-based composition containing hydrogen peroxide, with an agent containing at least one substantive hair dye and an agent containing at least one carbonate mixed into a homogeneous composition, and these the hair is applied.

11. Use of substantive dyes from the group

3,4,5,6-Tetrabromphenolsulfonaphthalein

sulfobromophthalein

bromocresol

Bromthymolblau

tetrabromophenol

Acid Red 37 (Cl 17045)

Acid Orange 52 (Cl 13025)

Acid Orange 6 (Cl 14270)

Acid Red 26 (Cl 16150)

Disperse Blue 106 (Cl 111935)

Disperse Red 1 (Cl 1110)

Disperse Orange 3 (Cl 11005)

Disperse Red 17 (Cl 11210)

Disperse Red 179 (Cl 112290)

Acid Red 337 Cl 17102) Disperse Red 167 (Cl 11338)

Basic Red 18 (C M 1085)

Acid Orange 8 (Cl 15575)

Disperse Red 118 (CM 1152: 2)

Thionin (Cl 52000)

Basic Blue 17 (Cl 52040)

Basic Blue 24 (Cl 52030)

Basic Green 5 (Cl 52020)

4-nitro-o-phenylenediamine

2-nitro-p-phenylenediamine

4-amino-2-nitrophenol

Acid Yellow 24 (Cl 10315)

Disperse Red 17

3-diethylamino-7- (4-dimethylaminophenylazo) -5-phenyl-phenazinium chloride

(Cl 11050)

Acid Orange 5 (Cl 13080)

HC Red No. 8th

Basic Blue 77

Acid Red 51 (Cl 45430)

Acid Yellow 24 (Cl 10315)

1, 5-diphenylthiocarbazone

HC Yellow 13

N- (2-hydroxyethyl) -4-nitroaniline

4-Chloro-N- (2,3-dihydroxypropyl) -2-nitroaniline

3- (2 ', 6'-Diaminopyridyl-3-azo) pyridine

4- (2-thiazolylazo) resorcinol

dithizone

2-amino-1,4-naphthalenedione

3 ', 3 ", 5', 5" -Tetrabrom m-cresolsulfonaphthalein

Disperse Blue 102

Disperse Blue 148

Resolin Blue K-FBL

Resolin Blue K-2GLS

Disperse Blue 154

Disperse Blue 281 Disperse Blue 291 Disperse Blue 321 Disperse Blue 347 Disperse Red 338 Disperse Red 54 Disperse Red 258 Disperse Orange 66 Disperse Yellow 241 Disperse Blue 7 (Cl 62500) Disperse Blue 14 (Cl 61500) Disperse Blue 26 (Cl 63305) "Disperse Blue 35 Disperse Blue Disperse Blue 56 (CI 63285) Disperse Blue 60 (CI 61104) Disperse Blue 62 Disperse Blue 64 Disperse Blue 72 (CI 60725) Disperse Blue 77 Disperse Blue 79 (CI 11345) Disperse Blue 87 Disperse Blue 94 Disperse Blue 109 Disperse Blue 153 Disperse Blue 180 Disperse Blue 183 Disperse Blue 287 Disperse Blue 326 Disperse Blue 333 Disperse Blue 337 (Cl 11337) Disperse Blue 360 Disperse Blue 367 Disperse Green 9 Disperse Violet 8 (Cl 62030) Disperse Violet 17 (Cl 60712) Disperse Violet 26 (Cl 62025)

Disperse Violet 28 (Cl 61102)

Disperse Violet 33 (Cl 11218)

Disperse Violet 3

Disperse Violet 36

Disperse Violet 40

Disperse Violet 48

Disperse Violet 60

Disperse Violet 63

Disperse Violet 72 Cl 60725)

Disperse Violet 91

Basic Blue 54 C1 11052)

Basic Blue 67 Cl 45175)

Basic Brown 1 (Cl 21000)

Basic Brown 4 (Cl 21010)

Basic Orange 2 (Cl 11270)

Basic Red 46 "

Basic Red 104

Basic Violet 35

Basic Yellow 45

Basic Yellow 67

HC Yellow 4

3-nitro-4- (3'-hydroxypropyl) aminopheno

4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene

1-Amino-4-bis (2'-hydroxyethyl) amino-2-nitrobenzene

4-amino-3-nitrophenol

HC Blue 2

Direct Violet 51

Solvent Violet 12

Disperse Blue 1

1, 5-di (4 ^l -methyl-2'-sulfophenylamino) -anthraquinone (Cl 67710)

Disperse Violet 4 (Cl 61105)

1, 4-diamino-2-nitrobenzene (Cl 76070) HC Red 13

HC Violet 1, 4 D (1, 4-bis (2'-hydroxyethyl) amino-2-nitrobenzene)

HC Yellow 5

HC Orange 1

HC Red 1

1-Amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene

(4-amino-1- (2'-hydroxyethyl) amino-2-nitrobenzene)

1-amino-4- (2'-hydroxyethyl) amino-2-nitrobenzene

4-amino-3-nitrophenol

HC Red B 54

(1-hydroxy-4- (2'-hydroxyethyl) amino-3-nitrobenzene)

HC Red BN

(1-hydroxy-4- (3'-hydroxypropyl) amino-3-nitrobenzene)

1-hydroxy-4-bis (3'-hydroxypropyl) amino-3-nitrobenzene

1- (2'-Ureidoethyl) amino-4-nitrobenzene

HC Red 7

HC Red 10

HC Red 11

HC Red 13

2- (2'-Hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene

HC Blue H

HC BIue 12

HC Yellow 13

HC Yellow 6

1- (2'-Hydroxyethyl) amino-4-methyl-2-nitrobenzene

HC Yellow 12

4 ethylamino-3-nitrobenzoic acid

4-amino-2-nitrodiphenylamine-2'-carboxylic acid

4-dimethylamino-2-nitrodiphenylamine-2'-carboxylic acid

6-nitro-1,2,3,4-tetrahydroquinoxaline

Basic Violet 2

Basic Violet 14

Acid Red 52

Disperse Blue 3

1-propene (4'-amino-2'-nitrophenyl) amine Basic Blue 77

Basic Blue 124

Basic Blue 151 in carbonate and / or carbonate precursor-containing agents for the simultaneous dyeing and whitening of hair.